CN107858046B - A kind of superhydrophobic coating with self-cleaning and antibacterial function and preparation method thereof - Google Patents
A kind of superhydrophobic coating with self-cleaning and antibacterial function and preparation method thereof Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
本发明属于超疏水涂层制备技术领域，具体涉及一种具有自清洁和抗菌功能的超疏水涂层及其制备方法。利用聚偏氟乙烯的有机溶液和小分子量醇制备PVDF固态悬浮液A，然后在悬浮液A中加入ZIF纳米颗粒，之后再加入低表面能的氟化物获得超疏水涂层溶液；将超疏水涂层溶液涂覆在基底上，制备获得具有自清洁和抗菌功能的超疏水涂层。本发明提供了一种具有自清洁和抗菌功能的超疏水涂层，制备工艺简单,反应条件温和,可适用于多种不同的基底和大规模生产，热稳定性和化学稳定性好。超疏水涂层不仅对表面污染物具有自清洁功能，同时也可以杀死涂层表面的细菌，阻止生物膜的形成，在自清洁和抗菌领域具有极大的潜在应用价值。The invention belongs to the technical field of preparation of super-hydrophobic coatings, in particular to a super-hydrophobic coating with self-cleaning and antibacterial functions and a preparation method thereof. The PVDF solid suspension A was prepared by using an organic solution of polyvinylidene fluoride and a small molecular weight alcohol, and then ZIF nanoparticles were added to the suspension A, and then a low surface energy fluoride was added to obtain a superhydrophobic coating solution; The layer solution was coated on the substrate to prepare a superhydrophobic coating with self-cleaning and antibacterial functions. The invention provides a super-hydrophobic coating with self-cleaning and antibacterial functions, the preparation process is simple, the reaction conditions are mild, the coating can be applied to a variety of different substrates and large-scale production, and the thermal stability and chemical stability are good. The superhydrophobic coating not only has the self-cleaning function of surface pollutants, but also can kill the bacteria on the coating surface and prevent the formation of biofilm, which has great potential application value in the field of self-cleaning and antibacterial.
Description
Technical Field
The invention belongs to the technical field of super-hydrophobic coating preparation, and particularly relates to a super-hydrophobic coating with self-cleaning and antibacterial functions and a preparation method thereof.
Background
The research of the bionic super-hydrophobic surface is a new field in the research of a chemical simulation biological system. It is very common in nature that animals and plants achieve a self-cleaning function by forming a super-hydrophobic surface, such as lotus leaves, bird feathers, water strider legs, butterfly wings, and the like. The most typical example is a lotus leaf surface which is sludge but not stained, has an extremely strong self-cleaning capability and is called lotus leaf effect (lotus effect). The lotus leaf surface is composed of a plurality of mastoids, and the average diameter of the mastoids is 5-9 μm. The contact and rolling angles of water on the surface were 161.0 ± 2.7 ° and 2 °, respectively. Each papilla is composed of nanostructured branches with an average diameter of 124.3 ± 3.2 nm. The nano structure is also present on the surface of the lower layer of the lotus leaf, which can effectively prevent the lower layer of the lotus leaf from being wetted. These nanostructures, especially those on the micro-mastoid, play an important role in superhydrophobicity, and the self-cleaning feature is caused by both the micro-nanostructured mastoid on the rough surface and the presence of surface wax. The super-hydrophobic phenomenon of the lotus leaf surface provides a practical basis for preparing the bionic super-hydrophobic surface. The bionic super-hydrophobic surface material has a special micro-nano structure, so that a series of excellent performances such as self-cleaning and pollution prevention are shown.
Under the inspired of super-hydrophobic tissues and organs in nature such as lotus leaves, water strider legs, butterfly wings and the like, the design and research and development of the bionic super-hydrophobic surface material aim at simulating a biological functional structure, and more importantly, the preparation of the super-hydrophobic surface with adjustable components and structures is adopted, so that a new material which has hydrophobic self-cleaning property, high strength, heat resistance, acid and alkali resistance and the like and is excellent is obtained. The material has wide application prospect in national defense, industry, agriculture, medicine and daily life.
The wettability of a solid surface is determined by its chemical composition and microscopic geometry. It is well known that wetting properties are mainly influenced by the chemical composition of the surface of the solid, which is more easily wetted by some liquids and vice versa, the greater the free energy of the solid surface. The preparation of super-hydrophobic surfaces often requires the surface to be covered with fluorocarbon chains or silane chains to reduce the surface energy. However, the surface free energy is adjusted chemically by polishing on smooth surfaces, and usually the contact angle is only increased to 120 ° and not higher. To achieve higher contact angles, the surface microstructure of the material must be designed, and a surface with a fine roughness structure (relatively smaller than the micron scale of the liquid droplet) will effectively improve the hydrophobic (hydrophilic) properties of the hydrophobic (hydrophilic) surface.
