CN101745352A - Superhydrophobic surface material and special nano-particles thereof with core-shell structures - Google Patents
Superhydrophobic surface material and special nano-particles thereof with core-shell structures Download PDFInfo
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- CN101745352A CN101745352A CN200910241856A CN200910241856A CN101745352A CN 101745352 A CN101745352 A CN 101745352A CN 200910241856 A CN200910241856 A CN 200910241856A CN 200910241856 A CN200910241856 A CN 200910241856A CN 101745352 A CN101745352 A CN 101745352A
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Abstract
The invention discloses a superhydrophobic surface material and special nano-particles thereof with core-shell structures. The superhydrophobic material with surface having superhydrophobic performance is prepared by enabling the nano-particles with core-shell structures to form an interface in a certain strength with a substrate under the action of an adhesive, and then, hydrophobically treating the interface. The surface of the superhydrophobic material presents the superhydrophobic property and has a contact angle larger than 150 degrees and a rolling angle smaller than 5 degrees so that water drops on the surface can rapidly roll off. The superhydrophobic surface material provided by the invention has favorable purposes in the field of preparing an antifogging material, a waterproof material, a self-cleaning material, a lubricating drag-reducing material, and the like. The method for preparing the superhydrophobic material has the advantages of simple process and cheap raw materials, thereby being suitable for mass production.
Description
Technical field
The present invention relates to a kind of hydrophobic surface field that the present invention relates to, particularly superhydrophobic surface material and special-purpose nano particle thereof with nucleocapsid structure.
Background technology
Hydrophobic surface is meant and the material surface of water droplet contact angle greater than 90 degree; Super hydrophobic surface is meant with the contact angle of water droplet spends the material surfaces of while roll angles less than 5 degree greater than 150.The main points on constructing super-drainage surface are to construct certain roughness and carry out surface chemical modification.The Jiang Lei researcher of Institute of Chemistry, Academia Sinica in 2002 proposes also to exist nanostructured (Feng L on the mastoid process that the super-hydrophobic basic reason of lotus leaf surface is the lotus leaf surface micrometer structure, Li S H, Li Y S, Li H J, Zhang L J, Zhai J, Song Y L, Liu B Q, Jiang L, Zhu D B. " Super-hydrophobic Surface:From Natural to Artificial ", Adv.Mater.2002 141857).After this mainly concentrate on the control of nanostructured for the research of bionical super hydrophobic material.Main method has: template, photoetch method, sol-gal process, electrochemical method, self-assembly method, metal erosion method, electrical spinning method, solvent-nonsolvent method etc.Yet said method does not have good universality, has very high restrictive condition for material, can't produce on a large scale and use simultaneously.
Summary of the invention
The purpose of this invention is to provide superhydrophobic surface material and special-purpose nano particle thereof with nucleocapsid structure.
The invention provides three kinds of nano particles that are used to prepare superhydrophobic surface material, be respectively compound hollow ball of inorganic matter microcapsules, polyaniline-polystyrene and surperficial inorganic matter hollow microsphere with column structure with nucleocapsid structure with nucleocapsid structure.
The present invention also provides the superhydrophobic surface material that utilizes above-mentioned preparation of nanoparticles with nucleocapsid structure to obtain.
Nano particle with nucleocapsid structure provided by the invention is the inorganic matter microcapsules, is made up of the shell of stratum nucleare and the described stratum nucleare of encirclement; Wherein, the material that constitutes described stratum nucleare is selected from least a in calcium chloride, calcium hydroxide, calcium nitrate, calcium acetate, calcium phosphate, magnesium chloride, magnesium hydroxide, magnesium nitrate, magnesium acetate, magnesium phosphate, barium chloride, barium hydroxide, barium nitrate, barium acetate and the barium phosphate; The material that constitutes described shell is selected from least a in polystyrene, polyethylene, polymethyl methacrylate, polyethyl methacrylate, polypropylene, epoxy resin and the cellulose.
