CN104212413A - Liquid-filled porous silicon resin anti-icing material and preparation method thereof - Google Patents
Liquid-filled porous silicon resin anti-icing material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a liquid-filled porous silicon resin anti-icing material and a preparation method thereof. A fluorosilane-modified porous silicon resin and fluorine-containing liquid composite layer is combined on a base material of the liquid-filled porous silicon resin anti-icing material, wherein the fluorine-containing liquid is filled in the fluorosilane-modified porous silicon resin, and the porous silicon resin is obtained by uniformly mixing an inorganic silicon or organic silicon raw material, a catalyst solution and organic nanoparticle in a solvent to form a mixed solution, directly coating the mixed solution on the surface of the base material, and removing the organic nanoparticle after drying and curing the coating; the fluorine-containing liquid is selected from one or two of liquid perfluorocarbon and liquid fluorosilicone; the fluorine-containing liquid has a viscosity range of 0.1-500cm<2>/s at the room temperature; and the average particle size of the organic nanoparticle is 50-800nm. When the environment temperature and the environment humidity can cause the base material to ice, the surface of the liquid-filled porous silicon resin can prevent subcooled water from contacting the base material, and a liquid lubricating material can be used for greatly descending the adhesive power of the ice layer and is easy to separate from the surface under the action of gravity or wind power. The liquid-filled porous silicon resin anti-icing material can be efficiently acted under the weather conditions such as the environment temperature of 0 to -40 DEG C and the environment humidity of 40%-90%.
Description
Technical field
The invention belongs to material technology field, be specifically related to ice-covering-proof material of a kind of liquid filling porous silicon resin and preparation method thereof.
Background technology
Icing phenomenon is very common at occurring in nature, is present in widely the surface of various low temperature, and as the evaporator surface of outdoor and various refrigeration systems and the refrigerating apparatus of Cold Winter, icing has brought all multiple-energy-sources and safety problem.For example: icing can cause refrigerating apparatus heat transfer efficiency to decline to a great extent even losing efficacy; Serious icing can cause the aerial crash of aircraft and ecotope, traffic, electric power facility by considerable damage etc.Conventionally, ice detachment need expend a large amount of human and material resources and financial resources.Therefore, how effectively to solve or alleviate the icing problem of cold surface, reduce anti-icing energy consumption and the hot issue that becomes anti-icing research field of avoiding security incident.Existing ice-covering-proof technology mainly contains heating power deicing, several classes such as manual machine deicing and ice-covering-proof material.Wherein, the energy consumption of heating power deicing is large, and manual machine deicing efficiency is low, potential safety hazard is large.Ice-covering-proof material can fundamentally prevent that material surface from freezing or reducing icing degree, is the Perfected process that solves icing problem, thereby receives much attention.
At present, the anti-icing main policies of material is next ice-covering-proof by constructing special wetting property surface, comprises two classes: a class is hydrophilic surface, utilize hydroaropic substance to adsorb large water gaging, and add and can fall subzero material (CN1104674A, CN1632014A, CN1916094A).But the water regain of this class material and rate of water absorption are very large to anti-icing influential effect, weak effect under the environment of high humidity, consecutive low temperature, and fall subzero material and generally select small-molecule substance, easily to run off, work-ing life is limited.Another kind of is water repellent surface, reduces heat transfer efficiency by reducing water droplet and Surface Contact area, delays water droplet icing (CN1556161A, CN102660182A).But its hydrophobic performance is large to anti-icing influential effect, and can not reduce ice at surperficial adhesive power.Also have the anti-icing method that adopts compound surface, patent CN100593557C mixes with hydrophobic polymer hydrophilic, utilizes phase detachment technique to make the composite structure of strong hydrophilicity internal layer and super hydrophobic surface, has realized good anti-icing effect.
Adopt liquid surface layer to intercept adhesive power technology (the Wong T.S that contacts and reduce ice sheet of ice sheet and base material; Kang S.H.; Tang S.K.Y.; Smythe E.J.; Hatton B.D.; Grinthal A.; Aizenberg J.Nature2011,477,443-447) in.The key on this surface is at surface construction one deck liquid surface layer, conventionally utilizes the wicking action force retaining liquid of porous epoxy resin or fluorinated polymer material and liquid.Common vesicular structure preparation method comprises Lithographic template method, the brilliant method of reversion colloid, microphase-separated method etc., these methods or need specific installation, preparation method is numerous and diverse, or high to material selectivity, be not suitable for industrialized practical application.
Summary of the invention
The object of the present invention is to provide the ice-covering-proof material of a kind of low ice adhesion liquid filling porous silicon resin.