Polyvinylidene fluoride is a novel fluorocarbon thermoplastic resin, has excellent processability, mechanical strength, thermal stability and chemical stability, and has a low surface energy, and thus is widely used as a super-hydrophobic material. Superhydrophobic surfaces can prevent the adhesion of liquid and solid particles, but are susceptible to contamination by organics and microorganisms in the water. Much research has focused on the self-cleaning properties of these surfaces, but research into antimicrobial properties has been neglected. Therefore, the super-hydrophobic coating with the self-cleaning function and the antibacterial function has higher use value.
Disclosure of Invention
The invention aims to provide a super-hydrophobic coating with self-cleaning and antibacterial functions and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of a super-hydrophobic coating with self-cleaning and antibacterial functions comprises the steps of preparing a PVDF solid suspension A by utilizing an organic solution of polyvinylidene fluoride and low molecular weight alcohol, adding ZIF nano particles into the suspension A, and then adding low-surface-energy fluoride to obtain a super-hydrophobic coating solution; and coating the super-hydrophobic coating solution on a substrate to prepare the super-hydrophobic coating with self-cleaning and antibacterial functions.
Wherein the mass concentration of the polyvinylidene fluoride organic solution is 2-5%, and the mass ratio of the polyvinylidene fluoride organic solution to the small-component alcohol is 1: 9; the adding amount of the ZIF nano particles is 0.3-1.0% of the mass of the suspension A, and the adding amount of the low-surface-energy fluoride is 0.5-1.5% of the mass of the suspension A.
The solvent of the organic solution of polyvinylidene fluoride is preferably any one of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone.
The low molecular weight alcohol is preferably any one of methanol, ethanol, ethylene glycol, propanol, isopropanol, propylene glycol, glycerol, butanol or pentanol.
The ZIF nanoparticles are preferably selected from any one of ZIF-8, ZIF-67 and ZIF-7.
The preparation of ZIF nanoparticles is preferably, but not limited to, performed as follows: dissolving metal salt in an X1 solvent, dissolving an organic ligand in an X2 solvent, mixing and stirring the two to prepare a ZIF particle suspension, and centrifuging, washing, drying and grinding to prepare the ZIF nano-particles.
The fluoride having a low surface energy is preferably any one of heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, dodecafluoroheptylpropyltrimethoxysilane, nonafluorohexyltrimethoxysilane, nonafluorohexyltriethoxysilane, and pentafluorophenyl-triethoxysilane.
The substrate is preferably any one of non-woven fabrics, cotton cloth, filter paper, nylon cloth, commercial polyacrylonitrile films or polystyrene films.
Specifically, the preparation process of the super-hydrophobic coating solution is as follows: dropwise adding a polyvinylidene fluoride (PVDF) solution into low molecular weight alcohol, fully mixing for 10-20 min, and then carrying out ultrasonic treatment for 20-40 min to prepare a micron-sized PVDF solid suspension A; adding ZIF nano particles into the suspension A, fully mixing for 10-20 min, and then carrying out ultrasonic treatment for 30-60 min; and finally, adding low-surface-energy fluoride, and stirring for 10-12h to obtain the super-hydrophobic coating solution.
When the super-hydrophobic coating solution is coated on the substrate, any one of dipping, spin coating, spray coating, and drop coating may be employed.
The substrate treated by the super-hydrophobic coating solution can be dried by heating at 50-100 ℃ and can also be naturally dried.
Specifically, the invention relates to a preparation method of a super-hydrophobic coating with self-cleaning and antibacterial functions, which comprises the following steps:
(1) preparation of ZIF nanoparticles: dissolving metal salt in a solvent X1, dissolving an organic ligand in a solvent X2, mixing and stirring the two to obtain a ZIF particle suspension, and centrifuging, washing, drying and grinding to obtain ZIF powder;
(2) preparation of super-hydrophobic coating solution: and (2) dropwise adding a polyvinylidene fluoride (PVDF) solution with the mass fraction of 2-5% into the low-molecular-weight alcohol, wherein the mass ratio of the PVDF solution to the low-molecular-weight alcohol is 1: 9. Violently stirring for 10-20 min, and then carrying out ultrasonic treatment for 20-40 min to prepare micron-sized PVDF solid suspension; adding 0.3-1.0% by mass of ZIF nanoparticles into the suspension, vigorously stirring for 10-20 min, carrying out ultrasonic treatment for 30-60 min, finally adding 0.5-1.5% by mass of fluoride with low surface energy, and carrying out magnetic stirring for 12h to obtain a super-hydrophobic coating solution;
(3) preparing a super-hydrophobic coating: the coating solution is coated on a substrate by a deposition technology, and the super-hydrophobic coating with self-cleaning and antibacterial functions can be prepared by a heating evaporation or natural volatilization method.
