CN103450801A - Method for preparing micro-nano silicon-based super-hydrophobic coating and application thereof - Google Patents
Method for preparing micro-nano silicon-based super-hydrophobic coating and application thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 239000011248 coating agent Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000005543 nano-size silicon particle Substances 0.000 title abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000741 silica gel Substances 0.000 claims abstract description 43
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 43
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 18
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- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000005357 flat glass Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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Abstract
The invention belongs to the technical field of surface functional material manufacturing, and particularly relates to a method for preparing a micro-nano silicon-based super-hydrophobic coating on different substrates by thermally decomposing oxidized silica gel under the condition of normal pressure and aerobic atmosphere and application thereof. The method is characterized in that silica gel is decomposed to generate steam by heating at 150-330 ℃ under the condition of normal pressure and aerobic atmosphere, the steam is subjected to oxidation vapor deposition at 300-380 ℃ for 10-180 min, and the optical anti-reflection, colorless transparent or colored micro-nano silicon-based super-hydrophobic coating is formed on glass, metal and other substrates with the temperature resistance higher than 300 ℃. The method has the advantages of green and environment-friendly preparation process, easiness in operation, repeatability, capability of preparing large-size samples and the like. The coating has good water drop adhesion prevention function, can realize colorless transparency or color, can form an optical anti-reflection effect on a glass substrate, and has a surface anticorrosion effect on a metal substrate. The micro-nano silicon-based super-hydrophobic coating prepared by the invention can be widely applied to the fields of automobile windshields, radar antennas, solar cells, metal corrosion prevention and the like.
Description
Technical field
The invention belongs to surface functional material manufacturing technology field, particularly relate to and a kind ofly utilize thermolysis silica gel under normal pressure aerobic atmospheric condition to deposit method of micro nanometer silicon based super hydrophobic coating and uses thereof in different substrates.
Technical background
There is the function surface of the performances such as waterproof, snow defence, anticorrosion and anti-adhesive, can be widely used in the fields such as windshield, radar scanner, solar battery sheet and protection against corrosion, there is boundless application prospect.The super-hydrophobic coat surface built has above-mentioned functional performance.So-called super-hydrophobic coat surface refers to that the contact angle with water is greater than 150 ° and surface that roll angle is less than 10 ° is the research and development focus of high-technology field.
Silica gel is the polysiloxane with different molecular weight solidify to form by different chlorosilanes or siloxanes, it is not only a kind of chemical material that has both the uniqueness of organic and inorganic nature, but also be a kind of typical low surface energy functional high molecule material, its surface can be 20～23dyn/cm, be to build the ideal material of super-hydrophobic coat, especially have broad application prospects building aspect transparent super-hydrophobic coat.Up to the present, the super-hydrophobic coat functional materials that the application polysiloxane builds, also being confined to apply the silane hydrolysis condensation reaction prepares nano coating or prepares super-hydrophobic coat by the mode of carrying out chemically modified at uneven surface, as (the J.Zimmermann of Zimmermann research group, G. R.J.Artus, S.Seeger et.a1.Long term studies on the chemical stabilityof superhydrophobic silicone nanofilament coating[J] .Appl.Surf.Sci.2007, 253:5972-5979) by the hydrolyzing chlorosilane polycondensation, prepare the thread coating of the nanometer with superhydrophobic characteristic, this coating is to acid, alkali and organic solvent show satisfactory stability.And for example Seeger research group is by the polycondensation of trichloromethyl silane controlled hydrolysis, formed and be greater than super hydrophobic surface (the G. R.J.Artus of 150 ° with water contact angle at aluminium, glass and fiber surface, S.Jung, J.Zimmermann et.al.Silicone Nanofilaments and Their Application as Superhydrophobic Coatings[J] .Adv.Mater.2006,18:2758-2762; G. R.J.Artus, S.Seeger.Scale-Up of a Reaction Chamber for Superhydrophobic Coatings Based on Silicone Nanofilaments[J] .Ind.Eng.Chem.Res.2012,51:2631-2636).The people such as Japanese Yuan be take the nano-polyethylene imines of self-assembly and is controlled the hydrolytie polycondensation process of siloxanes as template for another example, prepare the thread coating of one dimension polysilsesquioxane nanometer containing multiple functional group, this coating has excellent ultra-hydrophobicity (J.J.Yuan after poly-perfluoro-methyl isopropyl ether is modified, N.Kimitsuka, R.H.Jin.Bioinspired Synthesis of a Soft-Nanofilament-Based Coating Consisting of Polysilsesquioxanes/Polyamine and Its Divergent Surface Control[J] .ACS Appl.Mater.