The above-mentioned method of preparation provided by the invention with nano particle-inorganic matter microcapsules of nucleocapsid structure, be to be prepared: the material of the described shell of described formation is added poor solvent and precipitates in organic solvent with behind the material mixing of the described stratum nucleare of described formation, clean described post precipitation and obtain described nano particle-inorganic matter microcapsules with nucleocapsid structure according to the method that comprises the steps.
In this method, described organic solvent is selected from carrene, chloroform, carbon tetrachloride, toluene, dimethylbenzene, pyridine, oxolane, N, dinethylformamide and N, at least a in the N-dimethylacetylamide; Described poor solvent is selected from least a in the alkane that benzinum, ethanol and carbon number are 4-10; The ratio of weight and number of the material of the material of the described shell of described formation, described organic solvent and the described stratum nucleare of described formation is 0.1-3: 1-100: 0.1-10, specifically can be 0.3-3: 10-30: 0.1-1,0.1-0.3: 10-30: 0.1-3,0.1-0.3: 10-30: 1-3,0.1-0.3: 30-100: 3-10 or 0.1-5: 15-50: 1-5, preferred 0.1-0.3: 10-30: 1-3.
The compound hollow ball of nano particle-polyaniline-polystyrene with nucleocapsid structure provided by the invention is made up of the shell of stratum nucleare and the described stratum nucleare of encirclement; Wherein, described stratum nucleare is a hollow; The material that constitutes described shell is the compound of polyaniline and polystyrene, and in this compound, polyaniline combines with physics mode (as physical absorption) with polystyrene.
The above-mentioned method with nano particle-polyaniline-compound hollow ball of polystyrene of nucleocapsid structure of preparation provided by the invention comprises the steps:
1) water, acid, aniline are mixed with the polystyrene hollow microsphere, stir, centrifugal;
2) separator that described step 1) is centrifugal after finishing is scattered in the mixed liquor that water and oxidant form, stirs, obtain described nano particle with nucleocapsid structure.
In the step 1) of this method, described acid is selected from least a in hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the phosphoric acid; The diameter of described polystyrene hollow microsphere is 100nm～100 μ m; The temperature of whipping step is 10-50 ℃, and the time of whipping step is 5 minutes-24 hours; The rotating speed of centrifugation step is 8000～12000 rev/mins, and the time of centrifugation step is 5-20 minute;
Described step 2) in, described oxidant is selected from least a in ferric trichloride, ammonium persulfate, potassium bichromate and the hydrogen peroxide; The temperature of whipping step is 10-50 ℃, and the time of whipping step is 10 minutes-24 hours;
Water in the described step 1), acid, aniline, described polystyrene hollow microsphere, described step 2) in water and described step 2) in the ratio of weight and number of oxidant be 1-30: 0.1-2: 0.1-2: 0.001-1: 10-1000: 0.1-2, specifically can be 10-30: 0.1-1.5: 0.1-1.5: 0.001-0.05: 50-900: 0.1-0.15,5-25: 0.1-1.5: 0.1-0.15: 0.005-0.09: 100-900: 0.1-1.5 or 10-25: 0.15-1.0: 0.15-1.0: 0.005-0.01: 100-500: 0.12-0.18.
Nano particle-surface with nucleocapsid structure provided by the invention has the inorganic matter hollow microsphere of column structure, is made up of the shell of stratum nucleare and the described stratum nucleare of encirclement; Wherein, described stratum nucleare is a hollow; The material that constitutes described shell is selected from a kind of in titanium dioxide, silica, zirconia, tin oxide and the aluminium oxide; The inorganic matter that has column structure at described shell material surface; Described inorganic matter is consistent with the shell material.
Above-mentioned nano particle-the surface with nucleocapsid structure of preparation provided by the invention has the method for the inorganic matter hollow ball of column structure, comprises the steps:
1) the polystyrene hollow microsphere is scattered in the water, centrifugal;
2) separator with described step 1) centrifugation step gained is scattered in the ethanol, and gradation adds the mixed liquor of inorganic matter presoma and ethanol, and is centrifugal, and the organic solution washing with polystyrene obtains described nano particle with nucleocapsid structure.