Another object of the present invention is to provide a kind of low ice adhesion liquid filling porous silicon resin ice-covering-proof material preparation method.
The ice-covering-proof material of liquid filling porous silicon resin of the present invention, on base material, in conjunction with porous silicon resin and fluorine-containing liquid composite bed by silicon fluoride modification, wherein, fluorine-containing liquid filling is in the porous silicon resin of silicon fluoride modification; Porous silicon resin is mixed and forms mixing solutions with organic nano particle by inorganic silicon or organosilicon raw material, catalyst solution in solvent, is directly coated in substrate surface, removes organic nano particle and obtain after to be dried solidifying; Described fluorine-containing liquid is selected from one or more in liquid fluorocarbon, liquid fluorine silicon; Described fluorine-containing liquid range of viscosities is at room temperature 0.1～500cm
2/ s; The average particle size range of described organic nano particle is 50～800nm.
The porous silicon resin of silicon fluoride modification is the base material that is coated with porous silicon resin to be joined in the encloses container that is placed with silicon fluoride or immerse in the solution that is dissolved with fluorine containing silane, to carry out surface chemical modification and form.
The ice-covering-proof material of liquid filling porous silicon resin of the present invention can make the adhesive power of ice and base material significantly reduce.The ice-covering-proof material of liquid filling porous silicon resin of the present invention is to be composited by porous silicon resin and the fluorine-containing liquid of silicon fluoride modification.
Described silicon fluoride is selected from one or more in trifluoroethyl Trimethoxy silane, trifluoroethyl Trimethoxy silane, hexafluoro butyl trimethoxy silane, hexafluoro butyl triethoxyl silane, five fluorine octyl group Trimethoxy silanes, five fluorine octyltri-ethoxysilane, perfluoro capryl Trimethoxy silane, perfluoro capryl triethoxy.
Described inorganic silicon raw material is water glass.Organosilicon raw material is selected from one or more in methyl silicate, tetraethoxy or positive isopropyl silicate.
Described catalyst solution is aqueous acid.Described acid is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, aqueous acetic acid.Described catalyst solution concentration range is 0.01～1mol/L.The volume ratio of catalyst solution and mixing solutions is 1:10～1:100.
Described organic nano particle is selected from one or more in polystyrene, polymethylmethacrylate, polyacrylonitrile, polylactide, poly(lactic acid), nano-cellulose.
Solvent in described mixing solutions is selected from one or more in water, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, acetone.
Contriver finds by further research, and due to the viscosity of fluorine-containing liquid and organic nano particle, both have synergistic function, all can all have impact to anti-icing performance.
Research of the present invention also shows, the viscosity of fluorine-containing liquid is preferably 0.1～50cm
2/ s; The particle size range of organic nano particle is preferably 200～500nm, can obtain the effect of best low ice adhesion.
The preparation method of the ice-covering-proof material of liquid filling porous silicon resin provided by the invention, comprise the steps: the preparation of (1) porous silicon resin: it is in 10%～50% inorganic silicon or organic silicon solution that organic nano particle is joined to massfraction, after mixing, add catalyst solution, the mixing solutions forming is directly coated in substrate surface, and after to be dried solidifying, high temperature ablation or dissolution with solvents are removed organic nano particle and obtained porous silicon resin surface.
(2) porous silicon resin surface chemical modification: there is porous silicon resin base material to be placed in to be placed with the encloses container of silicon fluoride on the surface that (1) is made or immerses the solution that is dissolved with fluorine containing silane carries out surface chemical modification.
(3) fluorine-containing liquid filling: adopt the methods such as spraying or immersion that fluorine-containing liquid is fixed in the porous silicon resin of surface chemical modification.
The mass ratio of described organic nano particle and inorganic silicon or organosilicon raw material is 1:1～1:4.
The method of described removal organic nano particle comprises high temperature ablation or dissolution with solvents.
The temperature province of described high temperature ablation is selected from 300～800 DEG C.The ablation time is selected from 30～1200min.
The solvent that the method for described dissolution with solvents is used is selected from one or more in chloroform, methylene dichloride, tetracol phenixin, tetrahydrofuran (THF), dimethyl formamide.Soak time is selected from 2～24h.
The time of described surface chemical modification is 2～48h.
Solvent in the solution of fluorine containing silane is selected from one or more in methyl alcohol, ethanol, acetone, benzene, chloroform.In described fluorine containing silane solution, the massfraction of silicon fluoride is 1%～20%.
The application of the ice-covering-proof material of liquid filling porous silicon resin of the present invention, preparation liquid filling porous silicon resin surface that can be on different base materials, obtains having low ice and adheres to ice-covering-proof material.