& Interf.2013,5:3126-3133).In addition, Chinese patent CN101727010A discloses a kind of method that mode of utilizing the organosilane low-surface-energy material to carry out finishing prepares super hydrophobic surface, at first the method by the laser interference etching forms the roughness of micro nano structure at substrate surface, and then carry out finishing with low surface energy materials such as silicon fluorides, prepared colour super-hydrophobic coating, its static contact angle is up to 163 °.Although these utilize silane to make great progress preparing super-hydrophobic coat, but also exist a lot of deficiencies, be mainly reflected in: can produce a large amount of hydrochloric acid after the hydrolyzing chlorosilane that hydrolytie polycondensation is used, the acid mist formed therefrom causes certain harm to environment; Simultaneous reactions is mainly the hydrolytie polycondensation that certainly volatilizees and carry out under certain humidity by chlorosilane, consuming time longer, generally all needs a few hours to arrive more than tens of hours, is difficult to prepare large size and batch samples; And the low surface energy material that surface modification method is used (as the perfluor siloxanes) price is very expensive, cause production cost higher, should not promote; The more important thing is, these methods are generally to carry out in the organic solvent the inside, and a large amount of organic solvents can bring serious environmental pollution.Above shortcoming has seriously restricted applying of super hydrophobic surface.Therefore, need the preparation technology of a kind of environmental protection, simple economy to prepare micro nanometer silicon based super hydrophobic coating.
Summary of the invention
The object of the present invention is to provide and a kind ofly apply cheap raw material and have vapour deposition under oxygen atmosphere to prepare the method for micro nanometer silicon based super hydrophobic coating at normal pressure; Another object of the present invention is, by the change condition, under the same device, prepare there is antireflection, water white transparency or colored silica-based super-hydrophobic coat.Concrete operations are as follows:
At first, at room temperature by silica gel in air set, then curing block silica gel is prepared into to the fine particle (seeing embodiment 2) of 3mm size.A certain amount of tiny silica gel particle is placed in to the thermolysis oxidation vapor phase growing apparatus interior (volume is about 1L) of our design, glass and the metal base (seeing embodiment 1) processed are placed in the thermooxidizing depositing system.Under normal pressure aerobic atmospheric condition, the thermolysis that process is different and oxide deposition temperature, oxide deposition time, on different base, prepare there is antireflection, water white transparency or colored micro nanometer silicon based super hydrophobic coating, residual gas is discharged after the tail gas clean-up treatment system is processed.As shown in Figure 1, its integral part mainly comprises atmosphere Controlling System, thermolysis system, thermooxidizing depositing system, tail gas clean-up treatment system to the apparatus system of silica gel thermolysis oxide deposition.Wherein the atmosphere control section is by N
2and O
2steel cylinder, flow valve, under meter and pipeline form; The thermolysis part is comprised of the electric heating panel that can independently control temperature; Thermooxidizing deposition part is comprised of the independent electric heating panel of controlling and support that can anchoring base; The tail gas clean-up treating part is comprised of pipeline, valve and alkali lye.
In above-mentioned preparation method, described silica gel includes but are not limited to one or more of depickling type silica gel, dealcoholizing-type silica gel, de-oxime type silica gel, de-the third type silica gel and de amide type silica gel.
In above-mentioned preparation method, described aerobic atmospheric condition refers to N
2and O
2mixed gas, N wherein
2with O
2volume ratio V preferably
n2/ V
o2be 3～5, controlled by flow valve and under meter.
In above-mentioned preparation method, described better decomposition temperature is 150 ℃～330 ℃, and better oxide deposition temperature is 300 ℃～380 ℃, and the better oxide deposition time is 10～180min.
In above-mentioned preparation method, described substrate includes but are not limited to the heatproofs such as sheet glass, aluminium flake, iron plate, copper sheet, stainless steel substrates in the substrate more than 300 ℃.
