CN110935607A - Method for preparing structural color material by ultrasonic spraying - Google Patents
Method for preparing structural color material by ultrasonic spraying Download PDFInfo
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- CN110935607A CN110935607A CN201911190302.9A CN201911190302A CN110935607A CN 110935607 A CN110935607 A CN 110935607A CN 201911190302 A CN201911190302 A CN 201911190302A CN 110935607 A CN110935607 A CN 110935607A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
- B05D3/104—Pretreatment of other substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
- B05D5/065—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects having colour interferences or colour shifts or opalescent looking, flip-flop, two tones
- B05D5/066—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects having colour interferences or colour shifts or opalescent looking, flip-flop, two tones achieved by multilayers
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Abstract
The invention relates to a method for preparing a structural color material by ultrasonic spraying, belonging to the field of preparation of new chromogenic materials. The invention forms a layered structure material on a substrate by inorganic nano particles respectively or alternately, and adds a surfactant component to assist the nano particles to form a film. The invention can well solve the problems of difficult patterning and incapability of amplification in the preparation process of the traditional structure chromogenic material, greatly improves the utilization efficiency of raw materials, better controls the thickness growth of a nanoparticle layer, better reduces the surface roughness of the coating of the obtained product, and can also realize multiple patterning preparation on the same substrate by an alternative method. The structural color-generating material prepared by the method is wide in applicable raw materials, comprises organic and inorganic nano particles, and has various preparation areas and shapes, so that the structural color-generating material has a good application prospect in the fields of coating, display and the like, and the preparation method can be combined with factories to realize industrial production.
Description
Technical Field
The invention belongs to the technical field of preparation of new chromogenic materials, and relates to a method for preparing a structural color material by ultrasonic spraying.
Background
Structural colors (also called physical colors) are colors generated by light refraction, diffusion reflection, diffraction or interference in some very thin fine structures. Compared with the plain color, the color filter has the advantages of high brightness, high saturation and difficult fading. The structural color material comprises a film interference material and a photonic crystal material, and structurally, the one-dimensional photonic crystal and the film interference are similar and are both spread on a plane, and light waves are interfered in the direction vertical to the plane, and the difference is that the former is a periodic dielectric structure consisting of two mediums with different refractive indexes, so that the common film interference material is difficult to prepare. The two structural color materials have simple structure and wide material selection, and have wide application prospect in the fields of display, coating and anti-counterfeiting, and the related research caused by the two structural color materials is increased day by day.
For preparing the one-dimensional structure color material, in terms of material selection, nanoparticle sol is mostly adopted as a raw material for realizing the functionality, and a polymer film can also be adopted. In the prior art, there are many methods for depositing one-dimensional thin films, such as: sol-gel methods, magnetron sputtering methods, chemical vapor deposition methods (CVD), atomic layer deposition methods, chemical deposition methods, and the like. In the sol-gel method, the film quality is affected by temperature and humidity, and a volatile solvent is required to be used, so that the thickness control of the film is also difficult. Magnetron sputtering, atomic layer deposition and CVD are all performed under vacuum, requiring high manufacturing costs and expensive equipment. The chemical deposition process, although it can be carried out at atmospheric pressure, requires the use of TiF6And the like are non-environmentally friendly solvents.
In the early 1991, Decher and hong introduced a layer-by-layer (LBL) manufacturing technique of multilayer thin films, i.e. the dipping method, which is based on the alternating adsorption of charged materials in aqueous solution by electrostatic attraction. The method has the outstanding characteristics of self-assembly process, including simple process, water-based deposition under normal temperature and pressure, controllable thickness and the like, but has the defects that the whole process depends on diffusion drive, the assembly period is too long, and large-area assembly is difficult. Also known as a self-assembly method is spin coating, which is a common assembly method in laboratories, and films with different thicknesses are obtained by changing the rotation speed and the solution concentration, but large-area assembly is difficult, and the waste of raw materials is very serious because of the mechanism limited to the introduction and removal of excess solution. Based on the principle of the dipping method, a spraying method is developed as a new method for realizing roll-to-roll large-area preparation by saving assembly time, but the method still stays in an assembly mode of a large-area liquid film, and the introduced excessive raw materials need to be cleaned by rinsing, so that the raw materials are wasted, direct patterning is difficult to realize, and the control of the film thickness is not very accurate.
