CN109468874B - Super-hydrophobic transparent conductive paper and preparation method thereof - Google Patents
Super-hydrophobic transparent conductive paper and preparation method thereof Download PDFInfo
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- CN109468874B CN109468874B CN201811282393.4A CN201811282393A CN109468874B CN 109468874 B CN109468874 B CN 109468874B CN 201811282393 A CN201811282393 A CN 201811282393A CN 109468874 B CN109468874 B CN 109468874B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/50—Spraying or projecting
Abstract
The invention relates to super-hydrophobic transparent conductive paper and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing nano silicon dioxide particles; (2) preparing a hydroxylated carbon nanotube; (3) uniformly mixing nano silicon dioxide particles with the hydroxylated carbon nano tubes, and performing super-hydrophobic modification on the nano silicon dioxide particles; (4) preparing transparent paper; (5) and (4) coating the mixture prepared in the step (3) on transparent paper, and drying at normal temperature to obtain the super-hydrophobic transparent conductive paper. The invention has the advantages that: as a novel composite material, the super-hydrophobic transparent conductive paper has good hydrophobic property, so that the performance is more stable; the prepared transparent paper has high strength and good conductivity, and plays an important role in actual life and production; the method has the advantages of simple process flow, easy operation, low cost, high production efficiency and easy realization of industrial production.
Description
Technical Field
The invention relates to super-hydrophobic paper and a preparation method thereof, in particular to super-hydrophobic transparent conductive paper and a preparation method thereof.
Background
The nano silicon dioxide is semitransparent and is white, nontoxic and amorphous fine powder. It has the following characteristics: the material has the advantages of porosity, large specific surface area, high dispersibility, light weight, good chemical stability, high temperature resistance, non-combustion, thixotropy, extinction property, hydrophilicity, insulativity and the like. In the paper industry, the whiteness, strength and abrasion resistance of paper can be effectively improved; in the pesticide industry, the nano silicon dioxide can be used as an anti-caking agent and a dispersing agent, and the high-grade nano silicon dioxide can also be used as a toothpaste friction agent and a medicament excipient dispersing agent; as a delustering agent, the nano silicon dioxide can partially replace expensive titanium dioxide in the fields of paint, printing ink, cosmetics, coating and the like. Because the polysiloxane in the nano silicon dioxide, the active silanol group on the outer surface and the adsorbed water, the nano silicon dioxide is hydrophilic and is difficult to wet and disperse in an organic phase. In addition, due to the existence of hydroxyl on the surface, the surface energy is large, the aggregate always tends to agglomerate, and the application performance of the product is affected, so that the superhydrophobic modification of the surface of the nano-silica particle is needed.
In natural environment, a great deal of super-hydrophobic phenomena exist, such as leaves of certain plants, wings of butterflies, opposite feet of insects and the like, the most typical super-hydrophobic phenomenon in human life is lotus leaf effect, and the lotus leaf effect endows the lotus leaf with excellent self-cleaning capability, and the super-hydrophobic phenomenon is widely concerned by people due to the excellent performance. The superhydrophobic phenomenon generally refers to a phenomenon in which a contact angle is 150 ° or more and a rolling angle is less than 10 ° or less when a water droplet is dropped on a surface of a sample. A true super-hydrophobic surface has both a large static contact angle and a small rolling angle. Due to the surface structure characteristics of the lotus leaf effect, one derives two conditions required to prepare a superhydrophobic surface: (1) constructing a micro-nano dual coarse structure on the surface of the material; (2) and (3) carrying out low surface energy substance modification on the surface of the micro-nano double coarse structure. Such as sol-gel, laser or chemical etching, solvent evaporation, templating, sublimation, and polymer curing and shaping. Deep research on the super-hydrophobic surface structure has important significance for understanding the super-hydrophobic phenomenon in nature and designing novel and practical super-hydrophobic materials. Meanwhile, the super-hydrophobic material has wide application prospect in industrial production and daily life of people.