In the time that envrionment temperature and ambient moisture can cause base material to freeze, described liquid filling porous silicon resin surface can stop supercooled water contact substrate, liquid lubrication layer also can make the adhesive power of ice sheet significantly decline, and easily under gravity or wind effect, departs from surface.The weather conditions such as it is 0 DEG C～-40 DEG C that material of the present invention can efficiently act on envrionment temperature, and ambient moisture is 40%～90%.
Described base material can be copper, iron, aluminium, titanium, glass, pottery etc.
The invention provides the ice-covering-proof material of a kind of liquid filling porous silicon resin.This surface is mixed and is directly coated in substrate surface with organic nano particle by inorganic silicon conventional in industrial production or organosilicon raw material, after to be dried solidifying, go organic nano particle to obtain porous silicon resin, then obtain ice-covering-proof material through surface fluorination and modification and the non-volatile hydrophobic liquid of filling.Wherein the porous silicon resin of surface modification can effectively be fixed on surface by non-volatile hydrophobic liquid, thereby forms one deck liquid surface layer.
The ice-covering-proof material of liquid filling porous silicon resin of the present invention has the following advantages than other ice-covering-proof material: the ice adhesion that (1) is ultralow: due to the present invention form can ice-covering-proof effect the fluorine containing silane modified liquid layer that has isolation and lubrication concurrently, both can delay the formation of ice sheet, can greatly reduce again ice and substrate adhesive power, make substrate surface icing less and easily under wind-force and action of gravity, remove.The adhesive power of material of the present invention can remain on below 100kPa substantially, and wherein embodiment 1-4 can remain on below 50kPa, referring to Fig. 1,2.Specifically can be further, than various unmodified base materials, referring to Fig. 3, can find out, the ice adhesion of base material is at least more than 800Kpa.Therefore, the ice-covering-proof material of liquid filling porous silicon resin prepared by the present invention is carrying out modification to porous silicon resin, while all shows good ice-covering-proof ability in conjunction with resulting materials on the basis of the comprehensive action of organic nano particle and fluorine-containing liquid viscosity, and ice adhesion obviously weakens.Illustrate that material surface and ice sheet have been carried out good isolation by the liquid filling porous silicon resin in the present invention program, its lubrication also makes ice adhesion obviously decline.Simultaneously, comparison diagram 1 and Fig. 2, the ice adhesion that can find out ice-covering-proof material (embodiment 1～4) prepared by the organic nano particle of selecting the fluorine-containing liquid-mixing unification of low viscosity more determine particle diameter is less than the fluorine-containing liquid of high viscosity, ice-covering-proof material (embodiment 5～8) that small particle size/greatly prepared by particle diameter organic nano particle.In conjunction with comparative example 9 and 10, in the present invention, fluorine-containing fitting of fluids scope is 0.1～500cm
2/ s, is preferably 0.1～50cm
2/ s, organic nano particle particle diameter range of choice is 50～800nm, is preferably 200～500nm.(2) wearing quality is strong: the present invention uses silicone material, satisfactory mechanical property; The fluorine-containing liquid stabilising using is good, and environment tolerance is strong, and fluorine-containing material surface can be low, is not easy contaminated; Flowing fluid layer can also be repaired local damage.
Brief description of the drawings:
Fig. 1. the ice-covering-proof material of liquid filling porous silicon resin of the embodiment of the present invention 1～4 preparation envrionment temperature for-20 DEG C, ambient moisture be 60%, after freezing 12 hours, carry out the result of ice adhesion size test.
Fig. 2. the ice-covering-proof material of liquid filling porous silicon resin of embodiment 5～8 preparation envrionment temperature for-40 DEG C, ambient moisture be 90%, after freezing 12 hours, carry out the result of ice adhesion size test.
Fig. 3. various unmodified base materials are that 0 DEG C, ambient moisture are 40% in envrionment temperature, after freezing 12 hours, carry out the result of ice adhesion size test.
Fig. 4. the silicone surface SEM photo of (b) after dry solidification in embodiment 1 (a) and intensification ablation.
Fig. 5. in comparative example 9, selecting particle diameter is silicone surface SEM photo prepared by 20nm and 1000nm polystyrene nanoparticle.
Fig. 6. comparative example 10 the ice-covering-proof material of liquid filling porous silicon resin is that 0 DEG C, ambient moisture are 40% in envrionment temperature, after freezing 12 hours, carries out the result of ice adhesion size test.
Embodiment
By specific embodiment, the present invention is described below, but embodiment is only for explanation, does not limit the scope of the invention.In the situation that not departing from aforesaid method thought range of the present invention, various replacements and the change made according to ordinary skill knowledge and customary means, all should be within the scope of the present invention.
