CN110240117B - Ultrathin transparent nano/micron structure self-assembled film and green preparation method thereof - Google Patents
Ultrathin transparent nano/micron structure self-assembled film and green preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultrathin transparent nano/micron structure self-assembled film and a green preparation method thereof. The preparation method comprises the following steps: dispersing the nano/micro structure and/or the modified substance thereof in a first liquid phase system to form nano/micro structure dispersion liquid; spraying the nano/micro structure dispersion liquid to the surface of a second liquid phase system in a spraying mode, and removing the second liquid phase system to obtain a nano/micro structure film; and extruding the nano/micron structure film to enable the nano/micron structure film to be self-assembled on a gas-liquid interface to form a compact and stable nano/micron structure self-assembled film with controllable thickness. The nano/micron particles and the modified film thereof have good comprehensive performance and can be widely used on optical and electrical devices and nano coatings; meanwhile, the preparation process is simple in flow, convenient to operate, low in requirement on environmental factors, free of any influence and capable of meeting the requirements of large-area and large-batch industrial production.
Description
Technical Field
The invention relates to a green preparation method of a nano/micron structure self-assembled film, in particular to a self-supporting ultrathin transparent conductive self-assembled film comprising multi-scale nano/micron particles or wires, a green preparation method and application thereof, belonging to the technical field of material science.
Background
The self-assembly nano film is an ordered film which has stable thermodynamics and lower energy and is formed by the fact that molecules with certain functional characteristics are spontaneously adsorbed on a solid-liquid interface, a gas-liquid interface or a gas-solid interface through chemical bond action. The self-assembly film preparation technology mainly comprises electrostatic force self-assembly, covalent bond self-assembly, molecular deposition self-assembly and the like.
The air-water interface nano film self-assembly research covers two aspects of basic theory and practical application, and relates to various fields of biological medicine, life science such as cell membranes, paint coatings, food such as hot concentrated milk and hot concentrated soybean milk, surface conjunctiva after cooling, petroleum exploitation and processing, daily chemical industry such as detergents, cosmetics, novel materials and the like. The air-water interface nano film provides a new approach for preparing transparent conductive films, super-hydrophobic layers, nano or micron ordered arrays, nano particle or nano wire self-assembly, nano catalyst preparation, Raman enhancement materials, novel catalytic materials, photoelectric materials and the like.
In recent years, various methods for preparing continuous nano/micro particles and modified films thereof have been studied. The existing method for preparing nano/micron particles and modified membranes thereof usually has the defects of complex preparation method process, high equipment requirement, need of using toxic solvents, unsuitability for large-scale production and the like. Therefore, how to develop a simple, environment-friendly and efficient preparation of a continuous ultrathin nano/micron particle self-assembled film is one of the important challenges facing scientists in the field.
Disclosure of Invention
In view of the defects of the prior art, the main object of the present invention is to provide a self-supporting ultrathin transparent conductive nano/micro structure self-assembled film, and a green preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
among some embodiments of the present invention is a green process for preparing an ultra-thin transparent nano/micro structured self-assembled film, comprising:
(1) dispersing the nano/micro structure and/or the nano/micro structure modifier in a first liquid phase system to form a nano/micro structure dispersion liquid;
(2) spraying the nano/micron structure dispersion liquid on the surface of a second liquid phase system in a spraying mode, and removing the second liquid phase system after the first liquid phase system volatilizes to obtain a nano/micron structure film;
(3) extruding the nano/micron structure film by using the surface tension of the liquid to enable the nano/micron structure film to be self-assembled on a gas-liquid interface to form a compact and stable nano/micron structure film, and obtaining a nano/micron structure self-assembled film with a uniform and controllable structure;
wherein the dispersity of the nano/micro structure and/or the nano/micro structure modifier in the first liquid phase system is larger than that in the second liquid phase system, and the first liquid phase system cannot be mutually soluble with the second liquid phase system.
In some embodiments, the method of making comprises: when the nano/micron structure dispersion liquid is sprayed on the surface of the second liquid phase system, the spraying speed is 5 ml/min-500 ml/min.