Because the paper has the properties of reproducibility, environmental protection, lightness, mechanical flexibility, disposability and the like, but simultaneously has some defects: the paper has good electrical insulation and general mechanical strength, because the paper contains hydrophilic functional groups, the paper has very good hygroscopicity, the paper is wetted and expanded, and the surface of the paper is easily stained by the external environment and is not easy to clean; when compounded with other compounds, the mechanical properties of the material can be reduced, and the service life of the material can be affected. Therefore, the paper is expected to be widely applied in more fields, especially in microelectronic products, batteries and other energy sources, even in the field of solar energy. (1) The paper must have good hydrophobic properties. The existence of the super-hydrophobic surface of the paper enables the moisture of the paper material not to be changed easily due to the change of the external environment, so that the performance is more stable, and the super-hydrophobic surface has the unique self-cleaning function and enables the surface of the plant fiber to have the characteristics of dirt resistance and dirt resistance. (2) In order to apply the paper fiber in the energy fields of microelectronics, electric conduction and the like, the paper must have higher electric conductivity. Therefore, the paper material must be combined with some conductive substances, such as metals, carbon nanotubes, graphene, semiconductors, and organic conductive polymers, in a certain stable form, so that the paper material has higher conductivity.
Transparent Conductive Electrodes (TCEs) play an important role in the production and performance of thin film optoelectronic devices. An ideal TCE must have high transparency for maximum absorption of sunlight by the solar cell conversion layer, while having high conductivity to reduce energy loss due to electrical resistance. The leading product in the market of thin film optoelectronic devices is a conductive metal oxide such as Indium Tin Oxide (ITO), which is widely used as a conductive material for a transparent conductive electrode due to its high conductivity (10 Ω/sq) and high transparency (85%). Despite the excellent properties of ITO thin films, the high price of indium, its own fragility and expensive deposition techniques have prevented ITO from being a low cost production material and used in the construction of flexible solar cell modules. In recent years, there are new materials replacing indium tin oxide, such as Carbon Nanotubes (CNTs), etc., and TCEs are built with substrates by solution methods, so that flexible electronic products can be manufactured using cost-effective roll-to-roll manufacturing techniques. Therefore, the use of highly transparent conductive paper as a substrate for printed electronic devices is particularly important.
The Chinese patent application with the publication number CN101544838 provides a super-hydrophobic nano silicon dioxide/high polymer composite membrane and a preparation method thereof. The method comprises subjecting polyethylene glycol monomethyl ether (MPEG) and Polydiethoxysiloxane (PEDS) to transesterification reaction to synthesize MPEG-g-PEDS graft polymer, subjecting to sol-gelation reaction, dispersing gel powder as filler into polymer solution, coating the solution on a substrate, and drying to obtain a film. After the composite membrane is soaked in water/ethanol solution, surface molecular self-assembly is carried out by using a surface modifier, and after residual liquid is washed away by using n-hexane, the composite membrane is dried, so that the super-hydrophobic nano silicon dioxide/high polymer composite membrane can be obtained. Although the method relates to a super-hydrophobic nano silicon dioxide/high polymer composite membrane, the production process is complex and is not suitable for large-scale production and application.
The Chinese patent application with the publication number of CN1O614946OA provides high-strength high-antibacterial-property waterproof conductive paper and a preparation method thereof, silver nitrate and a nano-cellulose suspension are uniformly mixed, a sodium borohydride solution is added, a nano-cellulose solid-supported nano-silver compound is prepared through reaction, aniline and persulfuric acid are added to prepare a nano-cellulose/silver/polyaniline compound, beeswax is added finally, the nano-cellulose silver polyaniline beeswax compound is obtained after the mixture is uniformly stirred at a high temperature, and the obtained compound is coated on the surface of paper to obtain the high-strength high-antibacterial-property waterproof conductive paper. However, the method does not achieve the super-hydrophobic effect, the contact angle of the method to water is only 125 degrees, and the process is relatively complicated; the poor solubility and mechanical properties of polyaniline also affect the conductivity of paper.
Chinese patent application publication No. CN107034722 provides a method for preparing carbon nanotube conductive paper, in which carbon nanotubes are graphitized to remove impurities inside the carbon nanotubes, thereby improving the microstructure of the carbon nanotubes, increasing crystallinity, making the atomic arrangement regular and dense, and being more easily dispersed among paper fibers, and significantly improving the overall performance of the carbon nanotube conductive paper. The conductivity and the thermal conductivity of the graphitized modified conductive paper are greatly improved. However, the method is only limited to improving the conductivity of the paper, but does not improve the super-hydrophobic property and the transparency of the paper; the use of graphitized carbon nanotubes to enhance electrical conductivity is not widely used in the country for cost and technical reasons.
Disclosure of Invention
The invention aims to solve the technical problem of providing the super-hydrophobic transparent conductive paper and the preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of super-hydrophobic transparent conductive paper comprises the following steps:
(1) preparing nano silicon dioxide particles;
(2) preparing a hydroxylated carbon nanotube;
(3) uniformly mixing nano silicon dioxide particles with the hydroxylated carbon nano tubes, and performing super-hydrophobic modification on the nano silicon dioxide particles;
(4) preparing transparent paper;
(5) and (4) coating the mixture prepared in the step (3) on transparent paper, and drying at normal temperature to obtain the super-hydrophobic transparent conductive paper.