In the step 1) of this method, the diameter of described polystyrene hollow microsphere is 400nm-100 μ m;
Described step 2) in, described inorganic matter presoma is selected from Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4, Na
2SiO
3, TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4, TiOSO
4, SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4, Sn (OCH
2CH
2CH
2CH
3)
4, ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2}
4, Zr (OCH
2CH
2CH
2CH
3)
4, AlCl
3, Al (OCH
3)
4, Al (OCH
2CH
3)
4, Al{OCH (CH
3)
2}
4, Al (OCH
2CH
2CH
2CH
3)
4And Al
2(SO
4)
3In any one; In the organic solution of described polystyrene, organic solvent is selected from toluene, dimethylbenzene, carrene, chloroform, oxolane, N, dinethylformamide, N, at least a in N-dimethylacetylamide, cyclohexane and the ethyl acetate is as long as the consumption of this organic solvent guarantees polystyrene is dissolved fully; The ratio of weight and number of the mixed liquor of described polystyrene hollow microsphere, described water, described ethanol, each described inorganic matter presoma that adds and ethanol is 0.1-1: 1-20: 5-100: 0.1-2, but concrete 0.1-0.2: 1-5: 20-100: 0.1-0.2,0.2-1: 5-20: 20-100: 0.2-2 or 0.15-0.5: 3-15: 10-50: 0.1-1.5 are preferred: 0.2: 5: 20: 0.2.The rotating speed of described centrifugation step is 5000-15000 rev/min, preferred 12000 rev/mins; The centrifugal time is 2-20 minute, preferred 5 minutes; The number of times that adds described inorganic matter presoma and ethanol is 8-15; In the mixed liquor of described inorganic matter presoma and ethanol, the volume ratio of described inorganic matter presoma and ethanol is 1: 1.
Superhydrophobic surface material provided by the invention is made up of in substrate, adhesive and the aforementioned three kinds of nano particles with nucleocapsid structure provided by the invention any one.
In this material, described substrate is selected from least a in glass, pottery, stone material, metal, alloy and the macromolecular material; Described stone material can be sheet material; Described adhesive is selected from least a in epoxy resin, phenolic resins, acrylate, polyurethane, unsaturated polyester (UP), Lauxite, rubber and the inorganic matter; Wherein, at least a in the preferred iron of described metal, nickel, copper, zinc, aluminium, titanium and the cadmium; In the preferred iron of described alloy, nickel, copper, zinc, aluminium, titanium and the cadmium at least two kinds; Described macromolecular material is at least a in polyethylene, polypropylene, polyvinyl chloride, polyester, polyamide, polyurethane, wool and linen-cotton preferably, can be film, perforated membrane, fiber or porous fibre and fabric thereof.
Preparation provided by the invention is above-mentioned by described substrate, described adhesive and described method with nano particle-described superhydrophobic surface material that the inorganic matter hollow microcapsule is formed of nucleocapsid structure, comprises the steps:
1) with described nano particle-inorganic matter hollow microcapsule and the bonding formation coating of described substrate with nucleocapsid structure;
2) described coating is soaked in stearate or the stearic solution, reaction finishes and obtains described superhydrophobic surface material.
Step 2) in, described stearate is selected from least a in potassium stearate and the odium stearate; Described stearate or stearic mass percentage concentration are 0.1～2%, specifically can be 0.5-2%, 1.0-1.5% or 1.0-2.0%; In described stearate or the stearic solution, solvent is selected from water or water and ethanol with any mixed liquor than mixing; The time of reaction is 1～24 hour, and the temperature of reaction is 5-60 ℃.
Preparation provided by the invention has the method for the described superhydrophobic surface material that the nano particle of the inorganic matter hollow ball of column structure forms by described substrate, described adhesive and the compound hollow ball of polyaniline-polystyrene or surface, comprises the steps:
1) with compound hollow ball of polyaniline-polystyrene or surperficial nano particle and the bonding formation coating of described substrate with inorganic matter hollow ball of column structure;
2) described coating is soaked in the organic solvent of the silane coupler that alkyl replaces, reaction finishes and obtains described superhydrophobic surface material.