The experimental technique using in following embodiment if no special instructions, is ordinary method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
Embodiment 1
(1) preparation of porous silicon resin
It is in 10% sodium silicate aqueous solution (mass ratio of polystyrene and water glass is 1:1) that the polystyrene nanoparticle of certain mass (median size is 500nm) is joined to massfraction, after mixing, add the aqueous hydrochloric acid (aqueous hydrochloric acid is 1:20 with mixed liquor volume ratio) of 0.1mol/L, then solution is directly coated in to copper sheet surface, after solution dry solidification, put into retort furnace and be warming up to 800 DEG C of ablation 30min, after cooling, take out copper sheet and obtain the surperficial copper sheet that has porous silicon resin.
(2) porous silicon resin surface chemical modification
There is the copper sheet of porous silicon resin to be placed in to be placed with the encloses container 24h of trifluoroethyl Trimethoxy silane on the surface that step (1) is made, obtains the copper sheet of the porous silicon resin of surface chemical modification.
Fig. 4 shows that nanoparticle is evenly dispersed in silicone resin, in film forming and dry solidification process, does not reunite.In intensification ablation process, in silicone resin, organic nano particle is removed, and has formed vesicular structure, and pore structure is even, and occurrence of large-area is not caved in and empty structure.
(3) fluorine-containing liquid filling
Be 0.1cm by viscosity
2the fluorocarbon liquid of/s evenly sprays on the copper sheet that the porous silicon resin of the surface chemical modification that step (2) makes covers by the method for spraying, obtains the ice-covering-proof material of liquid filling porous silicon resin.
When envrionment temperature is 0～-40 DEG C, ambient moisture is 40%～90% can cause copper sheet surface to freeze time, the above-mentioned ice-covering-proof material of liquid filling porous silicon resin making can stop supercooled water contact copper sheet, the adhesive power of the icing minimizing in copper sheet surface and ice sheet is reduced greatly, and the ice sheet on copper sheet surface can depart under the effect of gravity or wind-force.
Embodiment 2
(1) preparation of porous silicon resin
It is in methyl silicate/methanol solution of 20% (mass ratio of polymethylmethacrylate and methyl silicate is 1:2) that the polymethyl methacrylate nano particle of certain mass (median size is 400nm) is joined to massfraction, after mixing, add the aqueous sulfuric acid (aqueous sulfuric acid is 1:10 with mixed liquor volume ratio) of 0.3mol/L, then solution is directly coated in to iron plate surface, after solution dry solidification, put into retort furnace and be warming up to 300 DEG C of ablation 1200min, after cooling, take out iron plate and obtain the surperficial iron plate that has porous silicon resin.
(2) porous silicon resin surface chemical modification
There is the copper sheet of porous silicon resin to be placed in to be placed with the encloses container 48h of trifluoroethyl triethoxyl silane on the surface that step (1) is made, obtains the iron plate of the porous silicon resin of surface chemical modification.
(3) fluorine-containing liquid filling
Be 50cm by viscosity
2the fluorocarbon liquid of/s evenly sprays on the iron plate that the porous silicon resin of the surface chemical modification that step (2) makes covers by the method for spraying, obtains the ice-covering-proof material of liquid filling porous silicon resin.
When envrionment temperature is 0～-40 DEG C, ambient moisture is 40%～90% can cause iron plate surface to freeze time, the above-mentioned ice-covering-proof material of liquid filling porous silicon resin making can stop supercooled water contact iron plate, the adhesive power of the icing minimizing in iron plate surface and ice sheet is reduced greatly, and the ice sheet on iron plate surface can depart under the effect of gravity or wind-force.
Embodiment 3
(1) preparation of porous silicon resin
It is in tetraethoxy/ethanolic soln of 40% (mass ratio of nano-cellulose and tetraethoxy is 1:4) that the nano-cellulose of certain mass (median size is 300nm) is joined to massfraction, after mixing, add the aqueous nitric acid (aqueous nitric acid is 1:30 with mixed liquor volume ratio) of 0.5mol/L, then solution is directly coated in to glass sheet surface, after solution dry solidification, put into retort furnace and be warming up to 500 DEG C of ablation 800min, after cooling, take out iron plate and obtain the surperficial sheet glass that has porous silicon resin.
(2) porous silicon resin surface chemical modification
The surface that step (1) is made has the sheet glass of porous silicon resin to be soaked in 6h in the methanol solution that massfraction is 1% hexafluoro butyl trimethoxy silane, obtains the sheet glass of the porous silicon resin of surface chemical modification.
(3) fluorine-containing liquid filling
It is 1cm that the sheet glass that the porous silicon resin of the surface chemical modification that step (2) is made covers is dipped into viscosity
2in the fluorine silicon solution of/s, then take out and wipe the unnecessary fluorine silicon liquid in surface away, obtain the ice-covering-proof material of liquid filling porous silicon resin.