In view of the defects of the prior art in preparing large-area patterned one-dimensional structure color films, an assembly idea needs to be converted, the advantages of being easy to realize and combined with industrial roll-to-roll processing by combining a spraying method are combined, and the idea of trace spraying is introduced, so that the process is accurately controlled, the assembly process is simple, the assembly condition is mild, and the utilization efficiency of raw materials is improved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a structural color material by ultrasonic spraying. The method has the advantages that the process is accurately controlled by adopting trace spraying, the surfactant is introduced, the uniformity of the formed polymer nano particle or inorganic nano particle coating is greatly improved, two different operation processes are combined, after drying and curing, the structural color material with beautiful color, low surface roughness, rich patterns and flexible area is obtained, and the whole process takes water as a solvent and is environment-friendly.
A method for preparing a structural color material by ultrasonic spraying comprises the following steps:
step 1) preparation of inorganic nanoparticle dispersion
Diluting the inorganic nano-particle dispersion liquid stock solution or the inorganic nano-particle powder by using deionized water, performing ultrasonic dispersion for 10-30 min, and filtering to remove particles with the particle size of more than 220nm to obtain the diluted inorganic nano-particle dispersion liquid.
The inorganic nano-particles are titanium dioxide, silicon dioxide, zirconium dioxide or zinc oxide.
Step 2) preparing a dilute surfactant solution
Diluting the surfactant powder with deionized water, and performing ultrasonic dispersion for 10-30 min to obtain a surfactant dilute solution.
The surfactant is polyvinylpyrrolidone, polyethylene glycol, sodium dodecyl benzene sulfonate, stearic acid, alkyl glucoside, fatty glyceride, sorbitan fatty acid ester or polysorbate (also called structure directing agent); polyvinylpyrrolidone and polyethylene glycol are preferred.
Step 3) preparing structural color material by ultrasonic spraying
Mixing the diluted inorganic nano dispersion liquid obtained in the step 1) with the surfactant diluent obtained in the step 2), adding deionized water for dilution, and performing ultrasonic dispersion for 10-30 min to obtain a raw material liquid; in the raw material liquid, the mass percentage concentration of the inorganic nano particles is 0.01 wt% -0.4 wt%, and more preferably 0.05 wt% -0.2 wt%; the mass percentage concentration of the surfactant is 0.001 wt% -0.1 wt%, and more preferably 0.005 wt% -0.05 wt%; the mass ratio of the inorganic nanoparticles to the surfactant is 10: 1-1: 1.
Adopting a silicon wafer as a substrate, and carrying out plasma cleaning treatment on the substrate, wherein the cleaning gas is nitrogen, ammonia or air, and the cleaning time is 30-300 s; preferably, the cleaning gas is nitrogen, and the cleaning time is 60-120 s.
Then, assembling on the substrate by adopting an ultrasonic spraying method, which comprises the following steps: spraying the raw material liquid on a substrate by an ultrasonic spraying machine, controlling the temperature of the substrate to be 35-60 ℃, and controlling the spraying times to be 1-20 (preferably 5-15); independently assembling an inorganic nanoparticle layer on a substrate, or alternately assembling two different inorganic nanoparticle layers, drying a sample at 25-150 ℃ for 1-60 min (preferably at 90-110 ℃ for 5-10 min), then assembling the next layer, and drying and curing at 90-110 ℃ for 5-60 min on a heating plate after all the assemblies are finished to obtain a structural color material; when the single assembly is carried out, after the complete assembly is finished, the drying and curing are carried out, and then the surfactant component is removed by processing at 300-1000 ℃ for 30-180 min (more preferably, the processing at 400-500 ℃ is carried out for 60-120 min).
When preparing the inorganic nano dispersion liquid, the average particle diameter of the particles in the inorganic nano dispersion liquid is 10 nm-80 nm, and the PDI (polymer dispersibility index) of the particles in the inorganic nano dispersion liquid is not more than 0.30.
In the preparation process, a surfactant is added and the substrate is subjected to plasma cleaning, so that the wettability of a liquid film is increased, the surface tension of the liquid is reduced, and the nanoparticles are connected to form a film.
During assembly, the assembly is from bottom to top in a direction perpendicular to the plane of the substrate. When the multi-layer materials are assembled layer by layer, the upper layer is used as a new substrate of the next layer, and the principle is the same as the above.
The structural color-generating material prepared by the invention is a material with a certain angle dependence of structural color.