The purposes of super-hydrophobic coat prepared by the present invention:
For meeting different needs, super-hydrophobic coat prepared by the present invention can be white, black, brown, water white or have antireflective effect.As embodiment 3, get 1g depickling type silica gel particle and be placed on the thermolysis system, will be placed on the thermooxidizing depositing system at the bottom of glass chip, pass into mixed gas (N
2with O
2volume ratio V
n2: V
o2=5: 1) to state of saturation, decomposition temperature is made as 150 ℃, the oxide deposition temperature is made as 300 ℃, after oxide deposition 180min, obtain the super-hydrophobic coat that white nanofiber forms on glass substrate, reach 170 ± 3 ° with the contact angle of 4 μ L water droplets, scanning electron microscope and contact angle test result are in shown in Fig. 2; And for example embodiment 4, get 0.4g de amide type silica gel particle, pass into mixed gas (V
n2: V
o2=3: 1) to state of saturation, decomposition temperature is made as 330 ℃, and the oxide deposition temperature is made as 380 ℃, reacts 120min, obtains the super-hydrophobic nano coating of black on glass substrate, with the contact angle of 4 μ L water droplets, can reach 170 ± 2 °, and test result is in shown in Fig. 3.As embodiment 5, get 6g mixing silica gel particle (depickling type and dealcoholizing-type silica gel mix in mass ratio at 1: 1), pass into mixed gas (V
n2: V
o2=3: 1) to state of saturation, decomposition temperature is made as 330 ℃, and the oxide deposition temperature is made as 340 ℃, after reaction 120min, obtain the brown super-hydrophobic coat that 1～2 μ m spherical particle forms on glass substrate, contact angle can reach 165+3 °, and test result is in shown in Fig. 4.As embodiment 6, get the de-oxime type silica gel particle of 3g, pass into mixed gas (V
n2: V
o2=9: 2) to state of saturation, decomposition temperature is made as 180 ℃, and the oxide deposition temperature is made as 350 ℃, after reaction 10min, on the copper sheet substrate, also white super-hydrophobic coat can be obtained, with the contact angle of 4 μ L water droplets, 163+2 ° can be reached, roll angle～4 °, test result is in shown in Fig. 5.Embodiment 7 for another example, get de-the third type silica gel particle of 0.1g and place the thermolysis system, pass into mixed gas (V
n2: V
o2=4: 1) to state of saturation, decomposition temperature is made as 300 ℃, the oxide deposition temperature is made as 320 ℃, after oxide deposition 10min, prepare colourless transparent hydrophobic coating on glass substrate, with the contact angle of 4 μ L water droplets up to 171+4 °, roll angle～2 °, the visible light permeability test result is in shown in Fig. 6.This transparent hydrophobic coating has antireflective effect, than the maximum of coating not, can improve 5% left and right transmitance.Near maximum transmission absorbing wavelength 520nm has reached 95%, and test result is in shown in Fig. 7.
Method provided by the invention can prepare the large size super-hydrophobic coat, and this coating has potential application in waterproof, aspect anticorrosion.As embodiment 8, get 10g depickling type silica gel particle and place silica gel thermolysis system, pass into mixed gas (V
n2: V
o2=4: 1) to state of saturation, in decomposition temperature, be that 280 ℃, oxide deposition temperature are to carry out oxide deposition 150min under 370 ℃ of conditions, prepare to have and be of a size of 10 * 10cm
2the transparent hydrophobic sheet glass.Result shows that super-hydrophobic coat has extraordinary rainwater-proof adhesiving effect, and the sample edge zone is because not depositing silica-based coating, and result has a large amount of water droplets to adhere to, and has a strong impact on its light transmission, and test result is in shown in Fig. 8.And for example embodiment 9, get 6g dealcoholizing-type silica gel particle, pass into mixed gas (V
n2: V
o2=4: 1) to state of saturation, decomposition temperature is made as 200 ℃, and the oxide deposition temperature is made as 340 ℃, after reaction 60min, on iron plate, aluminium flake and three kinds of substrates of stainless steel substrates, all obtains super-hydrophobic coat.Be positioned over acid mist corrosion case (the long-pending 5L that is about of casing respectively together with the tinsel of the super-hydrophobic tinsel for preparing and coating not, the hydrochloric acid volumetric concentration is about 1.6%) in, under room temperature after the corrosion of the acid mist of 16h, not too large variation before and after tinsel corrosion after coating, do not change obviously (result is in shown in Fig. 9) after the corrosion of the tinsel of coating.
Preparation method provided by the invention, compare the silica gel materials low price with existing technology of preparing; Adopt the method for normal atmosphere vapor deposition, method is relatively simple.The present invention has environmental protection, easy handling, reproducible, can prepare the advantages such as large size sample; Can also prepare water white transparency and colour super-hydrophobic coating with antireflection effect, meet different needs.Simultaneously, the super-hydrophobic coat that prepared by the inventive method has good anticorrosion ability.The micro nanometer silicon based super hydrophobic coating that we prepare can be widely used in the fields such as windshield, radar scanner, solar battery sheet, protection against corrosion.