When envrionment temperature is 0～-40 DEG C, ambient moisture is 40%～90% can cause glass sheet surface to be frozen time, the above-mentioned ice-covering-proof material of liquid filling porous silicon resin making can stop supercooled water contact sheet glass, the adhesive power of the icing minimizing of glass sheet surface and ice sheet is reduced greatly, and the ice sheet of glass sheet surface can depart under the effect of gravity or wind-force.
Embodiment 4
(1) preparation of porous silicon resin
It is (polyacrylonitrile is 1:4 with the mass ratio of positive isopropyl silicate) in positive isopropyl silicate/propanol solution of 50% that the polyacrylonitrile nano particle of certain mass (median size is 200nm) is joined to massfraction, after mixing, add the phosphate aqueous solution (phosphate aqueous solution is 1:100 with mixed liquor volume ratio) of 0.8mol/L, then solution is directly coated in to aluminium flake surface, after solution dry solidification, immerses 12h in tetrahydrofuran (THF) and remove the surperficial aluminium flake that has porous silicon resin of polyacrylonitrile nano particle acquisition.
(2) porous silicon resin surface chemical modification
The surface that step (1) is made has the aluminium flake of porous silicon resin to be soaked in 48h in the methanol solution that massfraction is 5% hexafluoro butyl triethoxyl silane, obtains the aluminium flake of the porous silicon resin of surface chemical modification.
(3) fluorine-containing liquid filling
It is 30cm that the aluminium flake that the porous silicon resin of the surface chemical modification that step (2) is made covers is dipped into viscosity
2in the fluorine silicon liquid of/s, then take out and wipe the unnecessary fluorine silicon liquid in surface away, obtain the ice-covering-proof material of liquid filling porous silicon resin.
When envrionment temperature is 0～-40 DEG C, ambient moisture is 40%～90% can cause aluminium flake surface to freeze time, the above-mentioned ice-covering-proof material of liquid filling porous silicon resin making can stop supercooled water contact aluminium flake, the adhesive power of the icing minimizing in aluminium flake surface and ice sheet is reduced greatly, and the ice sheet on aluminium flake surface can depart under the effect of gravity or wind-force.
Embodiment 5
(1) preparation of porous silicon resin
It is in tetraethoxy/aqueous isopropanol of 50% (mass ratio of polylactide and tetraethoxy is 1:3) that the polylactide nanoparticles of certain mass (median size is 600nm) is joined to massfraction, after mixing, add the aqueous formic acid (aqueous formic acid is 1:100 with mixed liquor volume ratio) of 1mol/L, then solution is directly coated in to titanium plate surface, after solution dry solidification, immerses 12h in chloroform and remove the surperficial titanium sheet that has porous silicon resin of polylactide nanoparticles acquisition.
(2) porous silicon resin surface chemical modification
The surface that step (1) is made has the titanium sheet of porous silicon resin to be soaked in 2h in the ethanolic soln that massfraction is 10% five fluorine octyl group Trimethoxy silanes, obtains the titanium sheet of the porous silicon resin of surface chemical modification.
(3) fluorine-containing liquid filling
It is 300cm that the titanium sheet that the porous silicon resin of the surface chemical modification that step (2) is made covers is dipped into viscosity
2in the fluorine silicon solution of/s, then take out and wipe the unnecessary fluorine silicon liquid in surface away, obtain the ice-covering-proof material of liquid filling porous silicon resin.
When envrionment temperature is 0～-40 DEG C, ambient moisture is 40%～90% can cause titanium plate surface to freeze time, the above-mentioned ice-covering-proof material of liquid filling porous silicon resin making can stop supercooled water contact titanium sheet, the adhesive power of the icing minimizing of titanium plate surface and ice sheet is reduced greatly, and the ice sheet of titanium plate surface can depart under the effect of gravity or wind-force.
Embodiment 6
(1) preparation of porous silicon resin
It is (poly(lactic acid) is 1:2 with the mass ratio of positive isopropyl silicate) in positive isopropyl silicate/butanol solution of 20% that the nano polylactic acid particle of certain mass (median size is 150nm) is joined to massfraction, after mixing, add the acetic acid aqueous solution (acetic acid aqueous solution is 1:60 with mixed liquor volume ratio) of 0.2mol/L, then solution is directly coated in to ceramic plate surface, after solution dry solidification, immerses 2h in benzene and remove the surperficial ceramic plate that has porous silicon resin of nano polylactic acid particle acquisition.
