CN102453465B - Adhesive super-hydrophobic material and preparation method thereof - Google Patents
Adhesive super-hydrophobic material and preparation method thereof Download PDFInfo
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- CN102453465B CN102453465B CN201010521305.9A CN201010521305A CN102453465B CN 102453465 B CN102453465 B CN 102453465B CN 201010521305 A CN201010521305 A CN 201010521305A CN 102453465 B CN102453465 B CN 102453465B
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Abstract
The invention relates to an adhesive super-hydrophobic material and a preparation method thereof. The material refers to silicon dioxide nanoparticles containing organic groups. A surface with dual nanometer roughness is obtained by taking the material as a constructing unit and depositing on a substrate. The surface has super-hydrophobic performance and very high adhesion, a contact angle is 140-170 degrees, and water drops are prevented from falling off under the condition of inclination or reversion. The method has the advantages of easiness for operating, readily-available raw materials, low cost and wide application prospects on conveying, transfer and separation of water.
Description
Technical field
The present invention relates to a kind of super-hydrophobic adhesive type material and preparation method thereof.
Background technology
The super-hydrophobic apparent contact angle that refers to the upper water in surface exceedes a kind of special surface phenomenon of 150 °.In recent years, super hydrophobic surface has caused that people pay close attention to greatly, and it has a wide range of applications in the fields such as many fields such as self-cleaning material, microfluidic device, catalysis, oil recovery, covering with paint, waterproof and biomaterial.Most typical example is exactly the lotus leaf surface of occurring in nature, and water droplet can Free-rolling on blade face, pollutents such as being attached to dust on blade face can be taken away, thereby make surface keep clean.Two kinds of methods of the general employing of preparation of tradition super hydrophobic surface: a kind of is the material of modifying low surface energy at uneven surface; Another kind is to build coarse structure at water repellent surface.About the method for production of super-hydrophobic uneven surface, mainly contain phase separation method, template, sol-gel method, Electrospinning Method, etching method, etch, self-assembly, chemical vapour deposition and additive method.According to liquid, at surperficial rolling effect, super hydrophobic surface can be divided into again scolds water type and adhesive type super hydrophobic surface.Scold the contact angle of water type super hydrophobic surface and water droplet to be greater than 150 °, but very little to water droplet adhesive power, water droplet is easy to tumble from surface.There is in a large number this super hydrophobic surface in nature, such as lotus leaf, the feather of bird and water worm etc. be all this low adhesive power scold water type surface.Due to this super hydrophobic surface self-cleaning performance, the synthetic of this surface is all absorbed in a large amount of research.Adhesive type super hydrophobic surface is not only greater than 150 ° with the contact angle of water droplet, and water droplet is had to very strong adhesive power, and by surface tilt or inversion, water droplet can not roll.Although this super hydrophobic surface can not automatically cleaning, the adhesive power that this kind is high to liquid, is conducive in micron level, water droplet be operated, and shifts at free of losses liquid, and the aspects such as microfluidic control system and biosensor show good application prospect.Comparatively speaking, the research of adhesive type super hydrophobic surface is less.Existing research all concentrates in the structure control of effects on surface, utilizes capillary force to adhere to liquid.The method that develops a kind of easy synthetic super-hydrophobic adhesive type surface has great importance
Summary of the invention
The invention provides a kind of adhesive super-hydrophobic material and preparation method thereof.
This material is a kind of nano SiO 2 particle that contains organic group, regulates and controls adhesive power size by the chemical composition of control surface.Using this material as construction unit, on matrix, deposit the surface that obtains having two-dimensional nano roughness.Matrix can be sheet glass, silicon chip, metal or metal oxide.
Two kinds of methods of the general employing of preparation of tradition super hydrophobic surface: a kind of is the material of modifying low surface energy at uneven surface; Another kind is to build coarse structure at water repellent surface.From upper different, it is that construction unit deposits on matrix that the present invention adopts the nano SiO 2 particle of low surface energy organic matter modified, obtains having the surface of double Nanometer Roughness.A low surface energy material and roughness step in deposition process realizes.Operate more simple, convenient.Traditional coarse structure only has a heavy roughness, or a bicron rank roughness and a heavy Nano grade roughness.Surface prepared by the present invention has double nanometer coarse structure.Nano SiO 2 particle body is assembled into a heavy Nanometer Roughness, and the silica sphere of the synthetic organic decoration of the present invention itself is very coarse, forms the second heavy nanometer coarse structure, and double coarse structure is all at Nano grade.