The accompanying drawing explanation
Fig. 1: the special silica gel thermolysis oxide deposition of the present invention prepares the principle of device schematic diagram of super-hydrophobic coat:
Wherein 1. thermolysis systems, 2. thermooxidizing depositing system, 3. atmosphere Controlling System, 4. tail gas clean-up treatment system;
The field emission scanning electron microscope figure of Fig. 2: embodiment 3 resulting white super-hydrophobic coats, the upper right corner is water and surperficial contact angle figure;
The field emission scanning electron microscope figure of the resulting black super-hydrophobic coat of Fig. 3: embodiment 4, the upper right corner is water and surperficial contact angle figure;
The field emission scanning electron microscope figure of Fig. 4: embodiment 5 resulting brown super-hydrophobic coats, the upper right corner is water and surperficial contact angle figure;
The field emission scanning electron microscope figure of Fig. 5: embodiment 6 resulting white super-hydrophobic coats, the upper right corner is water and surperficial contact angle figure;
The digital photograph of the resulting water white transparency super-hydrophobic coat of Fig. 6: embodiment 7, the upper right corner is water and surperficial contact angle figure;
The ultraviolet-visible absorption spectroscopy figure of the resulting water white transparency super-hydrophobic coat of Fig. 7: embodiment 7:
Wherein after a. deposited coatings, before the b. deposited coatings;
The digital photograph of the anti-adhesion properties of the resulting large size transparent hydrophobic coating of Fig. 8: embodiment 8 sample when raining (the arrow indicating area is the sample edge zone, do not deposit super-hydrophobic coat and adhere to water droplet);
The resulting super-hydrophobic tinsel of Fig. 9: embodiment 9 and the digital photograph before and after the tinsel surface corrosion of deposited coatings not:
Wherein iron, aluminium and the stainless steel substrates of (a1), (b1), (c1) deposition super-hydrophobic coat corrode front pattern; (a2), pattern after iron, aluminium and the stainless steel substrates corrosion of (b2), (c2) deposition super-hydrophobic coat; (a3), (b3), (c3) do not deposit iron, aluminium and the rear pattern of stainless steel substrates corrosion of super-hydrophobic coat.
Embodiment
Below in conjunction with embodiment, the present invention is conducted further description, is not intended to limit the present invention:
The processing of substrate: the method for the invention has very strong compatibility to material, the size and shape of substrate, plane, curved surface or irregular substrate are all applicable, and the typical substrates that is applicable to the present invention's use can be sheet glass, iron plate, aluminium flake, copper sheet, stainless steel substrates etc.The various impurity that adhere to for removing substrate surface, we put into the vitriol oil (massfraction is 98%) and H by sheet glass
2o
2mixing solutions (the volume ratio V of (massfraction is 30%)
h2SO4: V
h2O2=7: 3) boil 30min to overflowing without bubble, a large amount of distilled water flushings of cooling rear taking-up, then dry up with nitrogen, stand-by; We put into the ultrasonic 60min of dehydrated alcohol by tinsel, take out and use a large amount of distilled water flushings, then dry up with nitrogen, stand-by.
The preparation of vapor deposition source: multiple silica gel is coated in respectively to clean, smooth ptfe substrate surface uniformly, after solidifying 48h at normal temperatures, is processed into 3mm left and right particle of uniform size standby.
The depickling type silica gel particle of getting 1g embodiment 2 preparations is placed on the thermolysis system, will be placed on the thermooxidizing depositing system at the bottom of the glass chip in embodiment 1.Pass into mixed gas (V
n2: V
o2=5: 1) to state of saturation, decomposition temperature is made as 150 ℃, and the oxide deposition temperature is made as 300 ℃, after oxide deposition 180min, obtains white super-hydrophobic coat on glass substrate, with the contact angle of 4 μ L water droplets up to 170 ± 3 °.Test result is in shown in Fig. 2.
The de amide type silica gel particle of getting 0.4g embodiment 2 preparations is placed on the thermolysis system, will be placed on the thermooxidizing depositing system at the bottom of the glass chip in embodiment 1.Pass into mixed gas (V
n2: V
o2=3: 1) to state of saturation, decomposition temperature is made as 330 ℃, and the oxide deposition temperature is made as 380 ℃, after reaction 120min, obtains the black super-hydrophobic coat on glass substrate, with the contact angle of 4 μ L water droplets, can reach 170 ± 2 °.Test result is in shown in Fig. 3.
Embodiment 5
The mixing silica gel particle (depickling type and dealcoholizing-type silica gel mix in mass ratio at 1: 1) of getting 6g embodiment 2 preparations is placed on the thermolysis system, will be placed on the thermooxidizing depositing system at the bottom of the glass chip in embodiment 1.Pass into mixed gas (V
n2: V
o2=3: 1) to state of saturation, decomposition temperature is made as 330 ℃, and the oxide deposition temperature is made as 340 ℃, after reaction 120min, obtains brown super-hydrophobic coat on glass substrate, with the contact angle of 4 μ L water droplets, can reach 165 ± 3 °.Test result is in shown in Fig. 4.