Among a plurality of antibacterial materials, the Zeolite Imidazole Framework (ZIF) is an important organic-inorganic mixed crystal porous material and has the advantages of large surface area, high crystallinity, large pore volume, adjustable pore size, thermal stability, chemical stability and the like. The preparation method is already the prior art and is not described in detail here.
The ZIF nano particles have excellent thermal stability and chemical stability, can exist in a solution relatively stably, and gradually and slowly release metal ions and organic ligands with antibacterial effect, so that the aim of long-term continuous antibacterial can be fulfilled. According to the invention, the super-hydrophobic coating is prepared based on ZIF nanoparticles, the surface of the super-hydrophobic coating has a micro-nano composite structure, 2 microliter of water is dripped on the surface of the coating, the contact angle is 159-166 degrees, and the rolling angle is less than 5 degrees, so that the super-hydrophobic coating has excellent self-cleaning capability due to the extremely high static contact angle and the small rolling angle. In addition, compared with Ag particles and TiO which are widely used2The particles and ZIF nanoparticles have excellent antibacterial effect and relatively low production cost, can realize the antibacterial function under the normal temperature condition, and do not need additional conditions such as ultraviolet and the like. As a novel multifunctional super-hydrophobic coating, the coating is expected to be widely applied in the fields of self-cleaning and antibiosis, and the bacteriostatic rate of the coating can basically reach 100%.
In the preparation of the superhydrophobic coating, a solution of polyvinylidene fluoride (PVDF) is added to a low molecular weight alcohol to perform a phase inversion process, followed by sonication to prepare PVDF colloidal suspension particles. And then adding ZIF nano particles into the system, preparing PVDF/ZIF-8 composite colloid suspension particles through ultrasonic and stirring treatment, and modifying by using fluoride to obtain the super-hydrophobic antibacterial feeding solution. The coating solution can be coated on different substrates by methods of drop coating, dip coating, spray coating and the like. The prepared coating surface not only has a rough micro-nano structure but also has lower surface energy, so that the coating has excellent super-hydrophobic property and shows excellent self-cleaning function and antibacterial function.
Compared with the prior art, the invention has the following advantages:
the super-hydrophobic coating with the self-cleaning and antibacterial functions has the advantages of simple preparation process, mild reaction conditions, suitability for various different substrates and large-scale production, and good thermal stability and chemical stability. The super-hydrophobic coating not only has a self-cleaning function on surface pollutants, but also can kill bacteria on the surface of the coating, prevent the formation of a biological film, and has great potential application value in the fields of self-cleaning and antibiosis.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of the superhydrophobic coating in example 1;
FIG. 2 is an atomic force microscope image of the surface of the superhydrophobic coating in example 1;
FIG. 3 is a static photograph of drops of water in example 1 dropped on a substrate coated with a superhydrophobic coating solution, the substrate being (a) a PAN film, (b) a fabric, (c) a filter paper, (d) a nonwoven fabric, respectively;
fig. 4 is a water droplet in example 1 dropped on a PAN film substrate sprinkled with activated carbon powder and having a super-hydrophobic coating;
FIG. 5 is a water drop of example 1 on a blank substrate sprinkled with activated carbon powder;
FIG. 6 is a graph showing the antibacterial effect of a blank control of the antibacterial test in example 1;
fig. 7 is a graph showing the antibacterial effect of the superhydrophobic coating in example 1.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
A super-hydrophobic coating with self-cleaning and antibacterial functions is prepared by the following steps:
1) synthesizing ZIF-8 nano-particles in an aqueous solution by using triethylamine as a guiding agent: 0.733g of Zn (NO) was taken3)2·6H2O was dissolved in 100mL of deionized water, 3.244g of 2-methylimidazole (Hmim) and 4g of Triethylamine (TEA) were dissolved in another 100mL portion of deionized water, and an aqueous solution of zinc nitrate was rapidly added to the stirred solution of Hmim and TEA at room temperature and stirring was continued for 10 min. The precipitate was then collected by centrifugation at 8000rpm for 10min and washed with deionized water, repeated three times. The obtained ZIF-8 nanoparticles were vacuum dried at 40 ℃ for 24h and then ground for future use.