The invention provides a preparation method of super-hydrophobic transparent conductive paper, which comprises the steps of firstly, uniformly mixing 5mL of ammonia water and 65mL of absolute ethyl alcohol, then adding a uniform mixed solution of 5mL of tetraethyl silicate and 25mL of absolute ethyl alcohol, stirring a reaction solution for 12 hours by using a magnetic stirrer, then centrifuging the system at a high speed under the condition of 6600 r/min-10000 r/min for 3 hours, removing a supernatant, filtering, washing by using absolute ethyl alcohol, drying a cleaned product at the temperature of 60-80 ℃ in vacuum for 3 hours, and preparing nano silicon dioxide particles.
The invention provides a preparation method of super-hydrophobic transparent conductive paper, which comprises the following steps: firstly, 30mL of 65% nitric acid solution is weighed into a 100mL three-neck flask, then 30mL of distilled water is weighed into the three-neck flask, the nitric acid solution with uniform concentration is obtained after stirring for 15 minutes, 1g of carbon nano tube is weighed into the three-neck flask containing the nitric acid solution, the stirring is carried out for 10 minutes, the carbon nano tube is uniformly dispersed into the nitric acid solution, a reflux condensing device is installed, the stirring is carried out for 4 hours at 80 ℃, the cooling is carried out to the room temperature, then the reaction liquid is poured into 1000mL of distilled water, standing and layering are carried out, supernatant liquid is poured out, the operation is repeated for multiple times, the pH value of the liquid is 7, a sand core funnel is used for filtering the product, the filter cake is washed with the distilled water for multiple times, then the product is placed into a vacuum drying oven at 65 ℃ for drying for 24 hours, and then the product is ground and dried by a grinding body.
The invention provides a preparation method of super-hydrophobic transparent conductive paper, which comprises the following steps of dispersing nano silicon dioxide particles and hydroxylated carbon nano tubes into absolute ethyl alcohol, then carrying out ultrasonic mixing on the system uniformly for 30 minutes, and then carrying out super-hydrophobic modification on the nano silicon dioxide particles and the hydroxylated carbon nano tubes, wherein the modification method comprises the following steps: dispersing 5g of nano-scale silicon dioxide particles into 50mL of toluene, performing ultrasonic dispersion for 30min, and adding one of silane coupling agent or fluorine-containing silane chloride to prepare the super-hydrophobic nano-silicon dioxide particle hydroxylated carbon nanotube.
The invention provides a preparation method of super-hydrophobic transparent conductive paper, wherein the silane coupling agent can be one of vinyltrimethoxysilane (A-171), vinyltriethoxysilane (A-151), gamma-aminopropyltriethoxysilane (DB-550), gamma-glycidoxypropyltrimethoxysilane (DB-560), gamma-methacryloxypropyltrimethoxysilane (DB-570) or gamma-mercaptopropyltriethoxysilane (DB-580), and the fluorine-containing silazane can be one of tridecafluorooctyltrimethoxysilane, perfluorohexyltrichlorosilane or perfluorooctyltrichlorosilane.
The invention provides a preparation method of super-hydrophobic transparent conductive paper, wherein the super-hydrophobic nano silicon dioxide particles account for 4-8% by mass, the hydroxylated carbon nano tubes account for 0.2-1% by mass, and the absolute ethyl alcohol accounts for 91-95.8% by volume.
The invention provides a preparation method of super-hydrophobic transparent conductive paper, which comprises the steps of oxidizing cellulose by 2,2,6, 6-tetramethylpiperidine oxide to prepare nano-cellulose, and then carrying out vacuum filtration to prepare the transparent paper.
The invention provides a preparation method of super-hydrophobic transparent conductive paper, wherein the method for preparing nano-cellulose by oxidizing cellulose with 2,2,6, 6-tetramethylpiperidine oxide comprises the following steps: completely dissolving 2,2,6, 6-tetramethylpiperidine oxide and sodium bromide in a beaker, adding sodium hypochlorite, uniformly mixing, pouring into paper pulp, stirring for 4 hours in an electric stirrer, controlling the pH value to be between 10 and 10.5, adding absolute ethyl alcohol to stop reaction, and homogenizing the reaction solution under high pressure to obtain the nano-cellulose.