(2) porous silicon resin surface chemical modification
The surface that step (1) is made has the ceramic plate of porous silicon resin to be soaked in 10h in the acetone soln that massfraction is 15% five fluorine octyltri-ethoxysilane, obtains the ceramic plate of the porous silicon resin of surface chemical modification.
(3) fluorine-containing liquid filling
It is 500cm that the ceramic plate that the porous silicon resin of the surface chemical modification that step (2) is made covers is dipped into viscosity
2in the fluorine carbon solution of/s, then take out and wipe the unnecessary fluorocarbon liquid in surface away, obtain the ice-covering-proof material of liquid filling porous silicon resin.
When envrionment temperature is 0～-40 DEG C, ambient moisture is 40%～90% can cause ceramic plate surface to freeze time, the above-mentioned ice-covering-proof material of liquid filling porous silicon resin making can stop supercooled water contact ceramic plate, the adhesive power of the icing minimizing in ceramic plate surface and ice sheet is reduced greatly, and the ice sheet on ceramic plate surface can depart under the effect of gravity or wind-force.
Embodiment 7
(1) preparation of porous silicon resin
It is in methyl silicate/aqueous solution of 8% (mass ratio of polystyrene and methyl silicate is 1:3) that the polystyrene nanoparticle of certain mass (median size is 800nm) is joined to massfraction, after mixing, add the aqueous hydrochloric acid (aqueous hydrochloric acid is 1:30 with mixed liquor volume ratio) of 1mol/L, then solution is directly coated in to glass sheet surface, after solution dry solidification, immerses 4h in tetrahydrofuran (THF) and remove the surperficial ceramic plate that has porous silicon resin of polystyrene nanoparticle acquisition.
(2) porous silicon resin surface chemical modification
The surface that step (1) is made has the sheet glass of porous silicon resin to be soaked in 15h in the acetone soln that massfraction is 6% perfluoro capryl Trimethoxy silane, obtains the sheet glass of the porous silicon resin of surface chemical modification.
(3) fluorine-containing liquid filling
It is 100cm that the sheet glass that the porous silicon resin of the surface chemical modification that step (2) is made covers is dipped into viscosity
2in the fluorine carbon solution of/s, then take out and wipe the unnecessary fluorocarbon liquid in surface away, obtain the ice-covering-proof material of liquid filling porous silicon resin.
When envrionment temperature is 0～-40 DEG C, ambient moisture is 40%～90% can cause glass sheet surface to be frozen time, the above-mentioned ice-covering-proof material of liquid filling porous silicon resin making can stop supercooled water contact sheet glass, the adhesive power of the icing minimizing of glass sheet surface and ice sheet is reduced greatly, and the ice sheet of glass sheet surface can depart under the effect of gravity or wind-force.
Embodiment 8
(1) preparation of porous silicon resin
It is in tetraethoxy/propanol solution of 12% (mass ratio of polymethylmethacrylate and tetraethoxy is 1:1) that the polymethyl methacrylate nano particle of certain mass (median size is 50nm) is joined to massfraction, after mixing, add the aqueous nitric acid (aqueous nitric acid is 1:20 with mixed liquor volume ratio) of 0.6mol/L, then solution is directly coated in to glass sheet surface, after solution dry solidification, immerses 4h in chloroform and remove the surperficial ceramic plate that has porous silicon resin of polymethyl methacrylate nano particle acquisition.
(2) porous silicon resin surface chemical modification
The surface that step (1) is made has the sheet glass of porous silicon resin to be soaked in 15h in the chloroformic solution that massfraction is 8% perfluoro capryl Trimethoxy silane, obtains the sheet glass of the porous silicon resin of surface chemical modification.
(3) fluorine-containing liquid filling
It is 500cm that the sheet glass that the porous silicon resin of the surface chemical modification that step (2) is made covers is dipped into viscosity
2in the fluorine silicon solution of/s, then take out and wipe the unnecessary fluorocarbon liquid in surface away, obtain the ice-covering-proof material of liquid filling porous silicon resin.
When envrionment temperature is 0～-40 DEG C, ambient moisture is 40%～90% can cause glass sheet surface to be frozen time, the above-mentioned ice-covering-proof material of liquid filling porous silicon resin making can stop supercooled water contact sheet glass, the adhesive power of the icing minimizing of glass sheet surface and ice sheet is reduced greatly, and the ice sheet of glass sheet surface can depart under the effect of gravity or wind-force.
Comparative example 9
In the preparation of the ice-covering-proof material of liquid filling porous silicon resin of the present invention, the first step is prepared porous silicon resin, and to select the scope of organic nano particle be 50～800nm.For the necessity of checking organic nano particle particle diameter selection of the present invention, this comparative example, according to the preparation process of embodiment 1, prepares porous silicon resin and selects the scope of organic nano particle to use the polystyrene nanoparticle that median size is 20nm and 1000nm to prepare liquid filling porous silicon resin on copper sheet surface.