In some embodiments, the method of making comprises: and removing the second liquid phase system by adopting a peristaltic pump pumping mode.
Further, the speed of pumping the second liquid phase system by adopting a peristaltic pump is 5 mL/min-20 mL/min.
Preferably, the time of the extrusion treatment is 5s to 60 s.
Preferably, the pressure adopted by the extrusion treatment is 7.2-7.8 mN/m.
In some embodiments, the preparation method further comprises step (4): and transferring the ultrathin transparent nano/micron structure self-assembly film to a selected interface for self-assembly to form a hybrid film which is self-assembled by different structure nano film layers.
Preferably, the hybrid film comprises at least one nano/micro structure or nano/micro structure modification.
Further, the preparation method further comprises the following steps: and (4) repeating the step (3) and/or the step (4) for more than two times circularly until the required ultrathin transparent nano/micron structure self-assembled film is obtained.
Furthermore, the cycle number is 5-10.
Further, the nano/micro structure and/or the nano/micro structure modification comprises a one-dimensional material, a two-dimensional material or a three-dimensional material.
Further, the nano/micro structures and/or the modifications of the nano/micro structures have at least one dimension which is larger than 1 nanometer and smaller than 1000 micrometers.
Further, the nano/micro structure includes nano/micro particles and/or nano/micro wires.
Further, the nano/micro particles include any one or a combination of two or more of metal nanoparticles, metal and/or non-metal oxide particles, polymer particles, and nanocarbon materials.
Further, the self-assembly temperature of the nano/micro structure film on a gas-liquid interface is 20-100 ℃, and the self-assembly time is 10-1000 s.
Also provided in some embodiments of the present invention are ultrathin transparent nano/micro structured self-assembled films prepared by the foregoing methods.
Preferably, the thickness of the film is 20 nm-10 μm, the surface roughness is less than 1.5nm, and the light transmittance is greater than 86%.
The invention also provides the application of the ultrathin transparent nano/micro structure self-assembly film in preparing transparent devices, transparent conductive films, super-hydrophobic coatings, nano or micro ordered arrays, nano particle or nano wire self-assembly materials, nano catalyst materials or Raman enhancement materials.
For example, the embodiment of the present invention further provides a device, which comprises the aforementioned ultra-thin transparent nano/micro structure self-assembled film.
Preferably, the device comprises an optical device, an electronic device or an optoelectronic device.
Compared with the prior art, the invention has the beneficial effects that:
1) the green preparation method of the ultrathin transparent nano/micron structure self-assembled film provided by the invention has the advantages of simple process, easiness in implementation, no need of expensive preparation instruments, high-temperature action and catalysts, and low time consumption;
2) the green preparation method of the ultrathin transparent nano/micron structure self-assembled film provided by the invention can effectively control the thickness of the nano/micron particles and the modified substance film thereof by controlling the concentration of the nano/micron particles and the modified substance dispersion liquid thereof;
3) the green preparation method of the ultrathin transparent nano/micron structure self-assembled film only uses ethanol and water in cleaning, can reduce the surface pollution of nano/micron particles and modified films thereof, and is environment-friendly, simple and environment-friendly;
4) the nano/micron particles and the modified conductive film thereof prepared by the invention have good strength and can form a stable self-supporting structure;
5) the nano/micron particles and the modified conductive film thereof prepared by the invention have good conductive performance and higher transparency, and can be applied to transparent or conductive devices.
In a word, the nano/micron particles and the modified substance film thereof prepared by the invention have good comprehensive performance and can be widely used on optical and electric devices. Meanwhile, the preparation method has the advantages of simple process flow, convenient operation, low requirement on environmental factors, no influence, capability of meeting the requirements of large-area and large-batch industrial production, obvious effect and capability of continuously collecting nano/micron particles and modified substance films thereof on a large scale.
Drawings
FIGS. 1-2 are schematic views of the process for preparing the ultra-thin transparent polystyrene microsphere self-assembled film in example 1 of the present invention.
FIG. 3 is a photograph showing an object of the self-assembled film of ultra-thin transparent polystyrene microspheres obtained in example 1 of the present invention.