The step 2 of this method) in, the silane coupler that described alkyl replaces is selected from (C
2H
5O)
3Si-(CH
2)
nCH
3, (CH
3O)
3Si-(CH
2)
nCH
3And Cl
3Si-(CH
2)
nCH
3In at least a; Described n is the integer of 0-17; The mass percentage concentration of the organic solvent of the silane coupler that described alkyl replaces is 0.1%～10%, specifically can be 0.1-5%, 1-5%, 1-9%, 0.1-9% or 0.1-1%; The temperature of reaction is 10-50 ℃; The time of reaction is 5 minutes～24 hours.
In addition, the application of superhydrophobic surface material provided by the invention in antifog, the waterproof of preparation, automatically cleaning or lubrication drag reduction material also belongs to protection scope of the present invention.
In the above-mentioned method for preparing super hydrophobic material, the bonding method of step 1) can be various methods commonly used, as any one method among following method a, b and the c:
Method a: treat in the described adhesive solvent evaporates fully after, any one powder with nano particle of nucleocapsid structure that the invention described above is provided is covered in the substrate surface that scribbles described adhesive, the thickness of adhesive is 1 micron～1 millimeter, solidifies down at 5 ℃～150 ℃ to get final product;
Method b: the dispersion liquid (mass percentage concentration of described dispersion liquid is 1%～90%) that any one that the invention described above is provided has a nano particle of nucleocapsid structure is applied to substrate with adhesive with immersing the method that lifts coating (rate of extension 0.05～150 cm per minute), spin coating (10～8000 rev/mins of rotary speeies), brushing, spraying or blade coating, solidifies down at 5 ℃～150 ℃ to get final product;
Method c: use method for sizing and fiber or its fabric compound any one dispersion liquid (mass percentage concentration of described dispersion liquid is 1%～90%) that the invention described above provides with nano particle of nucleocapsid structure, starching speed is 0.05～15000 cm per minute), curing gets final product under 5 ℃～150 ℃.
The invention provides the nano particle that a class has nucleocapsid structure, and utilize above-mentioned particle at different base surface construction super hydrophobic surface.This hydrophobic material surface shows super-hydrophobic character, and contact angle is greater than 150 degree, and roll angle is less than 5 degree, and water droplet can tumble rapidly on its surface.Material fields such as superhydrophobic surface material provided by the invention is antifog in preparation, waterproof, automatically cleaning, lubrication drag reduction all have favorable application.The method of the above-mentioned hydrophobic material of preparation provided by the invention, technology is simple, and the used prices of raw and semifnished materials are cheap, are suitable for large-scale production.
Description of drawings
Fig. 1 is the electron scanning micrograph of the calcium hydroxide microcapsules of the embodiment of the invention 1.
Fig. 2 is the electron scanning micrograph of the superhydrophobic surface material that is obtained by the modification of calcium hydroxide microcapsules of the embodiment of the invention 1.
Fig. 3 is the static contact angle photo of the water droplet of the embodiment of the invention 1 at superhydrophobic surface material.
Fig. 4 is the electron scanning micrograph of the polyaniline with the bionical micron-nanometer hierarchical structure-polystyrene complex microsphere of the embodiment of the invention 2.
Fig. 5 is the static contact angle photo of the water droplet of the embodiment of the invention 2 at superhydrophobic surface material.
Fig. 6 is the stereoscan photograph of the polystyrene hollow microsphere with column structure of the embodiment of the invention 3
Fig. 7 is the static contact angle photo of the water droplet of the embodiment of the invention 3 at superhydrophobic surface material.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Embodiment 1
1. the polymethyl methacrylate with 0.5 gram is dissolved in the 20ml carrene, adds the calcium hydroxide of 1.5g, mixes the back and drips the 80ml benzinum.With the products therefrom suction filtration, clean repeatedly 3～4 times with benzinum, promptly obtain the inorganic matter microcapsules.
With ECA with (2000 rev/mins of the methods of spin-coating, 20 seconds) on sheet glass, film, behind room temperature oven dry 30min, the alcohol dispersion liquid of the complex microsphere of the bionical micron-nanometer hierarchical structure of having of step 1 gained is sprayed on the above-mentioned sheet glass, continues to solidify 2 hours in room temperature.