The invention provides a preparation method of super-hydrophobic transparent conductive paper, which is characterized in that a mixture of super-hydrophobic conductive nano silicon dioxide particles and 0-1% of hydroxylated carbon nano tubes is uniformly distributed on the transparent paper, the method is one of spin coating, spray coating or coating, and then drying is carried out at normal temperature to prepare the super-hydrophobic transparent conductive paper.
The invention has the technical effects that:
1. the nano silicon dioxide particles can be in a good dispersion state by utilizing ultrasonic waves, so that flocculation is not easy to occur among the nano silicon dioxide particles, and simultaneously, the mixing and reaction of reactants in microscopic particles can be accelerated.
2. As a novel composite material, the super-hydrophobic transparent conductive paper has good hydrophobic property, the contact angle can reach 155 degrees, and the existence of the super-hydrophobic surface of the paper enables the moisture of the paper material not to be easily changed due to the change of the external environment, so that the performance is more stable.
3. The transparent paper has high strength and good conductivity, and can replace high-cost Indium Tin Oxide (ITO) to be used as a Transparent Conductive Electrode (TCEs), thereby having important effects on the production and performance of thin-film photoelectric devices.
4. The method has the advantages of simple process flow, easy operation, low cost, high production efficiency and easy realization of industrial production.
The invention will be further explained with reference to the drawings.
Drawings
FIG. 1 scanning electron micrograph of nanosilicon dioxide
FIG. 2 scanning electron microscope image of mixture of nano-silica particles and hydroxylated carbon nanotubes
FIG. 3 is a graph showing the relationship between the transparency of paper and the content of hydroxylated carbon nanotubes
FIG. 4 shows water surface contact angle of super-hydrophobic transparent conductive paper
FIG. 5 is a graph showing the detection of conductivity of hydroxylated carbon nanotubes with different contents and transparent paper
Detailed Description
The present invention is described below by way of specific examples, but the present invention is not limited to these examples, and it should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations in light of the above disclosure.
Example 1
(1) Preparing nano silicon dioxide particles;
the preparation method of the nano silicon dioxide particles comprises the steps of firstly, uniformly mixing 5mL of ammonia water and 65mL of absolute ethyl alcohol, then adding a uniform mixed solution of 5mL of tetraethyl silicate and 25mL of absolute ethyl alcohol, stirring the reaction solution for 12 hours by using a magnetic stirrer, then centrifuging the system at a high speed under the condition of 6600r/min for 3 hours, removing the supernatant, filtering, washing by using absolute ethyl alcohol, drying the cleaned product in vacuum for 3 hours, and thus obtaining the nano silicon dioxide particles. The method for modifying the nano silicon dioxide particles by super-hydrophobicity comprises the following steps: dispersing 5g of nano-scale silicon dioxide particles into 50mL of toluene, and performing ultrasonic dispersion for 30min to obtain the nano-scale silicon dioxide particles, wherein the scanning electron microscope image of the nano-scale silicon dioxide is shown in figure 1.
(2) Preparing a hydroxylated carbon nanotube;
the preparation method of the hydroxylated carbon nanotube comprises the following steps: firstly, 30mL of 65% nitric acid solution is weighed into a 100mL three-neck flask, then 30mL of distilled water is weighed into the three-neck flask, the nitric acid solution with uniform concentration is obtained after stirring for 15 minutes, 1g of carbon nano tube is weighed into the three-neck flask containing the nitric acid solution, the stirring is carried out for 10 minutes, the carbon nano tube is uniformly dispersed into the nitric acid solution, a reflux condensing device is installed, the stirring is carried out for 4 hours at 80 ℃, the cooling is carried out to the room temperature, then the reaction liquid is poured into 1000mL of distilled water, standing and layering are carried out, supernatant liquid is poured out, the operation is repeated for multiple times, the pH value of the liquid is 7, a sand core funnel is used for filtering the product, the filter cake is washed with the distilled water for multiple times, then the product is placed into a vacuum drying oven at 65 ℃ for drying for 24 hours, and then the product is ground and dried by a grinding body.
(3) Uniformly mixing nano silicon dioxide particles with the hydroxylated carbon nano tubes, and performing super-hydrophobic modification on the nano silicon dioxide particles;
the preparation method comprises the following steps of weighing the super-hydrophobic nano-silica particles with the mass percentage of 5%, the hydroxylated carbon nano-tubes with the mass percentage of 1% and the absolute ethyl alcohol with the volume percentage of 94%, adding the weighed super-hydrophobic nano-silica particles and the hydroxylated carbon nano-tubes into the absolute ethyl alcohol, adding vinyl trimethoxy silane (A-171), uniformly mixing to perform super-hydrophobic modification, and obtaining a scanning electron microscope image of a mixture of the nano-silica particles and the hydroxylated carbon nano-tubes as shown in figure 2.