FIG. 4 is a scanning electron microscope of the self-assembled film of ultra-thin transparent polystyrene microspheres obtained in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be explained in more detail below. It is to be understood, however, that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with one another to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
As described above, in view of the disadvantages of the prior art, the present inventors have conducted extensive and intensive studies and extensive practices for a long time to propose a solution of the present invention, which is based mainly on a green preparation method of ultra-thin films by self-assembling particles (or threads) having a size of several nanometers to several hundred micrometers at an air-liquid interface by a simple spraying method. For example, a dispersion of nano/micro particles and their modifications is sprayed onto a liquid surface through a sprayer, and then a dense ultra-thin film is formed by pressing the particles on the surface. The technical solution, the implementation process and the principle thereof will be further explained with reference to the drawings.
The invention provides a preparation method of an ultrathin transparent nano/micron structure self-assembled film, wherein the thickness, transparency and conductivity of the film can be adjusted by the amount of nano/micron structure dispersion liquid sprayed and the concentration of a nano/micron structure and/or a modifier thereof.
One aspect of the embodiments of the present invention provides a green preparation method of an ultrathin transparent nano/micro structure self-assembled film, which includes:
(1) dispersing nano/micro structures (which are understood to be nano structures, micro structures or a composite structure of the nano structures and the micro structures) and/or nano/micro structure modifications in a first liquid phase system to form a nano/micro structure dispersion liquid;
(2) spraying the nano/micron structure dispersion liquid on the surface of a second liquid phase system in a spraying mode, and removing the second liquid phase system after the first liquid phase system volatilizes to obtain a nano/micron structure film;
(3) extruding the nano/micron structure film by using the surface tension of the liquid to enable the nano/micron structure film to be self-assembled on a gas-liquid interface to form a compact and stable nano/micron structure film, and obtaining a nano/micron structure self-assembled film with a uniform and controllable structure;
wherein the dispersity of the nano/micro structure and/or the nano/micro structure modifier in the first liquid phase system is larger than that in the second liquid phase system, and the first liquid phase system cannot be mutually soluble with the second liquid phase system.
Wherein the first liquid phase system is preferably a volatile liquid phase system.
Wherein the nano/micro structure and/or the nano/micro structure modifier is a one-dimensional, two-dimensional or three-dimensional material.
In some embodiments, the method of making comprises: when the nano/micron structure dispersion liquid is sprayed on the surface of the second liquid phase system, the spraying speed is 5 ml/min-500 ml/min.
Further, when the nano/micro structure dispersion liquid is sprayed on the surface of the second liquid phase system, the spraying area generated by the spray head is the same as or close to the film forming area of the prepared nano/micro structure film (namely the area of the prepared target film).
Further, during spraying, the size of the sprayed droplets was 5 x 10-3mm～5*10-1mm。
In some embodiments, the method of making comprises: and removing the second liquid phase system by adopting a peristaltic pump pumping mode.
Further, the speed of pumping the second liquid phase system by adopting a peristaltic pump is 5 mL/min-20 mL/min.
Preferably, the time of the extrusion treatment is 5s to 60 s.
Preferably, the pressure adopted by the extrusion treatment is 7.2-7.8 mN/m.
In some embodiments, the preparation method further comprises step (4): and transferring the ultrathin transparent nano/micron structure self-assembly film to other selected interfaces (solid phase interfaces or liquid phase interfaces) for self-assembly to form a hybrid film which is self-assembled by nano film layers with different structures.
Preferably, the hybrid film comprises at least one nano/micro structure or nano/micro structure modification.
Further, the preparation method further comprises the following steps: and (4) repeating the step (3) and/or the step (4) for more than two times circularly until the required ultrathin transparent nano/micron structure self-assembled film is obtained.
Furthermore, the cycle number is 5-10.
In some embodiments, the method of making further comprises: adding the nano/micron structure and/or nano/micron structure modifier into the first liquid phase system, and performing ultrasonic dispersion to form nano/micron structure dispersion liquid.
Further, the time of ultrasonic dispersion is 0.5-20 h.