3. the coating that makes in the step 2 is soaked in mass percentage concentration and is in the solution of 1% potassium stearate, reacted 8 hours, the surfacing that can obtain having superhydrophobic property after dry.
The electron scanning micrograph of these inorganic matter microcapsules as shown in Figure 1.The electron scanning micrograph of this superhydrophobic surface material as shown in Figure 2.Water droplet at the static contact angle of this surfacing as shown in Figure 3.Water droplet is 162.1 degree in the static contact angle measured value of this surfacing.Water droplet is 2 degree in the roll angle measured value of this surfacing.
Embodiment 2
1. the polystyrene hollow microsphere aqueous solution (solid content is 27.5%) that with the 100mg diameter is 1 micron is dispersed in the 2mol/L hydrochloric acid solution of 30ml, add the 3.6ml aniline monomer, mix, stirred at ambient temperature 24 hours, the even mixed liquor that obtains centrifugal 5 minutes with 12000 rev/mins speed, the centrifugal separator that obtains is scattered in the FeCl of 0.2mol/L
3In the aqueous solution, at room temperature stirred 24 hours.Centrifugal, the washing of speed with 8000 rev/mins, promptly obtaining diameter is the polyaniline-polystyrene complex microsphere of the bionical micron-nanometer hierarchical structure of 1 micron have.
2. with weight percent concentration the acetone soln of 20% F46 type novolac epoxy resin, select N for use, the N-dimethyl benzylamine is as curing agent, its weight is 10% of described weight epoxy, mixes, with (2000 rev/mins of the methods of spin-coating, 20 seconds) on poly (methyl methacrylate) plate, film, 80 ℃ of oven dry after 20 minutes, the alcohol dispersion liquid of the complex microsphere with micron-nanometer hierarchical structure of step 1 gained is sprayed on the above-mentioned sheet glass, continue to solidify 2 hours at 100 ℃.
3. it is that 1% octadecyl replaces in the hexane solution of trichlorosilane that above-mentioned rough surface with intensity is soaked in mass percentage concentration, at room temperature reacts 4 hours, and with n-hexane flushing twice, alcohol flushing twice promptly obtains superhydrophobic surface material.
This have the micron-nanometer hierarchical structure polyaniline-polystyrene complex microsphere electron scanning micrograph as shown in Figure 4.Water droplet at the static contact angle of this superhydrophobic surface material as shown in Figure 5.
This diameter with polyaniline-polystyrene complex microsphere of micron-nanometer hierarchical structure is 1 micron, and the length of the polyaniline mastoid process of microsphere surface is 30nm.Water droplet is 153.7 degree in the static contact angle measured value of this superhydrophobic surface material.Water droplet is 3 degree in the roll angle measured value of this surfacing.
Embodiment 3
1. the polystyrene hollow microsphere that with the 20mg diameter is 1 micron is dispersed in the water, after 24 hours with emulsion centrifugal 5 minutes with 12000 rev/mins speed, the centrifugal separator that obtains is washed twice with ethanol, be scattered in the ethanol, per hour add the tetrabutyl titanate of 0.2ml and the mixed solution of ethanol (both volume ratios are 1: 1), add altogether 15 times, the mixed liquor that obtains is centrifugal, clean the back repeatedly with ethanol and wash 2～3 times, promptly obtain the titanium dioxide hollow microballoon that the surface has column structure with the toluene solution of polystyrene.
2. with weight percent concentration the acetone soln of 20% bisphenol A type epoxy resin (E51 type), with the triethylene tetramine of weight epoxy 5% as curing agent, mix, with (2000 rev/mins of the methods of spin-coating, 20 seconds) on plastic sheet, film, 60 ℃ of oven dry after 10 minutes, the alcohol dispersion liquid of the polystyrene complex microsphere with column structure of step 1 gained is sprayed on the above-mentioned sheet glass, continue to solidify 2 hours at 80 ℃.
3. it is that 1% octadecyl replaces in the n-decane solution of trichlorosilane that above-mentioned rough surface with intensity is soaked in mass percentage concentration, at room temperature reacts 4 hours, and with n-hexane flushing twice, alcohol flushing twice promptly obtains superhydrophobic surface material.