(4) Preparing transparent paper;
the method for preparing the nano-cellulose by oxidizing the cellulose with 2,2,6, 6-tetramethylpiperidine oxide comprises the following steps: firstly weighing 40g of softwood pulp, then weighing 0.64g of 2,2,6, 6-tetramethylpiperidine oxide and 6.4g of sodium bromide, completely dissolving the materials in a beaker, then adding 500mL of sodium hypochlorite, uniformly mixing, then pouring the mixture into paper pulp, stirring for 4 hours in an electric stirrer, controlling the pH value to be between 10 and 10.5, finally adding absolute ethyl alcohol until the reaction liquid turns white, terminating the reaction, finally adding absolute ethyl alcohol to terminate the reaction, homogenizing the reaction liquid under high pressure to prepare nano cellulose, and carrying out vacuum filtration for 12 hours to prepare transparent paper.
(5) And (4) coating the mixture prepared in the step (3) on transparent paper, and drying at normal temperature to obtain the super-hydrophobic transparent conductive paper. The method comprises the steps of spraying a mixture of 5% of superhydrophobic nano-silica particles and 1% of hydroxylated carbon nanotubes on transparent paper, and drying at normal temperature to obtain the superhydrophobic transparent conductive paper, wherein the relation curve of the hydroxylated carbon nanotubes with different contents and the transparency of the paper is shown in the attached drawing 3, the water surface contact angle of the superhydrophobic transparent conductive paper is shown in the attached drawing 4, the conductivity detection curve of the hydroxylated carbon nanotubes with different contents and the transparent paper is shown in the attached drawing 5, and as shown in the attached drawing 5, the conductivity of the superhydrophobic transparent conductive paper is increased along with the increase of the content of the hydroxylated carbon nanotubes.
Example 2
(1) Preparing nano silicon dioxide particles;
the preparation method of the nano silicon dioxide particles comprises the steps of firstly, uniformly mixing 5mL of ammonia water and 65mL of absolute ethyl alcohol, then adding a uniform mixed solution of 5mL of tetraethyl silicate and 25mL of absolute ethyl alcohol, stirring the reaction solution by using a magnetic stirrer for 12 hours, then centrifuging the system at a high speed under the condition of 8000r/min for 3 hours, removing the supernatant, filtering, washing by using absolute ethyl alcohol, drying the cleaned product in vacuum for 3 hours, and thus obtaining the nano silicon dioxide particles. The method for modifying the nano silicon dioxide particles by super-hydrophobicity comprises the following steps: dispersing 5g of nano-scale silicon dioxide particles into 50mL of toluene, and performing ultrasonic dispersion for 30min to obtain the nano-scale silicon dioxide particles, wherein the scanning electron microscope image of the nano-scale silicon dioxide is shown in figure 1.
(2) Preparing a hydroxylated carbon nanotube;
the preparation method of the hydroxylated carbon nanotube comprises the following steps: firstly, 30mL of 65% nitric acid solution is weighed into a 100mL three-neck flask, then 30mL of distilled water is weighed into the three-neck flask, the nitric acid solution with uniform concentration is obtained after stirring for 15 minutes, 1g of carbon nano tube is weighed into the three-neck flask containing the nitric acid solution, the stirring is carried out for 10 minutes, the carbon nano tube is uniformly dispersed into the nitric acid solution, a reflux condensing device is installed, the stirring is carried out for 4 hours at 80 ℃, the cooling is carried out to the room temperature, then the reaction liquid is poured into 1000mL of distilled water, standing and layering are carried out, supernatant liquid is poured out, the operation is repeated for multiple times, the pH value of the liquid is 7, a sand core funnel is used for filtering the product, the filter cake is washed with the distilled water for multiple times, then the product is placed into a vacuum drying oven at 65 ℃ for drying for 24 hours, and then the product is ground and dried by a grinding body.
(3) Uniformly mixing nano silicon dioxide particles with the hydroxylated carbon nano tubes, and performing super-hydrophobic modification on the nano silicon dioxide particles;
the weight percentage of the super-hydrophobic nano-silica particles is 6%, the weight percentage of the hydroxylated carbon nano-tubes is 0.6%, and the volume percentage of the absolute ethyl alcohol is 93.4%, the weighed super-hydrophobic silica particles and the hydroxylated carbon nano-tubes are added into the absolute ethyl alcohol, then the gamma-methacryloxypropyl trimethoxy silane (DB-570) is added, the mixture is uniformly mixed for super-hydrophobic modification, and the scanning electron microscope picture of the mixture of the nano-silica particles and the hydroxylated carbon nano-tubes is shown as the attached figure 2.