Preferably, the first liquid phase system includes any one or a combination of two or more of ethanol, propanol, glycerol, water, and the like, but is not limited thereto, and care should be taken when combining the components so that the components are not miscible with the second liquid phase system.
Preferably, the concentration of the nano/micro structure dispersion liquid is 0.005 mg/mL-2.0 mg/mL. The thickness of the nanometer/micrometer particles and the modified substance film can be effectively controlled by controlling the concentration of the nanometer/micrometer particles and the modified substance dispersion liquid thereof.
In some embodiments, the nano/micro structured modification is formed by a blending or grafting reaction of the nano/micro structure with a modifying agent.
Preferably, the nano/micro structure modifier comprises an organic substance and/or an inorganic substance.
Preferably, the preparation method of the nano/micro structure modified substance comprises the following steps: and reacting the uniformly mixed reaction system containing the nano/micron structure and the modifier at 40-60 ℃ for 4-7 h, centrifuging and drying.
Preferably, the modifier comprises an oligomer and/or a polymer biopolymer.
Further, the nano/micro structure modifier comprises a modifying group comprising-NH2Any one or a combination of two or more of-COOH, -OH and the like, but not limited thereto.
Further, the nano/micro structure and/or the nano/micro structure modification comprises a one-dimensional material, a two-dimensional material or a three-dimensional material.
Further, the nano/micro structures and/or the modifications of the nano/micro structures have at least one dimension larger than 1 nanometer and smaller than 1000 micrometers (between a few nanometers and a few hundred micrometers).
Further, the nano/micro structures include nano/micro particles (nano particles, micro particles, or a composite structure of both) and/or nano/micro wires (nano wires, micro wires, or a composite structure of both).
Further, the nano/micro particles include metal nanoparticles, for example, nano gold or nano silver particles, etc.; metal and non-metal oxide particles, such as silica nanoparticles, titania nanoparticles, ferroferric oxide magnetic nanoparticles, and the like; polymer particles such as polystyrene microspheres and modifications thereof, etc. may also be included; nanocarbon materials such as, but not limited to, carbon nanotubes, graphene, buckyballs, carbon black particles, and the like may also be included.
In some embodiments, the second liquid phase system comprises organic solvents such as water, carbon disulfide, chloroform, ionic liquids, etc., wherein care is taken when combining the components that are not miscible with the first liquid phase system.
Further, the self-assembly temperature of the nano/micro structure film on a gas-liquid interface is 20-100 ℃, and the self-assembly time is 10-1000 s.
In a more specific embodiment, the preparation method comprises:
1) providing one or more nano/micro particles, or a modification thereof;
2) uniformly dispersing the nano/micron particles in a certain solvent;
3) spraying the dispersion liquid onto the surface of the solution by a spraying method;
4) pumping the solution by a peristaltic pump or other instruments or materials to obtain a nano/micro particle film;
5) self-assembling the nano/micron particle film on a gas-liquid interface to form a compact and stable film;
6) transferring the formed film to other interfaces for self-assembly to further form a mixed film;
7) cycled to form a multilayer hybrid film composed of one or more nano/micro particles.
In a more specific embodiment, the preparation method may further include:
1. taking a certain amount of nano/micron particles and modified substances thereof, adding a certain amount of functional modifier, carrying out water bath at 40-60 ℃ for 4-7 h, centrifuging and drying.
2. Carrying out ultrasonic dispersion on the functionalized nano/micron particles and modified substances thereof by using a certain solvent, wherein the concentration is 0.05 mg/mL-2 mg/mL, and obtaining nano/micron particles and modified substance dispersion liquid thereof;
3. spraying the nano/micron particles and the modified substance dispersion liquid thereof obtained in the step 2 to the interface of a certain solution through a sprayer, and then pumping out the solution at a certain speed through a peristaltic pump, thereby forming a transparent nano/micron particle and modified substance film with uniform thickness;
4. extruding the uniform and transparent nano/micron particles and the modified substance film thereof obtained in the step (3) by a method of sucking interfacial liquid by objects such as a peristaltic pump and the like to form uniform, transparent and compact nano/micron particles and the modified substance film thereof;
5. further transferring the nano/micron particles and the modified hybrid film thereof obtained in the step 4 to any solid interface;
6. and (3) standing the nano/micron particle and modified substance hybrid film obtained in the step (5), drying, and repeating the step (4) and the step (5) to obtain the self-supporting ultrathin transparent conductive nano/micron particle and modified substance film thereof.