Fig. 5 is the silicone surface SEM photo of selecting 20nm (a) and 1000nm (b) polystyrene nanoparticle to prepare in comparative example 9.
No matter be that 20nm or the polystyrene nanoparticle of 1000nm are all undesirable for the preparation of the result of porous silicon resin.When particle diameter is too small, because nanoparticle is embedded in silicone resin completely, form unicellular structure after ablation, hole is almost can't see on surface.Can not form liquid film on surface at the fluorine-containing liquid of liquid compound tense like this, cannot realize anti-icing function.In the excessive comparative example of particle diameter, can see surface except forming the hole close with nano particle diameter size, also form big area defect.Because fluorine-containing liquid main capillary force that relies in pore structure is fixed, defect can cause the fluorine-containing unstabilizing liquid in this region, and the liquid surface layer of formation is imperfect.Therefore, this structure is also disadvantageous to fluorine-containing liquid again, easily forms ice and adheres to concentrated area, makes anti-icing degradation.Therefore,, according to experiment and analysis, in the present invention, the particle size range of nanoparticle is chosen as 50～800nm.
Comparative example 10
In the preparation of the ice-covering-proof material of liquid filling porous silicon resin of the present invention, the impact of the viscosity that contriver has further examined or check fluorine-containing liquid on material anti-icing performance, and the impact of evaporating property on the long-acting usability of material.Because fluorine-containing liquid viscosity is relevant to its molecular weight, viscosity is lower than 0.1cm
2the fluorine-containing liquid of/s is small-molecule substance, has obvious volatility, and the fluorine-containing liquid viscosity of therefore selecting in the present invention is greater than 0.1cm
2/ s.In this comparative example, according to the preparation process of embodiment 1, use viscosity from 0.1cm
2/ s～1000cm
2the fluorocarbon liquid of/s is as the filling liquid of step (3).
Fig. 6 is that comparative example 10 the ice-covering-proof material of liquid filling porous silicon resin is that 0 DEG C, ambient moisture are 40% in envrionment temperature, after freezing 12 hours, and the result of carrying out the test of ice adhesion size.
In Fig. 6, ice sheet adhesive power is along with the rising of viscosity has different-effect.(<50cm within the scope of low viscosity
2/ s), and ice-covering-proof material adhesion minimum (<50KPa) prepared by fluorocarbon liquid and fluorine silicon liquid, ice-covering-proof effect is excellent.(50～500cm within the scope of medium-viscosity
2/ s), ice-covering-proof material adhesion also less (<100KPa) prepared by fluorine-containing liquid, has good ice-covering-proof ability.But, but the viscosity of fluorine-containing liquid exceedes 500cm
2after/s, the ice-covering-proof successful decline (ice adhesion >145KPa) of material.The range of viscosities of the fluorine-containing liquid of therefore, selecting in the present invention is 0.1～500cm
2/ s, preferable range is 0.1～50cm
2/ s.
Claims (15)
1. the ice-covering-proof material of liquid filling porous silicon resin, is characterized in that: on base material, in conjunction with porous silicon resin and fluorine-containing liquid composite bed by silicon fluoride modification, wherein, fluorine-containing liquid filling is in the porous silicon resin of silicon fluoride modification; Porous silicon resin is mixed and forms mixing solutions with organic nano particle by inorganic silicon or organosilicon raw material, catalyst solution in solvent, is directly coated in substrate surface, removes organic nano particle and obtain after to be dried solidifying; Described fluorine-containing liquid is selected from one or both in liquid fluorocarbon, liquid fluorine silicon; Described fluorine-containing liquid range of viscosities is at room temperature 0.1～500cm
2/ s; The average particle size range of described organic nano particle is 50～800nm.
2. the ice-covering-proof material of liquid filling porous silicon resin according to claim 1, is characterized in that: described fluorine-containing liquid range of viscosities is at room temperature 0.1～50cm
2/ s; The average particle size range of described organic nano particle is 200～500nm.
3. the ice-covering-proof material of liquid filling porous silicon resin according to claim 1, is characterized in that: the porous silicon resin of silicon fluoride modification is the base material that is coated with porous silicon resin to be joined in the encloses container that is placed with silicon fluoride or immerse in the solution that is dissolved with fluorine containing silane, to carry out surface chemical modification and form.