(4) Preparing transparent paper;
the method for preparing the nano-cellulose by oxidizing the cellulose with 2,2,6, 6-tetramethylpiperidine oxide comprises the following steps: firstly weighing 40g of softwood pulp, then weighing 0.64g of 2,2,6, 6-tetramethylpiperidine oxide and 6.4g of sodium bromide, completely dissolving the materials in a beaker, then adding 500mL of sodium hypochlorite, uniformly mixing, pouring the mixture into paper pulp, stirring for 4 hours in an electric stirrer, controlling the pH value to be between 10 and 10.5, finally adding absolute ethyl alcohol until the reaction liquid turns white, terminating the reaction, and finally adding absolute ethyl alcohol to terminate the reaction. And (3) homogenizing the reaction solution under high pressure to prepare nano cellulose, and performing vacuum filtration for 12 hours to prepare the transparent paper.
(5) And (4) coating the mixture prepared in the step (3) on transparent paper, and drying at normal temperature to obtain the super-hydrophobic transparent conductive paper. The method comprises the steps of spin-coating a mixture of 6% of superhydrophobic nano-silica particles and 0.6% of hydroxylated carbon nanotubes on transparent paper, and drying at normal temperature to obtain the superhydrophobic transparent conductive paper, wherein a relation curve of the hydroxylated carbon nanotubes with different contents and the transparency of the paper is shown in a figure 3, a water surface contact angle of the superhydrophobic transparent conductive paper is shown in a figure 4, a detection curve of the conductivity of the hydroxylated carbon nanotubes with different contents and the transparent paper is shown in a figure 5, and as shown in the figure 5, the conductivity of the superhydrophobic transparent conductive paper is increased along with the increase of the content of the hydroxylated carbon nanotubes.
Example 3
(1) Preparing nano silicon dioxide particles;
the preparation method of the nano silicon dioxide particles comprises the steps of firstly, uniformly mixing 5mL of ammonia water and 65mL of absolute ethyl alcohol, then adding a uniform mixed solution of 5mL of tetraethyl silicate and 25mL of absolute ethyl alcohol, stirring the reaction solution by using a magnetic stirrer for 12 hours, then centrifuging the system at high speed under the condition of 9000r/min for 3 hours, removing the supernatant, filtering, washing by using absolute ethyl alcohol, drying the cleaned product in vacuum for 3 hours, and thus obtaining the nano silicon dioxide particles. The method for modifying the nano silicon dioxide particles by super-hydrophobicity comprises the following steps: dispersing 5g of nano-scale silicon dioxide particles into 50mL of toluene, and performing ultrasonic dispersion for 30min to obtain the nano-scale silicon dioxide particles, wherein the scanning electron microscope image of the nano-scale silicon dioxide is shown in figure 1.
(2) Preparing a hydroxylated carbon nanotube;
the preparation method of the hydroxylated carbon nanotube comprises the following steps: firstly, 30mL of 65% nitric acid solution is weighed into a 100mL three-neck flask, then 30mL of distilled water is weighed into the three-neck flask, the nitric acid solution with uniform concentration is obtained after stirring for 15 minutes, 1g of carbon nano tube is weighed into the three-neck flask containing the nitric acid solution, the stirring is carried out for 10 minutes, the carbon nano tube is uniformly dispersed into the nitric acid solution, a reflux condensing device is installed, the stirring is carried out for 4 hours at 80 ℃, the cooling is carried out to the room temperature, then the reaction liquid is poured into 1000mL of distilled water, standing and layering are carried out, supernatant liquid is poured out, the operation is repeated for multiple times, the pH value of the liquid is 7, a sand core funnel is used for filtering the product, the filter cake is washed with the distilled water for multiple times, then the product is placed into a vacuum drying oven at 65 ℃ for drying for 24 hours, and then the product is ground and dried by a grinding body.