The environment-friendly preparation method of the ultrathin transparent nano/micron structure self-assembled film only uses ethanol and water in cleaning, can reduce the surface pollution of nano/micron particles and modified films thereof, and is environment-friendly, simple and environment-friendly.
The green preparation method of the ultrathin transparent nano/micron structure self-assembled film provided by the invention has the advantages of simple process, easiness in implementation, no need of expensive preparation instruments, high-temperature action and catalysts, and low time consumption.
Another aspect of the embodiments of the present invention also provides an ultra-thin transparent nano/micro structure self-assembled film prepared by the foregoing method.
Preferably, the film has a thickness of 20nm to 10 μm, a surface roughness of less than 1.5nm, and a light transmittance of more than 86%, and the result is satisfactory for the production of transparent devices and the like.
Further, the film comprises a nano/micro structure array and/or a nano/micro structure network which are composed of nano/micro structures and/or nano/micro structure modifiers.
In some embodiments, the nano/micro structured modification is formed by a blending or grafting reaction of the nano/micro structure with a modifying agent.
Preferably, the nano/micro structure modifier comprises an organic substance and/or an inorganic substance.
Further, the nano/micro structures include nano/micro particles (nano particles, micro particles, or a composite structure of both) and/or nano/micro wires (nano wires, micro wires, or a composite structure of both).
The other aspect of the embodiment of the invention also provides that the ultrathin transparent nano/micron structure self-assembled film has potential application value in the aspects of preparing transparent devices, transparent conductive films, super-hydrophobic coatings, nano or micron ordered arrays, nano particle or nano wire self-assembled materials, nano catalyst materials or Raman enhancement materials and the like.
For example, the embodiment of the present invention further provides a device, which comprises the aforementioned ultra-thin transparent nano/micro structure self-assembled film.
Preferably, the device comprises an optical device, an electronic device or an optoelectronic device.
By the technical scheme, the nano/micron particles and the modified conductive film thereof have good strength and can form a stable self-supporting structure; and the conductive performance is good, the transparency is high, and the conductive film can be applied to transparent or conductive devices.
In a word, the nano/micron particles and the modified substance film thereof prepared by the invention have good comprehensive performance and can be widely used on optical and electric devices. Meanwhile, the preparation method has the advantages of simple process flow, convenient operation, low requirement on environmental factors, no influence, capability of meeting the requirements of large-area and large-batch industrial production, obvious effect and capability of continuously collecting nano/micron particles and modified substance films thereof on a large scale.
The technical solution of the present invention is further explained below with reference to several preferred embodiments.
Example 1
1. As shown in fig. 1 and fig. 2, a certain amount of polystyrene microspheres are taken and ultrasonically dispersed by a certain amount of ethanol, wherein the concentration is 2 mg/mL;
2. spraying the polystyrene microsphere dispersion obtained in the step 1 to the interface of water through a sprayer at a spraying speed of 5ml/min, wherein the size of sprayed liquid drops is 5 x 10 during spraying-3mm, then pumping the solution out by a peristaltic pump at the speed of 5ml/min, and self-assembling for 800s at the temperature of 20-60 ℃ to form a polystyrene microsphere film with the thickness of 5-10 mu m;
3. extruding the uniform and transparent polystyrene microsphere film obtained in the step 2 for 60s by a method of sucking interfacial liquid through objects such as a peristaltic pump and the like under the pressure of 7.2mN/m, and self-assembling for 800s at the temperature of 40 ℃ to form a uniform, transparent and compact polystyrene microsphere film;
4. further transferring the polystyrene microsphere film obtained in the step 3 to any solid interface;
5. and (3) standing the polystyrene microsphere film obtained in the step (4), drying, and repeating the step (4) to obtain the self-supporting ultrathin polystyrene microsphere film with uniform thickness, wherein the thickness of the polystyrene microsphere film is 10 micrometers, the surface roughness of the polystyrene microsphere film is less than 1.5nm, the light transmittance of the polystyrene microsphere film is more than 86%, and the appearance structure characterization map of the polystyrene microsphere film is shown in the figures 3 and 4.