The de-oxime type silica gel particle of getting 3g embodiment 2 preparations is placed on the thermolysis system, and the copper sheet substrate in embodiment 1 is placed on to the thermooxidizing depositing system.Pass into mixed gas (V
n2: V
o2=9: 2) to state of saturation, decomposition temperature is made as 180 ℃, and the oxide deposition temperature is made as 350 ℃, after reaction 10min, obtains white super-hydrophobic coat on the copper sheet substrate, with the contact angle of 4 μ L water droplets, can reach 163 ± 2 °, roll angle～4 °.Test result is in shown in Fig. 5.
De-the third type silica gel particle of getting 0.1g embodiment 2 preparations is placed on the thermolysis system.Pass into mixed gas (V
n2: V
o2=4: 1) to state of saturation, in decomposition temperature, be that 300 ℃, oxide deposition temperature are under 320 ℃ of conditions, oxide deposition 10min, prepare and there is colourless transparent hydrophobic sheet glass, with the contact angle of 4 μ L water droplets be 171 ± 4 °, roll angle～2 °, perviousness and contact angle test result are in shown in Fig. 6.This transparent silicon based super hydrophobic coating has the antireflection effect, than maximum before coating not, can improve 5% left and right transmitance.This shows that micro-nano porous silicon-base coating has significant wideband antireflection, and near maximum transmission rate absorbing wavelength 520nm has reached 95%, and test result is in shown in Fig. 7.
Embodiment 8
The depickling type silica gel particle of getting 10g embodiment 2 preparations is placed on the thermolysis system.Pass into mixed gas (V
n2: V
o2=4: 1) to state of saturation, in decomposition temperature, be to carry out oxide deposition 150min under 280 ℃, the oxide deposition temperature condition that is 370 ℃, prepare to have and be of a size of 10 * 10cm
2the transparent hydrophobic sheet glass.Result shows, this sample has extraordinary rainwater-proof adhesiving effect (region intermediate), sample edge zone (as shown by arrows) is owing to needing fixed position there is no depositing silicon based super hydrophobic coating in preparing coating procedure, result has a large amount of water droplets to adhere to, have a strong impact on its light transmission, test result is in shown in Fig. 8.
Embodiment 9
Get the dealcoholizing-type silica gel particle of 6g embodiment 2 preparations and place silica gel thermolysis system, respectively the iron plate in embodiment 1, aluminium flake and stainless steel substrates substrate are placed to the oxide deposition system.Pass into mixed gas (V
n2: V
o2=4: 1) to state of saturation, decomposition temperature is made as 200 ℃, and the oxide deposition temperature is made as 340 ℃, after reaction 60min, on iron plate, aluminium flake and three kinds of substrates of stainless steel substrates, all obtains super-hydrophobic coat.Be positioned over acid mist corrosion case (the long-pending 5L that is about of casing respectively together with the tinsel of the super-hydrophobic tinsel for preparing and coating not, the hydrochloric acid volumetric concentration is about 1.6%) in, at room temperature after the acid mist corrosion of 16h, result shows to deposit not too large variation before and after the tinsel corrosion of coating, not the tinsel of deposited coatings obviously be corroded (result is in shown in Fig. 9).
Claims (4)
1. under a normal pressure aerobic atmospheric condition, the thermolysis silica gel prepares method of micro nanometer silicon based super hydrophobic coating and uses thereof, it is characterized in that under normal pressure aerobic atmospheric condition, by 150 ℃～330 ℃ heating, silica gel is decomposed, the steam decompose produced carries out oxide deposition 10～180min at 300 ℃～380 ℃ temperature, finally on different base, prepare there is antireflection, water white transparency or colored micro nanometer silicon based super hydrophobic coating.
2. super-hydrophobic coat preparation method as claimed in claim 1, is characterized in that silica gel includes but are not limited to one or more of depickling type silica gel, dealcoholizing-type silica gel, de-oxime type silica gel, de-the third type silica gel and de amide type silica gel.
3. super-hydrophobic coat preparation method as claimed in claim 1, is characterized in that described aerobic atmospheric condition refers to N
2and O
2mixed gas, N wherein
2with O
2volume ratio V preferably
n2/ V
o2be 3～5.
4. super-hydrophobic coat preparation method as claimed in claim 1, is characterized in that substrate includes but are not limited to sheet glass, aluminium flake, iron plate, copper sheet, stainless steel substrates and other energy heatproof in the substrate more than 300 ℃.
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