This superhydrophobic surface material is surperficial titanium dioxide hollow microballoon with column structure, and its electron scanning micrograph as shown in Figure 6.
Embodiment 4
1. the ethyl cellulose with 0.2 gram is dissolved in the 20ml carrene, adds the barium hydroxide of 2g, mixes the back and drips the 80ml benzinum.With the products therefrom suction filtration, clean repeatedly 3～4 times with benzinum, promptly obtain the inorganic matter microcapsules.
2. the dispersion liquid of the nano particle that makes (mass percentage concentration is 5%) is with immersing at the bottom of the method lift coating (rate of extension 0.05 cm per minute) is applied to aluminum plate foundation with ECA, cold curing makes nano particle and substrate form the coating with intensity.
3. the coating that makes in the step 2 is soaked in the solution of 0.5% potassium stearate (ethanol: water, 1: 1), reacted 8 hours, the surfacing that can obtain having superhydrophobic property after dry.Electron scanning micrograph and Fig. 2 of this material do not have substantive difference.Water droplet does not also have substantive difference at the static contact angle measured value and the water droplet of this surfacing in the roll angle measured value of this surfacing and the result of embodiment 1.
Embodiment 5
1. the polystyrene hollow microsphere aqueous solution (solid content is 37.5%) that with the 100mg diameter is 400 nanometers is dispersed in the 2mol/L hydrochloric acid solution of 30ml, add the 3.6ml aniline monomer, mix, stirred at ambient temperature 24 hours, the even mixed liquor that obtains centrifugal 5 minutes with 12000 rev/mins speed, the centrifugal separator that obtains is scattered in the FeCl of 0.2mol/L
3In the aqueous solution, at room temperature stirred 24 hours.Centrifugal, the washing of speed with 8000 rev/mins, promptly obtaining diameter is the polyaniline with the micron-nanometer hierarchical structure-polystyrene complex microsphere of 400 nanometers.
2. fabric face is scribbled the acetone soln that mass percentage concentration is 3% bisphenol A type epoxy resin E51 type, with the triethylene tetramine of weight epoxy 5% as curing agent, 60 ℃ the oven dry 10 minutes after, the alcohol dispersion liquid of the complex microsphere of the bionical micron-nanometer hierarchical structure of having of step 1 gained is sprayed on the above-mentioned fabrics, continue to solidify 2 hours at 80 ℃, make complex microsphere and substrate form coating with intensity.
3. above-mentioned fabrics is soaked in mass percentage concentration and is 1% myristyl and replace in the n-decane solution of trichlorosilane, at room temperature reacted 4 hours, with n-hexane flushing twice, alcohol flushing twice promptly obtains superhydrophobic surface material.
Stereoscan photograph and Fig. 4 of this superhydrophobic surface material do not have substantive difference.Water droplet the static contact angle measured value of this superhydrophobic surface material and water droplet the roll angle measured value of this surfacing all with embodiment 2 no substantive differences.
Claims (16)
1. the nano particle with nucleocapsid structure is made up of the shell of stratum nucleare and the described stratum nucleare of encirclement; It is characterized in that: the material that constitutes described stratum nucleare is selected from least a in calcium chloride, calcium hydroxide, calcium nitrate, calcium acetate, calcium phosphate, magnesium chloride, magnesium hydroxide, magnesium nitrate, magnesium acetate, magnesium phosphate, barium chloride, barium hydroxide, barium nitrate, barium acetate and the barium phosphate; The material that constitutes described shell is selected from least a in polystyrene, polyethylene, polymethyl methacrylate, polyethyl methacrylate, polypropylene, epoxy resin and the cellulose.
2. one kind prepares the described method with nano particle of nucleocapsid structure of claim 1, be to be prepared: the material of the described shell of described formation is added poor solvent and precipitates in organic solvent with behind the material mixing of the described stratum nucleare of described formation, clean described post precipitation and obtain described nano particle with nucleocapsid structure according to the method that comprises the steps.