Tests prove that the polystyrene microsphere film prepared by the embodiment has good comprehensive performance and can be widely used on optical and electrical devices. Meanwhile, the method has the advantages of simple process flow, convenient operation, low requirement on environmental factors, no influence and capability of meeting the requirements of large-area and large-batch industrial production.
Example 2
1. Taking a certain amount of nano gold modified polystyrene microspheres, and performing ultrasonic dispersion by using a certain amount of ethanol, wherein the concentration is 0.05 mg/mL;
2. spraying the nano-gold modified polystyrene microsphere dispersion liquid obtained in the step 1 to the interface of carbon disulfide through a sprayer at a spraying speed of 200ml/min, wherein the size of sprayed liquid drops is 5 x 10 in the spraying process-1mm, and then pumping the solution out at the speed of 20mL/min through a peristaltic pump, thereby forming the nano-gold modified polystyrene microsphere film with the thickness of 5-10 mu m;
3. extruding the uniform and transparent nanogold-modified polystyrene microsphere film obtained in the step 2 for 5 seconds by a method of sucking interfacial liquid through objects such as a peristaltic pump and the like under the pressure of 7.8mN/m, and self-assembling for 1000 seconds at the temperature of 20 ℃ to form a nanogold-modified polystyrene microsphere film which is uniform in electric conduction, transparent and compact;
4. further transferring the polystyrene microsphere film obtained in the step 3 to any solid interface;
5. and (3) standing the nano-gold modified polystyrene microsphere film obtained in the step (4), drying, and repeating the step (4) to obtain the self-supporting ultrathin nano-gold modified polystyrene microsphere film with uniform thickness, wherein the thickness of the nano-gold modified polystyrene microsphere film is 5 micrometers, the surface roughness of the nano-gold modified polystyrene microsphere film is less than 1.5nm, and the light transmittance of the nano-gold modified polystyrene microsphere film is greater than 86%.
Tests prove that the nano gold modified polystyrene microsphere film prepared by the embodiment has good comprehensive performance and can be widely used on optical and electrical devices. Meanwhile, the method has the advantages of simple process flow, convenient operation, low requirement on environmental factors, no influence and capability of meeting the requirements of large-area and large-batch industrial production.
Example 3
1. Taking a certain amount of carbon black nanoparticles, and performing ultrasonic dispersion by using a certain amount of propanol, wherein the concentration is 0.005 mg/mL;
2. spraying the nano carbon black particle dispersion liquid obtained in the step 1The container is sprayed to the chloroform interface at a spray rate of 500ml/min, and the size of the sprayed liquid drops is 5 x 10 during spraying-2mm, and then pumping the solution out at the speed of 10mL/min through a peristaltic pump, thereby forming a nano carbon black film with the thickness of 50-300 nm;
3. extruding the uniform and transparent carbon black nano-film obtained in the step 2 for 30s by a method of sucking interfacial liquid through objects such as a peristaltic pump and the like at a pressure of 7.5mN/m, and self-assembling for 10s at 100 ℃ to form a uniform, transparent and compact conductive carbon black nano-particle film;
4. further transferring the nano carbon black particle film obtained in the step 3 to any solid interface;
5. and (4) standing the nano carbon black particle film obtained in the step (4), drying, and repeating the step (4), thereby obtaining the self-supporting ultrathin uniform-thickness nano carbon black particle film with the thickness of 50 nm.
Tests prove that the carbon black particle film prepared by the embodiment has good comprehensive performance, the roughness is less than 1.5nm, the transparency can be higher than 86%, the conductivity is higher than 500-3000 s/m, and the carbon black particle film can be widely used on optical and electrical devices. Meanwhile, the method has the advantages of simple process flow, convenient operation, low requirement on environmental factors, no influence and capability of meeting the requirements of large-area and large-batch industrial production.