4. the ice-covering-proof material of liquid filling porous silicon resin according to claim 1, is characterized in that: described silicon fluoride is selected from one or more in trifluoroethyl Trimethoxy silane, trifluoroethyl Trimethoxy silane, hexafluoro butyl trimethoxy silane, hexafluoro butyl triethoxyl silane, five fluorine octyl group Trimethoxy silanes, five fluorine octyltri-ethoxysilane, perfluoro capryl Trimethoxy silane, perfluoro capryl triethoxy.
5. the ice-covering-proof material of liquid filling porous silicon resin according to claim 1, is characterized in that: described inorganic silicon raw material is water glass, and organosilicon raw material is selected from one or more in methyl silicate, tetraethoxy, positive isopropyl silicate;
6. the ice-covering-proof material of liquid filling porous silicon resin according to claim 1, is characterized in that: described catalyst solution is aqueous acid, and described acid is selected from one or more in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, aqueous acetic acid.
7. the ice-covering-proof material of liquid filling porous silicon resin according to claim 6, is characterized in that: described catalyst solution concentration range is 0.01～1mol/L; The volume ratio of catalyst solution and mixing solutions is 1:10～1:100.
8. the ice-covering-proof material of liquid filling porous silicon resin according to claim 1, is characterized in that: described organic nano particle is selected from one or more in polystyrene, polymethylmethacrylate, polyacrylonitrile, polylactide, poly(lactic acid), nano-cellulose.
9. the ice-covering-proof material of liquid filling porous silicon resin according to claim 1, is characterized in that: the mass ratio of described organic nano particle and inorganic silicon or organosilicon raw material is 1:1～1:4.
10. the ice-covering-proof material of liquid filling porous silicon resin according to claim 1, is characterized in that: the method for described removal organic nano particle comprises high temperature ablation or dissolution with solvents; The temperature province of described high temperature ablation is 300～800 DEG C, and the ablation time is 0.5～20h; The solvent using in described dissolution with solvents is selected from one or more in chloroform, methylene dichloride, tetracol phenixin, tetrahydrofuran (THF), dimethyl formamide, and soak time is 2～24h.
The ice-covering-proof material of 11. liquid filling porous silicon resin according to claim 1, is characterized in that: the solvent in described mixing solutions is selected from one or more in water, methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, acetone.
The ice-covering-proof material of 12. liquid filling porous silicon resin according to claim 1, is characterized in that: described base material is copper, iron, aluminium, titanium, glass or pottery.
Prepare the method for the ice-covering-proof material of liquid filling porous silicon resin described in claim 1-12 for 13. 1 kinds, it is characterized in that, comprise following process:
(1) preparation of porous silicon resin: it is in 10%～50% inorganic silicon or organic silicon solution that organic nano particle is joined to massfraction, after mixing, add catalyst solution, the mixing solutions forming is directly coated in substrate surface, and after to be dried solidifying, high temperature ablation or dissolution with solvents are removed organic nano particle and obtained porous silicon resin surface;
(2) porous silicon resin surface chemical modification: there is the base material of porous silicon resin to be placed in to be placed with the encloses container of silicon fluoride on the surface that (1) step is made or immerses and is dissolved with fluorine containing silane solution and carries out surface chemical modification;
(3) fluorine-containing liquid filling: adopt the method for spraying or immersion that fluorine-containing liquid is fixed in the porous silicon resin of surface chemical modification.
14. methods according to claim 12, is characterized in that: the time of described surface chemical modification is 2～48h.
15. methods according to claim 12, is characterized in that: in the solution of described fluorine containing silane, solvent is selected from one or more in methyl alcohol, ethanol, acetone, benzene, chloroform; In described fluorine containing silane solution, the massfraction of fluorine containing silane is 1%～20%.
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| CN106519968A (en) * | 2016-11-15 | 2017-03-22 | 中国科学院化学研究所 | Low-ice-adhesion anti-icing coating, and preparation method and application thereof |
| CN106865487A (en) * | 2017-01-10 | 2017-06-20 | 长春理工大学 | Liquid injection type superslide surface and its laser accurate micro-processing method |
| CN109111744A (en) * | 2017-06-26 | 2019-01-01 | 洛阳尖端技术研究院 | A kind of ice-covering-proof pad pasting and preparation method thereof |
| CN110023424A (en) * | 2016-10-20 | 2019-07-16 | 通用线缆技术公司 | Durable application composition and the coating formed by it |
| CN116162285A (en) * | 2023-03-01 | 2023-05-26 | 西南科技大学 | Preparation and application of porous PDMS (polydimethylsiloxane) impregnated organic oil anti-icing lubricating surface |
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| CN116162285A (en) * | 2023-03-01 | 2023-05-26 | 西南科技大学 | Preparation and application of porous PDMS (polydimethylsiloxane) impregnated organic oil anti-icing lubricating surface |
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