3. method according to claim 2, it is characterized in that: described organic solvent is selected from carrene, chloroform, carbon tetrachloride, toluene, dimethylbenzene, pyridine, oxolane, N, dinethylformamide and N, at least a in the N-dimethylacetylamide; Described poor solvent is selected from least a in the alkane that benzinum, ethanol and carbon number are 4-10; The ratio of weight and number of the material of the material of the described shell of described formation, described organic solvent and the described stratum nucleare of described formation is 0.1-3: 1-100: 0.1-10, preferred 0.1-0.3: 10-30: 1-3.
4. the nano particle with nucleocapsid structure is made up of the shell of stratum nucleare and the described stratum nucleare of encirclement; It is characterized in that: described stratum nucleare is a hollow; The material that constitutes described shell is the compound of polyaniline and polystyrene.
5. one kind prepares the described method with nano particle of nucleocapsid structure of claim 4, comprises the steps:
1) water, acid, aniline are mixed with the polystyrene hollow microsphere, stir, centrifugal;
2) separator that described step 1) is centrifugal after finishing is scattered in the mixed liquor that water and oxidant form, stirs, obtain described nano particle with nucleocapsid structure.
6. method according to claim 5 is characterized in that: in the described step 1), described acid is selected from least a in hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the phosphoric acid; The diameter of described polystyrene hollow microsphere is 100nm～100 μ m; Described step 2) in, described oxidant is selected from least a in ferric trichloride, ammonium persulfate, potassium bichromate and the hydrogen peroxide; The temperature of whipping step is 10-50 ℃, and the time of whipping step is 5 minutes-24 hours; The rotating speed of centrifugation step is 8000～12000 rev/mins, and the time of centrifugation step is 5-20 minute;
Water in the described step 1), acid, aniline, described polystyrene hollow microsphere, described step 2) in water and described step 2) in the ratio of weight and number of oxidant be 1-30: 0.1-2: 0.1-2: 0.001-1: 10-1000: 0.1-2;
Described step 2) in, the temperature of whipping step is 10-50 ℃, and the time of whipping step is 10 minutes-24 hours.
7. the nano particle with nucleocapsid structure is made up of the shell of stratum nucleare and the described stratum nucleare of encirclement; It is characterized in that: described stratum nucleare is a hollow; The material that constitutes described shell is selected from any one in titanium dioxide, silica, zirconia, tin oxide and the aluminium oxide; The inorganic matter that has column structure at described shell material surface; Constitute material that described shell material surface has the inorganic matter of column structure and be selected from titanium dioxide, silica, zirconia, tin oxide and the aluminium oxide any one.
8. one kind prepares the described method with nano particle of nucleocapsid structure of claim 7, comprises the steps:
1) the polystyrene hollow microsphere is scattered in the water, centrifugal;
2) separator with described step 1) centrifugation step gained is scattered in the ethanol, and gradation adds the mixed liquor of inorganic matter presoma and ethanol, and is centrifugal, and the organic solution washing with polystyrene obtains described nano particle with nucleocapsid structure.