2) Preparing a super-hydrophobic coating solution: first, 3g of PVDF was added to 97g N, N-dimethylacetamide and stirred for 2h to form a clear solution of PVDF. Secondly, 10g of PVDF solution is mixed with 90g of ethanol, the mixture is stirred vigorously for 20min, and then the mixture is treated ultrasonically for 30min to obtain a solid suspension of PVDF. Dispersing 0.5g of ZIF-8 nano particles in the system, performing ultrasonic treatment for 10min, finally adding 1.0g of tridecafluorooctyltriethoxysilane into the mixture, and performing magnetic stirring for 12h to obtain a super-hydrophobic coating solution;
3) preparing a super-hydrophobic coating: a Polyacrylonitrile (PAN) commercial ultrafiltration membrane is used as a substrate of a model substrate, a PAN membrane is fixed in a module, and the area of the surface of the PAN membrane which can be coated by a solution is 28.26cm2. 1mL of the superhydrophobic coating solution was dropped on the surface of the film by the dropping method, and then the film was put into an oven to be dried at 50 ℃ for 1h to evaporate the solvent, and in order to remove surface defects of the superhydrophobic coating, the coating was repeated once, and again dried at 50 ℃ for 1h to evaporate the solvent. Thereby preparing the ZIF-8 nano-particles based super-hydrophobic coating with self-cleaning and antibacterial functions.
The superhydrophobic coating solution can also be coated on the surface of filter paper, non-woven fabric, or textile, as in the following examples.
Detecting the self-cleaning function of the super-hydrophobic coating:
and (3) sticking the PAN film which is processed by the super-hydrophobic coating solution and is formed with the super-hydrophobic coating in the step 3) on a flat plate, then inclining the flat plate by about 10 degrees, and scattering activated carbon powder on the surface of the coating. Water was slowly dropped from above the film surface and the self-cleaning effect of the coating was observed. The microscopic morphology of the surface of the sample is observed by using a field emission scanning electron microscope (FESEM, FEI, Quanta250FEG) with magnification of 60000 times, and as shown in figure 1, the micro-nano structure is successfully constructed on the surface of the coating due to the combined action of the micron PVDF particles and the nano ZIF-8 particles. The surface roughness was observed by an atomic force microscope (AFM, Bruker Dimension Fastscan, USA), and as shown in fig. 2, the root mean square deviation Rq of the surface profile of the superhydrophobic coating was 207nm, demonstrating that the surface of the coating had a large roughness.
A contact angle measuring instrument is adopted to measure the contact angle of the surface of the prepared super-hydrophobic coating, as shown in figure 3, the contact angle of water drops of the polyacrylonitrile commercial ultrafiltration membrane, the filter paper, the non-woven fabric and the textile subjected to super-hydrophobic treatment is as high as 159-166 degrees, and the rolling angles are all smaller than 5 degrees. Due to the high contact angle and the small rolling angle, the coating has a good self-cleaning function, and water drops can easily roll off the surface quickly to take away pollutants on the surface as shown in figure 4. Whereas untreated base films do not have a self-cleaning function, as shown in fig. 5, water droplets adhere to the surface of the base film.
And (3) detecting the antibacterial activity of the super-hydrophobic coating:
coli stock (200uL) was added to a tube containing sterile Luria-Bertani (LB) broth (10mL) and then cultured at 37 ℃ in an incubator at 170rpm for 4 h. 10cm of each sample (blank and coating obtained in step 3)2The suspension system was aspirated from the tube after being cut into strips and dipped into tubes containing cultured E.coli broth (100uL) and sterile physiological saline solution (10mL) and incubated at 37 ℃ for 2h at 170rpm, and then a series of ten-fold dilutions were made with sterile saline solution. Finally, 100uL of the diluted solution was spread on agar medium and incubated at 37 ℃ for 12h, and bacterial colonies were counted for each sample. Three groups of antibacterial experiments were performed simultaneously for each sample, and the average value was used as the experimental result. The calculation of the bacterial inhibition rate is disclosed as follows:
wherein R is the bacteriostasis rate, and M and N are the colony numbers on the culture mediums of a blank control group and an experimental investigation group respectively. In the case of surface colonies in the blank control group, as shown in FIG. 6, a large number of colonies appeared on the surface of the medium. The bacteriostatic effect of the super-hydrophobic coating is shown in fig. 7, the number of colonies on the surface of the culture medium is 0, and the bacteriostatic rate reaches 100%.