The invention has the beneficial effects that: the preparation method of the structural chromogenic material has the advantages of simple preparation method, beautiful color, direct patterning, flexible preparation area and the like. The invention can well solve the problems of difficult patterning and incapability of amplification in the preparation process (dipping method, spin coating method and the like) of the traditional structure chromogenic material, greatly improves the utilization efficiency (more than 90 percent) of raw materials, better controls the thickness growth of a nanoparticle layer, better reduces the surface roughness of the coating of the obtained product, and can realize multiple patterning preparation on the same substrate by an alternative method. The structural color-generating material prepared by the invention is wide in applicable raw materials, comprises organic and inorganic nano particles, and has various preparation areas and shapes, so that the structural color-generating material has a good application prospect in the fields of coating, display and the like, and the preparation method can be combined with roll-to-roll processing of factories to realize industrial production.
Drawings
FIG. 1 is an SEM image of the structural color-producing material obtained in example 1.
FIG. 2 is a reflectance spectrum of the structure color-producing material obtained in example 2.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Weighing 0.5g of titanium dioxide nano powder, adding deionized water to 100g, dispersing for 30min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyvinylpyrrolidone, adding deionized water to 100g, and dispersing and dissolving for 10min by an ultrasonic cleaning machine for later use.
Weighing 10g of titanium dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyvinylpyrrolidone dilute solution, adding the titanium dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the titanium dioxide nano dispersion liquid to 100g, and performing ultrasonic dispersion for 20min to obtain a raw material liquid, wherein the mass ratio of the inorganic nano particles to the surfactant is 5: 1.
The substrate material used in the experiment was subjected to hydrophilic treatment in a plasma cleaner using nitrogen as the feed gas for 60 seconds. And (3) carrying out ultrasonic spraying on the raw material liquid, respectively and continuously spraying the raw material liquid on a silicon wafer for 5, 6, 7 and 8 times under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 35 ℃, and placing the silicon wafer on a heating plate at 25 ℃ for 1 hour after the spraying is finished, drying and curing to prepare the structural color film.
And then treating the mixture in a muffle furnace at 300 ℃ for 180min to remove the surfactant component in the mixture, thus obtaining the pure inorganic nano-particle structural color material.
FIG. 1 is an SEM image of a structure color-producing material obtained in example 1, which was coated with TiO 7 times2Scanning electron microscope with PVP complex filmThe photograph shows a coating thickness of 120nm and a refractive index of about 1.9 was measured.
Example 2
Weighing 1g of concentrated solution of silicon dioxide nano dispersion liquid (mass fraction is 30%), adding deionized water until the total mass is 60g, dispersing for 20min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyvinylpyrrolidone, adding deionized water to 100g, and dispersing and dissolving for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of silicon dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 5g of the polyvinylpyrrolidone dilute solution, adding the silicon dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the mixture to 100g, and performing ultrasonic dispersion for 30min to obtain a raw material liquid, wherein the mass ratio of the inorganic nano particles to the surfactant is 10: 1.
The substrate material used in the experiment is subjected to hydrophilic treatment in a plasma cleaning machine by using nitrogen as raw material gas, and the cleaning time is 120 s. And (3) carrying out ultrasonic spraying on the raw material liquid, respectively and continuously spraying 10, 12, 13 and 15 times on a silicon wafer under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 60 ℃, and placing on a heating plate at 150 ℃ for 1min after the spraying is finished, drying and curing to prepare the structural color film.
And then treating in a muffle furnace at 1000 ℃ for 30min to remove the surfactant component in the material, thus obtaining the pure nano-particle structural color material.
FIG. 2 is a reflection spectrum of the structure color-generating material obtained in example 2, in which the position of the maximum reflection peak is blue-shifted with the increase of the incident angle, and the interference rule of the thin film is satisfied.
Example 3
Weighing 1g of concentrated solution of zinc oxide nano dispersion liquid (mass fraction is 40%), adding deionized water until the total mass is 80g, dispersing for 10min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyethylene glycol, adding deionized water to 100g, and dispersing and dissolving for 20min by an ultrasonic cleaning machine for later use.
Weighing 10g of zinc oxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyethylene glycol dilute solution, adding into a beaker, adding deionized water to dilute to 100g, and performing ultrasonic dispersion for 10min to obtain a raw material solution, wherein the mass ratio of inorganic nano particles to the surfactant is 5: 1.