9. method according to claim 8 is characterized in that: in the described step 1), the diameter of described polystyrene hollow microsphere is 400nm-100 μ m;
Described step 2) in, described inorganic matter presoma is selected from Si (OCH
3)
4, Si (OCH
2CH
3)
4, Si{OCH (CH
3)
2}
4, Si (OCH
2CH
2CH
2CH
3)
4, Na
2SiO
3, TiCl
4, Ti (OCH
3)
4, Ti (OCH
2CH
3)
4, Ti{OCH (CH
3)
2}
4, Ti (OCH
2CH
2CH
2CH
3)
4, TiOSO
4, SnCl
4, Sn (OCH
3)
4, Sn (OCH
2CH
3)
4, Sn{OCH (CH
3)
2}
4, Sn (OCH
2CH
2CH
2CH
3)
4, ZrCl
4, Zr (OCH
3)
4, Zr (OCH
2CH
3)
4, Zr{OCH (CH
3)
2}
4, Zr (OCH
2CH
2CH
2CH
3)
4, AlCl
3, Al (OCH
3)
4, Al (OCH
2CH
3)
4, Al{OCH (CH
3)
2}
4, Al (OCH
2CH
2CH
2CH
3)
4And Al
2(SO
4)
3In any one; In the organic solution of described polystyrene, organic solvent is selected from toluene, dimethylbenzene, carrene, chloroform, oxolane, N, dinethylformamide, N, at least a in N-dimethylacetylamide, cyclohexane and the ethyl acetate;
The ratio of weight and number of the mixed liquor of described polystyrene hollow microsphere, described water, described ethanol, each described inorganic matter presoma that adds and ethanol is 0.1-1: 1-20: 5-100: 0.1-2, and is preferred: 0.2: 5: 20: 0.2;
Described step 1) and step 2) in the rotating speed of centrifugation step be 5000-15000 rev/min, preferred 12000 rev/mins; The centrifugal time is 2-20 minute, preferred 5 minutes; The number of times that adds described inorganic matter presoma and ethanol is 8-15; In the mixed liquor of described inorganic matter presoma and ethanol, the volume ratio of described inorganic matter presoma and ethanol is 1: 1.
10. a superhydrophobic surface material is made up of arbitrary described nano particle with nucleocapsid structure in substrate, adhesive and the claim 1,4 and 7.
11. material according to claim 10 is characterized in that: described substrate is selected from least a in glass, pottery, stone material, metal, alloy and the macromolecular material; Described adhesive is selected from least a in epoxy resin, phenolic resins, acrylate, polyurethane, unsaturated polyester (UP), Lauxite, rubber and the inorganic matter; Wherein, at least a in the preferred iron of described metal, nickel, copper, zinc, aluminium, titanium and the cadmium; In the preferred iron of described alloy, nickel, copper, zinc, aluminium, titanium and the cadmium at least two kinds; Described macromolecular material is at least a in polyethylene, polypropylene, polyvinyl chloride, polyester, polyamide, polyurethane, wool and linen-cotton preferably.
12. one kind prepares in claim 10 and 11 by the described method with described superhydrophobic surface material of the nano particle that nucleocapsid structure forms of described substrate, described adhesive and claim 1, comprises the steps:
1) with described nano particle and the bonding formation coating of described substrate of claim 1 with nucleocapsid structure;
2) described coating is soaked in stearate or the stearic solution, reaction finishes and obtains in claim 10 and 11 by the described described superhydrophobic surface material with nano particle that nucleocapsid structure forms of described substrate, described adhesive and claim 1.
13. method according to claim 12 is characterized in that: described step 2), described stearate is selected from least a in potassium stearate and the odium stearate; Described stearate or stearic mass percentage concentration are 0.1%～2%; In described stearate or the stearic solution, solvent is selected from water or water and ethanol with any mixed liquor than mixing; The time of reaction is 1～24 hour, and the temperature of reaction is 5-60 ℃.
14. one kind prepares in claim 10 and 11 by described substrate, described adhesive and claim 4 or 7 described methods with described superhydrophobic surface material of the nano particle that nucleocapsid structure forms, comprises the steps:
1) with claim 4 or 7 described nano particle and the bonding formation coating of described substrate with nucleocapsid structure;
2) described coating is soaked in the organic solvent of the silane coupler that alkyl replaces, reaction finishes and obtains in claim 10 and 11 by described substrate, described adhesive and claim 4 or 7 described described superhydrophobic surface materials with nano particle that nucleocapsid structure forms.
15. method according to claim 14 is characterized in that: described step 2), the silane coupler that described alkyl replaces is selected from (C
2H
5O)
3Si-(CH
2)
nCH
3, (CH
3O)
3Si-(CH
2)
nCH
3And Cl
3Si-(CH
2)
nCH
3In at least a; Described n is the integer of 0-17; The mass percentage concentration of the organic solvent of the silane coupler that described alkyl replaces is 0.1%～10%; The temperature of reaction is 10-50 ℃; The time of reaction is 5 minutes～24 hours.
16. claim 10 or the 11 described superhydrophobic surface materials application in antifog, the waterproof of preparation, automatically cleaning or lubrication drag reduction material.
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