From to carry out modulation adhesive power by control surface structure different, the present invention regulates and controls adhesive power size by controlling chemical composition, can obtain super-hydrophobic adhesive type material, contact angle is between 140-170 °, and thering is very strong adhesive power, water droplet does not return under landing in inclination or inverted situation.
Precipitation agent is water miscible, and silane is oil-soluble, for synthetic uniform particle diameter, the nano SiO 2 particle that contains organic group of high dispersive, must make precipitation agent and silane fully and uniform contact, the present invention adopt tensio-active agent and cosurfactant by ammonia soln high dispersive among oil phase, make silane and precipitation agent fully and uniform contact, precipitation from homogeneous solution.Can on matrix, form a super hydrophobic surface by simple deposition and burin-in process.
Described adhesive type super hydrophobic surface preparation process, can operate as follows:
A) dispersion and the precipitation from homogeneous solution thereof of inorganic precipitant in oil phase: tensio-active agent, organic phase, cosurfactant and ammoniacal liquor are configured to solution A according to a certain percentage.A certain amount of tetraethoxy or methyl silicate are silicon source, wiring solution-forming B.Under room temperature, in A microemulsion, add solution B, stir 6～48h.
The mass ratio of the final mixing solutions of gained is 1～10 tensio-active agent: 0.5～6 ammoniacal liquor: 5～15 organic phases: 0～6 cosurfactant: 1 silane: 0.05～1.5 organosilane.Ammonia concn is 1～30wt%.
Add the acetone breakdown of emulsion of 1-10 times of silicon source quality, the centrifugal solid that obtains, adds the alcohol reflux 5～30min of 5-50 times of silicon source quality, centrifugal, repeat 2～5 washings, be dispersed in ethanol, obtaining silicon-dioxide alcohol dispersion liquid silicon-dioxide quality concentration is 1～20wt%;
B) formation of super hydrophobic surface: matrix first cleans with ultrasonic detergent, then water, acetone clean 2～6 times repeatedly, and silicon-dioxide alcohol dispersion liquid is deposited on matrix surface, aging 1～48h at 20～200 DEG C, obtains super hydrophobic surface.
Described tensio-active agent is C8-20 linear alkylbenzene sulphonic acid or the α-sodium olefin sulfonate in anion surfactant, or be organic primary amine, Np series or the tween series of surfactants of the C8-20 long-chain in nonionogenic tenside, or be the hexadecyl trimethyl ammonium bromide in cats product.Described organic phase is hexanaphthene, normal hexane or toluene; Cosurfactant is propyl carbinol, Pentyl alcohol, n-hexyl alcohol or n-Octanol.Organic group be methyl, ethyl, propyl group, vinyl, phenyl, dodecyl, octadecyl, trifluoro propyl, perfluor certain herbaceous plants with big flowers base and pentafluorophenyl group one or several.Matrix is sheet glass, silicon chip, metal or metal oxide.
The nano SiO 2 particle of organic decoration prepared by the present invention, size is controlled, and particle diameter is at 20～1000nm (being shown in Fig. 1).Prepared surface has coarse structure (seeing Fig. 2).Prepared super-hydrophobic adhesive type surface contact angle is 140～170 °, and water droplet is not under 90 ° or 180 ° of inclinations can be rolled (seeing Fig. 3).
Brief description of the drawings
The transmission electron microscope photo of synthetic silica dioxide granule A in Fig. 1 example 1.
The super hydrophobic surface stereoscan photograph that adopts silicon-dioxide A to prepare in Fig. 2 example 7.
The super hydrophobic surface water droplet contact angle picture that adopts silicon-dioxide A to prepare in Fig. 3 example 7.
Embodiment
Tensio-active agent, organic phase, cosurfactant and ammoniacal liquor are configured to solution A according to a certain percentage.A certain amount of tetraethoxy or methyl silicate and organosilane wiring solution-forming B.
Under room temperature, in A microemulsion, splash into solution B, stir 6～48h.The mass ratio of the final mixing solutions of gained is 1～10 tensio-active agent: 0.5～6 ammoniacal liquor: 5～15 organic phases: 0～6 cosurfactant: 1 silane: 0.05～1.5 organosilane.Add the acetone breakdown of emulsion of 1-10 times of silicon source quality, the centrifugal solid that obtains, adds the alcohol reflux 5～30min of 5-50 times of silicon source quality, centrifugal, repeat 2～5 washings, be dispersed in ethanol, obtain silicon-dioxide alcohol dispersion liquid, silicon-dioxide quality concentration is 1～20wt%; Matrix first cleans with ultrasonic detergent, then water repeatedly, and acetone cleans 2～6 times, and silicon-dioxide alcohol dispersion liquid is deposited on matrix surface, keeps 1～48h at 20～200 DEG C, obtains super hydrophobic surface.