Example 4
1. Taking a certain amount of nano-silver modified silicon dioxide nano-particles, and performing ultrasonic dispersion by using a certain amount of glycerol, wherein the concentration is 0.05 mg/mL;
2. spraying the nano-silver modified silicon dioxide nano-particle dispersion liquid obtained in the step 1 to the interface of the ionic liquid through a sprayer at a spraying speed of 100ml/min, wherein the size of sprayed liquid drops is 8 x 10 in the spraying process-2mm, and then pumping the solution at the speed of 15mL/min by a peristaltic pump, thereby forming the nano-silver modified silicon dioxide nano-particle film;
3. extruding the uniform and transparent nano-silver modified silicon dioxide nano-particle film obtained in the step 2 for 20s by a method of sucking interfacial liquid through objects such as a peristaltic pump and the like under the pressure of 7.6mN/m, and self-assembling for 100s at the temperature of 80 ℃ to form a uniform, transparent and compact conductive nano-silver modified silicon dioxide nano-particle film;
4. further transferring the nano-silver modified silicon dioxide nano-particle film obtained in the step 3 to any solid interface;
5. and (4) standing the nano-silver modified silicon dioxide nano-particle film obtained in the step (4), drying, and repeating the step (4), thereby obtaining the self-supporting ultrathin nano-silver modified silicon dioxide nano-particle film with uniform thickness, wherein the thickness of the self-supporting ultrathin nano-silver modified silicon dioxide nano-particle film is 20 nm.
Tests prove that the nano-silver modified silicon dioxide nano particle film prepared by the embodiment has good comprehensive performance, the roughness is less than 1.5nm, the transparency can be higher than 86%, the conductivity is higher than 500-3000 s/m, and the nano-silver modified silicon dioxide nano particle film can be widely applied to optical and electrical devices. Meanwhile, the method has the advantages of simple process flow, convenient operation, low requirement on environmental factors, no influence and capability of meeting the requirements of large-area and large-batch industrial production.
Comparative example
The comparative example adopts the traditional knife coating method to prepare the nano carbon black film
1. Taking a certain amount of nano carbon black particles, and carrying out ultrasonic dispersion on the nano carbon black particles by using a certain polymer solution (such as a triethyl phosphate solution of 2% PVDF), wherein the concentration is 0.05 mg/mL;
2. and (3) preparing the nano carbon black particle dispersion liquid obtained in the step (1) on the surface of polytetrafluoroethylene by a blade coating method.
3. Standing and drying the nano carbon black particle film obtained in the step 2 to obtain a carbon black particle film, and drying to form a nano carbon black film with the thickness of 5-100 um;
4. further transferring the nano carbon black particle film obtained in the step 3 to any solid interface;
5. and (4) standing the nano carbon black particle film obtained in the step (4), drying, and repeating the step (4) to obtain the self-supporting carbon black particle composite film.
The film obtained by the method has the roughness of more than 1 mu m, the transparency of less than 10 percent, almost no conductivity and difficult transfer through tests.
By the technical scheme, the nano/micron particles and the modified film thereof prepared by the invention have good comprehensive performance and can be widely used on optical and electric devices; meanwhile, the preparation process is simple in flow, convenient to operate, low in requirement on environmental factors, free of any influence and capable of meeting the requirements of large-area and large-batch industrial production.