(3) Uniformly mixing nano silicon dioxide particles with the hydroxylated carbon nano tubes, and performing super-hydrophobic modification on the nano silicon dioxide particles;
the super-hydrophobic nano-silica particles account for 7% by mass, the hydroxylated carbon nano-tubes account for 0.1% by mass, and the absolute ethyl alcohol accounts for 92.9% by volume, the weighed super-hydrophobic silica particles and the hydroxylated carbon nano-tubes are added into the absolute ethyl alcohol, tridecafluorooctyltrimethoxysilane is added, the mixture is uniformly mixed for super-hydrophobic modification, and the scanning electron microscope picture of the mixture of the nano-silica particles and the hydroxylated carbon nano-tubes is shown as the attached figure 2.
(4) Preparing transparent paper;
the method for preparing the nano-cellulose by oxidizing the cellulose with 2,2,6, 6-tetramethylpiperidine oxide comprises the following steps: firstly weighing 40g of softwood pulp, then weighing 0.64g of 2,2,6, 6-tetramethylpiperidine oxide and 6.4g of sodium bromide, completely dissolving in a beaker, then adding 500mL of sodium hypochlorite, uniformly mixing, and pouring into paper pulp; stirring for 4 hours in an electric stirrer, controlling the pH value to be 10-10.5, finally adding absolute ethyl alcohol until the reaction solution turns white, terminating the reaction, and finally adding absolute ethyl alcohol to terminate the reaction. And (3) homogenizing the reaction solution under high pressure to prepare the nano-cellulose. And carrying out vacuum filtration for 12 hours to obtain the transparent paper.
(5) And (4) coating the mixture prepared in the step (3) on transparent paper, and drying at normal temperature to obtain the super-hydrophobic transparent conductive paper. The method comprises the steps of coating a mixture of 7% of superhydrophobic nano-silica particles and 0.4% of hydroxylated carbon nanotubes on transparent paper, and drying at normal temperature to obtain the relation curve of the hydroxylated carbon nanotubes with different contents of the superhydrophobic transparent conductive paper and the transparency of the paper, wherein the relation curve is shown in the attached drawing 3, the water surface contact angle of the superhydrophobic transparent conductive paper is shown in the attached drawing 4, the conductivity detection curve of the hydroxylated carbon nanotubes with different contents and the transparency of the paper is shown in the attached drawing 5, and as shown in the attached drawing 5, the conductivity of the superhydrophobic transparent conductive paper is increased along with the increase of the content of the hydroxylated carbon nanotubes.
In conclusion, by adopting the super-hydrophobic transparent conductive paper and the preparation method thereof, the prepared paper has good hydrophobic property, more stable performance, high strength and better conductivity, the method has simple flow, is easy to operate and has high production efficiency, and the industrial production is easy to realize.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (8)
1. A preparation method of super-hydrophobic transparent conductive paper is characterized by comprising the following steps:
(1) preparing nano silicon dioxide particles, namely uniformly mixing 5mL of ammonia water and 65mL of absolute ethyl alcohol, adding a uniform mixed solution of 5mL of tetraethyl silicate and 25mL of absolute ethyl alcohol, stirring the reaction solution for 12 hours by using a magnetic stirrer, centrifuging the system at a high speed, removing supernatant, filtering, washing by using absolute ethyl alcohol, and drying the cleaned product in vacuum to obtain the nano silicon dioxide particles;
(2) preparing hydroxylated carbon nanotubes, namely measuring 30mL of 65% nitric acid solution and 30mL of distilled water in a three-neck flask, stirring to obtain uniform-concentration nitric acid solution, weighing 1g of carbon nanotubes in the three-neck flask filled with the nitric acid solution, uniformly dispersing the carbon nanotubes in the nitric acid solution, installing a reflux condensing device, stirring at 80 ℃ for 4 hours, cooling to room temperature, pouring a reaction solution into the distilled water, standing for layering, pouring out supernatant, repeating the operation for multiple times to enable the pH of the liquid to be 7, filtering a product by using a sand core funnel, washing a filter cake by using the distilled water for multiple times, drying the product in a vacuum drying oven, and grinding and drying the product by using a grinding body to obtain the hydroxylated carbon nanotubes;
(3) uniformly mixing nano silicon dioxide particles and hydroxylated carbon nano tubes, carrying out super-hydrophobic modification on the nano silicon dioxide particles, dispersing 5g of nano silicon dioxide particles into 50mL of toluene, and adding one of silane coupling agent or fluorine-containing silane chloride to prepare the super-hydrophobic nano silicon dioxide particle hydroxylated carbon nano tubes;
(4) preparing transparent paper, namely oxidizing cellulose by 2,2,6, 6-tetramethylpiperidine oxide to prepare nano cellulose, and performing vacuum filtration to prepare the transparent paper;
(5) and (4) coating the mixture prepared in the step (3) on transparent paper, and drying at normal temperature to obtain the super-hydrophobic transparent conductive paper.