Below by embodiment, method provided by the invention is described in detail, but do not limit in any form the present invention.
Embodiment 1 silicon-dioxide A (Ph-SiO
2) preparation
Get 8.0g Np-12,15.0g hexanaphthene, 3.0g n-Octanol and 5.0g 10wt%, obtain solution A; 1.0g tetraethoxy 0.5g phenyl base Trimethoxy silane is solution C; Under agitation solution B is added in solution D to aging 8h; Then, add 8g acetone, stir 30min, the centrifugal solid that obtains;
In this solid, add 30g ethanol, heated and stirred 10min is centrifugal; Repeat this step 5 time, until removal of surfactant is clean; Gained solid is dispersed in 10g ethanol.As shown in Figure 1, can find out the nano SiO 2 particle of organic decoration, particle diameter is even, and particle diameter is at 100nm, and surface is very coarse.
The preparation of embodiment 2 silicon-dioxide B-L
The same materials A of preparation method of material B-L, difference is in the kind and add-on of organosilane, and the kind of the concrete organosilane adopting and add-on are in table 1, and the material obtaining is listed in table 1.
Kind and the add-on of the organosilane adopting in table 1 material B-H preparation
Embodiment 3 silicon-dioxide I (Me-SiO
2) preparation
Get 2.0g Sodium dodecylbenzene sulfonate, 10.0g normal hexane, 1.0g propyl carbinol and 4.0g 15wt% ammoniacal liquor and be mixed to get microemulsion A; 1.0g methyl silicate and 0.5g methyltrimethoxy silane are solution B.Under agitation solution B is splashed in solution D to aging 15h; Then add 10g acetone, stir 30min, the centrifugal solid that obtains;
In this solid, add 30g ethanol, heated and stirred 10min is centrifugal; Repeat this step 4 time, until removal of surfactant is clean.Gained solid is dispersed in 10g ethanol.
The preparation of embodiment 4 silicon-dioxide J-R
The preparation method of material J-R is with material I, and difference is kind and the add-on of organosilane, and the concrete organosilane adopting and add-on kind are in table 2, and the material obtaining is listed in table 2.
Kind and the add-on of the organosilane adopting in table 2 material J-R preparation
Embodiment 5 silicon-dioxide S (Do-SiO
2) preparation
Get 5.0g hexadecyl trimethyl ammonium bromide, 12.0g toluene, 2.0g Pentyl alcohol and 4.5g 5wt% ammoniacal liquor and be mixed to get microemulsion liquid A; 1.0g methyl silicate and 0.1g dodecyltrimethoxysilane are solution B; Under agitation solution C is splashed in solution A to aging 24h; Then, add 10g acetone, stir 30min, the centrifugal solid that obtains;
In this solid, add 30g ethanol, heated and stirred 10min is centrifugal; Repeat this step 3 time, until removal of surfactant is clean.Gained solid is dispersed in 10g ethanol.
The preparation of embodiment 6 silicon-dioxide U-Z
The preparation method of material T-Z is with material S, and difference is kind and the add-on of organosilane, and the concrete organosilane adopting and add-on kind are in table 3, and the material obtaining is listed in table 3.
Kind and the add-on of the organosilane adopting in table 3 silicon-dioxide T-Z preparation
The preparation of embodiment 7 super hydrophobic surfaces
Sheet glass first cleans with ultrasonic detergent, then water cleans 3 times repeatedly, and acetone cleans 4 times, dry.The A-Z silicon-dioxide alcohol dispersion liquid preparing is deposited on matrix surface, at 150 ° of temperature, aging 24h.
As shown in Figures 2 and 3, can find out, prepared surface has coarse structure.This surface has superhydrophobic property, and water droplet contact angle is greater than 150 °, and has very strong adhesion property, and water droplet can not fall down in inverted situation.
Super hydrophobic material prepared by method provided by the invention can adhere on different matrixes, form a super hydrophobic surface, have ultra-hydrophobic high sticking performance, the method is simple to operate, and raw material is easy to get, cost is low, shift at free of losses liquid, liquid carries biomaterial, microfluidic control system, biological micro liquid shifts, and the aspects such as parting material and biosensor are with a wide range of applications.