Example 2
A super-hydrophobic coating with self-cleaning and antibacterial functions is prepared by the following steps:
1) synthesizing ZIF-8 nano-particles in an aqueous solution by using triethylamine as a guiding agent: the same as example 1;
2) preparing a super-hydrophobic coating solution: first, 3g of PVDF was added to 97g N, N-dimethylformamide and stirred for 2h to form a clear solution of PVDF. Next, 10g of the PVDF solution was mixed with 90g of ethanol, vigorously stirred for 20min, and then the mixture was sonicated for 30min to give a solid suspension of PVDF. Dispersing 0.5g of ZIF-8 nano particles in the system, performing ultrasonic treatment for 10min, finally adding 1.0g of tridecafluorooctyltriethoxysilane into the mixture, and performing magnetic stirring for 12h to obtain a super-hydrophobic coating solution;
3) preparing a super-hydrophobic coating: the PAN film was used as a substrate (the same applies to the following), and the other examples were the same as example 1.
Carrying out self-cleaning function detection and antibacterial activity detection on the super-hydrophobic coating according to the method of the embodiment 1, wherein the contact angle is 163 degrees, and the rolling angle is 3 degrees; the bacteriostasis rate is 100 percent.
Example 3
A super-hydrophobic coating with self-cleaning and antibacterial functions is prepared by the following steps:
1) synthesizing ZIF-8 nano-particles in an aqueous solution by using triethylamine as a guiding agent: the resulting ZIF-8 nanoparticles were vacuum dried at 50 ℃ for 24h and then ground for use, otherwise as in example 1.
2) Preparing a super-hydrophobic coating solution: first, 3g of PVDF was added to 97g N-methylpyrrolidone and stirred for 2h to form a clear solution of PVDF. Next, 10g of the PVDF solution was mixed with 90g of ethanol, vigorously stirred for 30min, and then the mixture was sonicated for 30min to obtain a solid suspension of PVDF. Dispersing 0.5g of ZIF-8 nano particles in the system, performing ultrasonic treatment for 10min, finally adding 1.0g of tridecafluorooctyltriethoxysilane into the mixture, and performing magnetic stirring for 12h to obtain a super-hydrophobic coating solution;
3) preparing a super-hydrophobic coating: the same as in example 1.
Carrying out self-cleaning function detection and antibacterial activity detection on the super-hydrophobic coating according to the method of the embodiment 1, wherein the contact angle is 165 degrees, and the rolling angle is 2 degrees; the bacteriostasis rate is 100 percent.
Example 4
A super-hydrophobic coating with self-cleaning and antibacterial functions is prepared by the following steps:
1) synthesizing ZIF-8 nano-particles in an aqueous solution by using triethylamine as a guiding agent: the same as example 1;
2) preparing a super-hydrophobic coating solution: first, 3g of PVDF was added to 97g N, N-dimethylacetamide and stirred for 2h to form a clear solution of PVDF. Next, 10g of the PVDF solution was mixed with 90g of methanol, vigorously stirred for 20min, and then the mixture was sonicated for 30min to give a solid suspension of PVDF. Dispersing 0.5g of ZIF-8 nano particles in the system, performing ultrasonic treatment for 10min, finally adding 1.0g of tridecafluorooctyltriethoxysilane into the mixture, and performing magnetic stirring for 12h to obtain a super-hydrophobic coating solution;
3) preparing a super-hydrophobic coating: the same as in example 1.
Carrying out self-cleaning function detection and antibacterial activity detection on the super-hydrophobic coating according to the method of the embodiment 1, wherein the contact angle is 164 degrees, and the rolling angle is 2 degrees; the bacteriostasis rate is 100 percent.