2. The preparation method of the superhydrophobic transparent conductive paper according to claim 1, wherein the preparation method of the nano silica particles in the step (1) is that 5mL of ammonia water and 65mL of absolute ethyl alcohol are uniformly mixed, then a uniform mixed solution of 5mL of tetraethyl silicate and 25mL of absolute ethyl alcohol is added, a magnetic stirrer is used for stirring the reaction solution for 12 hours, then the system is subjected to high-speed centrifugation at 6600 r/min-10000 r/min for 3 hours, the supernatant is removed, the filtration is carried out, the washing is carried out with absolute ethyl alcohol, the washed product is subjected to vacuum drying at 60-80 ℃ for 3 hours, and the nano silica particles are prepared.
3. The method for preparing the superhydrophobic transparent conductive paper according to claim 1, wherein in the step (2), the method for preparing the hydroxylated carbon nanotube comprises: firstly, measuring 30mL of 65% nitric acid solution in a 100mL three-neck flask, measuring 30mL of distilled water in the three-neck flask, and stirring for 15 minutes to obtain a nitric acid solution with uniform concentration; weighing 1g of carbon nano tube in a three-neck flask filled with a nitric acid solution, and stirring for 10 minutes to uniformly disperse the carbon nano tube in the nitric acid solution; installing a reflux condensing device, stirring for 4 hours at 80 ℃, cooling to room temperature, then pouring the reaction liquid into 1000mL of distilled water, standing for layering, pouring out supernatant, repeating the operation for multiple times to enable the pH value of the liquid to be 7, filtering the product by using a sand core funnel, washing the filter cake by using distilled water for multiple times, then placing the product in a vacuum drying oven at 65 ℃ for drying for 24 hours, and then grinding and drying the product by using a grinding body to prepare the hydroxylated carbon nanotube.
4. The method for preparing the superhydrophobic transparent conductive paper according to claim 1, wherein in the step (3), the nano silica particles and the hydroxylated carbon nanotubes are dispersed in absolute ethyl alcohol, then the system is subjected to ultrasonic mixing for 30 minutes, and then the nano silica particles and the hydroxylated carbon nanotubes are subjected to superhydrophobic modification, wherein the modification method comprises the following steps: dispersing 5g of nano-scale silicon dioxide particles into 50mL of toluene, performing ultrasonic dispersion for 30min, and adding a silane coupling agent or one of fluorine-containing silicon chloride and alkane to prepare the super-hydrophobic nano-silica particle hydroxylated carbon nanotube.
5. The method for preparing the superhydrophobic transparent conductive paper according to claim 4, wherein the silane coupling agent is one of vinyltrimethoxysilane (A-171), vinyltriethoxysilane (A-151), gamma-aminopropyltriethoxysilane (DB-550), gamma-glycidoxypropyltrimethoxysilane (DB-560), gamma-methacryloxypropyltrimethoxysilane (DB-570) or gamma-mercaptopropyltriethoxysilane (DB-580), and the fluorosilane chloride is one of tridecafluorooctyltrimethoxysilane, perfluorohexyltrichlorosilane or perfluorooctyltrichlorosilane.
6. The preparation method of the superhydrophobic transparent conductive paper according to claim 5, wherein the mass percentage of the nano silica particles is 4-8%, the mass percentage of the hydroxylated carbon nanotubes is 0.2-1%, and the volume percentage of the absolute ethyl alcohol is 91-95.8%.
7. The method for preparing the superhydrophobic transparent conductive paper according to claim 1, wherein the method for preparing the nanocellulose by oxidizing the cellulose with 2,2,6, 6-tetramethylpiperidine oxide comprises the following steps: completely dissolving 2,2,6, 6-tetramethylpiperidine oxide and sodium bromide in a beaker, adding sodium hypochlorite, uniformly mixing, pouring into paper pulp, stirring for 4 hours in an electric stirrer, controlling the pH value to be between 10 and 10.5, adding absolute ethyl alcohol to stop reaction, and homogenizing the reaction solution under high pressure to obtain the nano-cellulose.
8. The method for preparing the superhydrophobic transparent conductive paper according to claim 1, wherein in the step (5), the mixture of the superhydrophobic conductive nano-silica particles and 0.2-1% of the hydroxylated carbon nanotubes is uniformly distributed on the transparent paper by one of spin coating, spray coating or coating, and then the mixture is dried at normal temperature to obtain the superhydrophobic transparent conductive paper.
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