Claims (5)
1. an adhesive super-hydrophobic material, is characterized in that: this material is a kind of nano SiO 2 particle that contains organic group; This material is attached to matrix surface and forms super hydrophobic surface, contact angle between 150～170 °, its to the adhesive power of water droplet can make water droplet tilt in 90 ° or inverted situation not can landing under;
Using described material as construction unit, on matrix, deposit the surface that obtains having double Nanometer Roughness.
2. according to adhesive super-hydrophobic material described in claim 1, it is characterized in that:
Matrix is sheet glass, silicon chip, metal or metal oxide.
3. according to adhesive super-hydrophobic material described in claim 1, it is characterized in that: described in contain organic group nano SiO 2 particle, organic group is one or more in methyl, ethyl, propyl group, vinyl, phenyl, dodecyl, octadecyl, trifluoro propyl, perfluor decyl and pentafluorophenyl group organic group, and mass content is 0.1～60%; The silica particles of organic decoration is coarse, and particle diameter is 20～1000nm.
4. a preparation method for adhesive type super hydrophobic surface described in claim 1, is characterized in that:
A) inorganic precipitant disperses and precipitation from homogeneous solution in oil phase: tensio-active agent, organic phase, cosurfactant and precipitation agent ammoniacal liquor are proportionally configured to microemulsion A; Tetraethoxy and organosilane are that silicon source or methyl silicate and organosilane are silicon source, wiring solution-forming B; Under room temperature, in A microemulsion, splash into solution B, stir 6～48h;
The mass ratio of the final mixing solutions of gained is 1～10 tensio-active agent: 0.5～6 ammoniacal liquor: 5～15 organic phases: 0～6 cosurfactant: 1 tetraethoxy or methyl silicate: 0.05～1.5 organosilane; Ammonia concn is 1～30wt%;
Add the acetone breakdown of emulsion of 1-10 times of silicon source quality, the centrifugal solid that obtains, adds the alcohol reflux 5～30min of 5-50 times of silicon source quality, centrifugal, repeat 2～5 washings, be dispersed in ethanol, obtain silicon-dioxide alcohol dispersion liquid, silicon-dioxide quality concentration is 1～20wt%;
B) formation of super hydrophobic surface: matrix first cleans with ultrasonic detergent, then water cleans 2～6 times, acetone and clean 2～6 times, and silicon-dioxide alcohol dispersion liquid is deposited on matrix surface, keeps 1～48h at 20～200 DEG C, obtains super hydrophobic surface;
Described organosilane is one or two or more kinds in methyltrimethoxy silane, ethyl trimethoxy silane, propyl trimethoxy silicane, vinyltrimethoxy silane, r-chloropropyl trimethoxyl silane, phenyltrimethoxysila,e, dodecyltrimethoxysilane, octadecyl base Trimethoxy silane, trifluoro propyl Trimethoxy silane, pentafluorophenyl group Trimethoxy silane and corresponding Ethoxysilane thereof.
5. according to preparation method claimed in claim 4, it is characterized in that: described tensio-active agent is C8-20 linear alkylbenzene sulphonic acid or the α-sodium olefin sulfonate in anion surfactant, or be organic primary amine, Np series or the tween series of surfactants of the C8-20 long-chain in nonionogenic tenside, or be the hexadecyl trimethyl ammonium bromide in cats product; Described organic phase is hexanaphthene, normal hexane or toluene; Cosurfactant is propyl carbinol, Pentyl alcohol, n-hexyl alcohol or n-Octanol.
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| CN103803556B (en) * | 2012-11-05 | 2016-03-23 | 中国科学院大连化学物理研究所 | A kind of dewatering nano silicon oxide hollow ball of organic decoration and preparation thereof |
| CN103232835B (en) * | 2013-05-14 | 2014-07-23 | 黑龙江大学 | Method for preparing silica fiber and silica microsphere composite super-hydrophobic material |
| CN104947169B (en) * | 2015-06-19 | 2017-05-17 | 浙江大学 | Preparation method of super-hydrophobic silicon dioxide film |
| CN108072620A (en) * | 2018-02-05 | 2018-05-25 | 西南石油大学 | It is a kind of using optical fiber evanescent field sensor research dyestuff solid-liquid interface adsorption dynamics adsorption kinetics method |
| CN108264678B (en) * | 2018-02-08 | 2021-01-26 | 青岛软盛塑业有限公司 | Hydrophobic bubble film and preparation method thereof |
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