Example 5
A super-hydrophobic coating with self-cleaning and antibacterial functions is prepared by the following steps:
1) synthesis of ZIF-8 nanoparticles in methanol solution: 1.465g of Zn (NO) are taken3)2·6H2Dissolving O in 100mL of methanol, dissolving 3.245g of 2-methylimidazole (Hmim) in another 100mL of methanol, then quickly adding a zinc nitrate/methanol solution into the stirred Hmim/methanol solution, slowly making the solution become turbid, continuously reacting for 1 hour at room temperature, centrifuging, taking a precipitate, washing for three times with the methanol solution, then drying in a vacuum drying oven at 50 ℃, and grinding for later use;
2) preparing a super-hydrophobic coating solution: first, 3g of PVDF was added to 97g N, N-dimethylacetamide and stirred for 2h to form a clear solution of PVDF. Next, 10g of the PVDF solution was mixed with 90g of methanol, vigorously stirred for 20min, and then the mixture was sonicated for 30min to give a solid suspension of PVDF. Dispersing 0.5g of ZIF-8 nano particles in the system, performing ultrasonic treatment for 10min, finally adding 1.0g of tridecafluorooctyltriethoxysilane into the mixture, and performing magnetic stirring for 12h to obtain a super-hydrophobic coating solution;
3) preparing a super-hydrophobic coating: the same as in example 1.
Carrying out self-cleaning function detection and antibacterial activity detection on the super-hydrophobic coating according to the method of the embodiment 1, wherein the contact angle is 162 degrees, and the rolling angle is 4 degrees; the bacteriostasis rate is 100 percent.
Example 6
A super-hydrophobic coating with self-cleaning and antibacterial functions is prepared by the following steps:
1) preparing ZIF-67 nanoparticles: taking 1.8g of Co (NO)3)2·6H2O was dissolved in 12mL of deionized water, and 22g of 2-methylimidazole was dissolved in 80mL of deionized water. I.e. n (Co (NO)3)2·6H2O n (2-methylimidazole) n (water) 1: 58. The two solutions were mixed and stirred at ambient temperature for 6h, then the solid ZIF-67 was collected by centrifugation and washed 3 times with deionized water. And finally, drying the prepared precipitate for 24 hours in vacuum at the temperature of 80 ℃ to obtain ZIF-67 nano particles.
2) Preparing a super-hydrophobic coating solution: first, 3g of PVDF was added to 97g N, N-dimethylacetamide and stirred for 2h to form a clear solution of PVDF. Next, 10g of the PVDF solution was mixed with 90g of methanol, vigorously stirred for 20min, and then the mixture was sonicated for 30min to give a solid suspension of PVDF. Dispersing 0.4g of ZIF-67 nanoparticles in the system, performing ultrasonic treatment for 10min, finally adding 1.0g of tridecafluorooctyltriethoxysilane into the mixture, and performing magnetic stirring for 12h to obtain a super-hydrophobic coating solution;
3) preparing a super-hydrophobic coating: the same as in example 1.
Carrying out self-cleaning function detection and antibacterial activity detection on the super-hydrophobic coating according to the method of the embodiment 1, wherein the contact angle is 166 degrees, and the rolling angle is 3 degrees; the bacteriostasis rate is 100 percent.
Example 7
A super-hydrophobic coating with self-cleaning and antibacterial functions is prepared by the following steps:
1) preparing ZIF-7 nanoparticles: 0.453g of Zn (NO)3)2·6H2O and 1.154g of benzimidazole were added to 150ml of N-dimethylformamide and stirred at room temperature for 23 hours. The product is then centrifuged and washed with methanolWashed three times. Dispersing the obtained precipitate in methanol, stirring for 24h, then centrifuging, and vacuum drying the precipitate at 50 ℃ for 24h to obtain ZIF-7 nanoparticles, because N, N-dimethylformamide is relatively difficult to remove;
2) preparing a super-hydrophobic coating solution: first, 3g of PVDF was added to 97g of DMAC and stirred for 2h to form a clear solution of PVDF. Next, 10g of the PVDF solution was mixed with 90g of methanol, vigorously stirred for 20min, and then the mixture was sonicated for 30min to give a solid suspension of PVDF. Dispersing 0.5g of ZIF-7 nano particles in the system, performing ultrasonic treatment for 10min, finally adding 1.0g of tridecafluorooctyltriethoxysilane into the mixture, and performing magnetic stirring for 12h to obtain a super-hydrophobic coating solution;
3) preparing a super-hydrophobic coating: the same as in example 1.
Carrying out self-cleaning function detection and antibacterial activity detection on the super-hydrophobic coating according to the method of the embodiment 1, wherein the contact angle is 163 degrees, and the rolling angle is 5 degrees; the bacteriostasis rate is 100 percent.
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| CN102179188B (en) * | 2011-03-24 | 2013-04-10 | 北京工业大学 | Super hydrophobic modification method for polyvinylidene fluoride hydrophobic membranes |
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