In addition, the inventor also uses other raw materials and other process conditions listed above to replace various raw materials and corresponding process conditions in examples 1-4 to perform corresponding experiments, and the obtained ultra-thin transparent nano/micro structure self-assembled film has ideal morphology, performance and the like, and is basically similar to the product in example 1.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A green preparation method of an ultrathin transparent nano/micron structure self-assembled film is characterized by comprising the following steps:
(1) dispersing a nano/micro structure and/or nano/micro structure modifier in a first liquid phase system to form a nano/micro structure dispersion liquid, wherein the concentration of the nano/micro structure dispersion liquid is 0.005 mg/mL-2.0 mg/mL, the nano/micro structure modifier is formed by blending or grafting a nano/micro structure and a modifier, the nano/micro structure modifier is an organic substance and/or an inorganic substance, and the nano/micro structure modifier comprises a modifying group selected from-NH and2any one or the combination of more than two of-COOH and-OH, wherein the nano/micron structure is selected from nano/micron particles and/or nano/micron lines, and the nano/micron particles are selected from any one or the combination of more than two of metal nanoparticles, metal and/or non-metal oxide particles and polymer particles;
(2) spraying the nano/micron structure dispersion liquid onto the surface of a second liquid phase system in a spraying mode, wherein the spraying speed is 5 ml/min-500 ml/min, and the size of sprayed liquid drops is 5 x 10 in the spraying process-3 mm ~ 5*10-1mm, after the first liquid phase system volatilizes, removing the second liquid phase system to obtain the nano/micron structure film;
(3) extruding the nano/micro structure film by using the surface tension of the liquid, wherein the time of the extrusion is 5-60 s, the pressure adopted by the extrusion is 7.2-7.8 mN/m, so that the nano/micro structure film is self-assembled on a gas-liquid interface to form a compact and stable nano/micro structure film, the nano/micro structure self-assembled film with a uniformly controllable structure is obtained, the self-assembly temperature of the nano/micro structure film on the gas-liquid interface is 20-100 ℃, and the time is 10-1000 s;
the dispersity of the nano/micro structure and/or nano/micro structure modifier in a first liquid phase system is larger than that in a second liquid phase system, and the first liquid phase system is not mutually soluble with the second liquid phase system, the first liquid phase system is selected from any one or combination of more than two of ethanol, propanol, glycerol and water, and the second liquid phase system is selected from any one or combination of more than two of water, carbon disulfide, chloroform and ionic liquid;
the thickness of the ultrathin transparent nano/micron structure self-assembled film is 20 nm-10 mu m, the surface roughness is less than 1.5nm, the light transmittance is greater than 86%, and the film comprises a nano/micron structure array and/or a nano/micron structure network which are formed by nano/micron structures and/or modified substances of the nano/micron structures.
2. The production method according to claim 1, characterized by comprising: when the nano/micron structure dispersion liquid is sprayed on the surface of the second liquid phase system, the generated spraying area is the same as the film forming area of the prepared nano/micron structure film.
3. The production method according to claim 1, characterized by comprising: removing the second liquid phase system by adopting a peristaltic pump pumping mode; and the speed of pumping the second liquid phase system by adopting a peristaltic pump is 5 mL/min-20 mL/min.
4. The production method according to any one of claims 1 to 3, characterized by further comprising step (4): and transferring the ultrathin transparent nano/micron structure self-assembly film to a selected interface for self-assembly to form a hybrid film self-assembled by nano film layers with different structures, wherein the hybrid film comprises at least one nano/micron structure or a nano/micron structure modifier.
5. The method of claim 4, wherein: the preparation method further comprises the following steps: repeating the step (3) and/or the step (4) for more than two times in a circulating way until the required ultrathin transparent nano/micron structure self-assembled film is obtained; the cycle number is 5-10.
6. The method of claim 4, wherein: the selected interface is a solid phase interface or a liquid phase interface.
7. The method of claim 1, further comprising: adding a modifier with a nano/micro structure and/or a nano/micro structure into a first liquid phase system, and performing ultrasonic dispersion to form nano/micro structure dispersion liquid; the ultrasonic dispersion time is 0.5-20 h.
8. The method of claim 1, wherein: the metal nanoparticles are selected from gold nanoparticles and/or silver nanoparticles.
9. The method of claim 1, wherein: the metal and/or nonmetal oxide particles are selected from any one or a combination of more than two of silicon dioxide nanoparticles, titanium dioxide nanoparticles and ferroferric oxide magnetic nanoparticles.
10. The method of claim 1, wherein: the polymer particles are polystyrene microspheres.
11. Use of the ultra-thin transparent nano/micro structure self-assembled film prepared by the preparation method of any one of claims 1-10 in preparation of super-hydrophobic coatings, nano or micro ordered arrays, nano particles or nano wires self-assembled materials, nano catalyst materials or raman enhancement materials.
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