The substrate material used in the experiment is subjected to hydrophilic treatment in a plasma cleaning machine by using nitrogen as raw material gas, and the cleaning time is 300 s. And (3) carrying out ultrasonic spraying on the raw material liquid, continuously spraying for 5 times on a silicon wafer under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 45 ℃, and drying and curing the silicon wafer on a heating plate at 90 ℃ for 10min after the spraying is finished to prepare the structural color film.
And then treating the mixture in a muffle furnace at 500 ℃ for 120min to remove the surfactant component in the mixture, thus obtaining the pure nano-particle structural color material.
Example 4
Weighing 0.5g of zirconium dioxide nano powder, adding deionized water to 100g, dispersing for 10min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyethylene glycol, adding deionized water to 100g, and dispersing and dissolving for 10min by an ultrasonic cleaning machine for later use.
Weighing 10g of zirconium dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 50g of the polyethylene glycol dilute solution, adding into a beaker, adding deionized water to dilute to 100g, and performing ultrasonic dispersion for 10min until the mass ratio of inorganic nano particles to the surfactant in the raw material liquid is 1: 1.
The substrate material used in the experiment was subjected to hydrophilic treatment in a plasma cleaner using nitrogen as a raw material gas for 30 seconds. And (3) carrying out ultrasonic spraying on the raw material liquid, continuously spraying for 15 times on a silicon wafer under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 55 ℃, and drying and curing for 5min on a heating plate at 110 ℃ after the spraying is finished to prepare the structural color film.
And then treating the mixture in a muffle furnace at 400 ℃ for 60min to remove the surfactant component in the mixture, thus obtaining the pure nano-particle structural color material.
Example 5
Weighing 0.5g of titanium dioxide nano powder, adding deionized water to 100g, dispersing for 30min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyvinylpyrrolidone, adding deionized water to 100g, and dispersing and dissolving for 10min by an ultrasonic cleaning machine for later use.
Weighing 10g of titanium dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyvinylpyrrolidone dilute solution, adding the titanium dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the titanium dioxide nano dispersion liquid to 100g, and performing ultrasonic dispersion for 30min to obtain a raw material liquid, wherein the mass ratio of the inorganic nano particles to the surfactant is 5: 1.
The substrate material used in the experiment is subjected to hydrophilic treatment in a plasma cleaning machine by using nitrogen as raw material gas, and the cleaning time is 120 s. And (3) carrying out ultrasonic spraying on the raw material liquid, continuously spraying the raw material liquid on a silicon wafer for 20 times under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 60 ℃, and drying and curing the raw material liquid on a heating plate at 100 ℃ for 1h after the spraying is finished to prepare the structural color film.
And then treating the mixture in a muffle furnace at 400 ℃ for 120min to remove the surfactant component in the mixture, thus obtaining the pure nano-particle structural color material.
Example 6
Weighing 1g of concentrated solution of silicon dioxide nano dispersion (mass fraction is 30%), adding deionized water until the total mass is 60g, dispersing for 30min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyvinylpyrrolidone, adding deionized water to 100g, and dispersing and dissolving for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of silicon dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyvinylpyrrolidone dilute solution, adding the silicon dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the mixture to 100g, and performing ultrasonic dispersion for 30min to obtain a raw material liquid, wherein the mass ratio of the inorganic nano particles to the surfactant is 5: 1.
The substrate material used in the experiment is subjected to hydrophilic treatment in a plasma cleaning machine by using nitrogen as raw material gas, and the cleaning time is 120 s. And (3) carrying out ultrasonic spraying on the raw material liquid, continuously spraying 12 times on a silicon wafer under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 60 ℃, and drying and curing on a heating plate at 100 ℃ for 1h after the spraying is finished to prepare the structural color film.
And then treating the mixture in a muffle furnace at 450 ℃ for 120min to remove the surfactant component in the mixture, thus obtaining the pure nano-particle structural color material.
Example 7
Weighing 1g of concentrated solution of zinc oxide nano dispersion liquid (mass fraction is 40%), adding deionized water until the total mass is 80g, dispersing for 30min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyethylene glycol, adding deionized water to 100g, and dispersing and dissolving for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of zinc oxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyethylene glycol dilute solution, adding into a beaker, adding deionized water to dilute to 100g, and performing ultrasonic dispersion for 30min to obtain a raw material solution, wherein the mass ratio of the inorganic nano particles to the surfactant is 5: 1.
The substrate material used in the experiment is subjected to hydrophilic treatment in a plasma cleaning machine by using nitrogen as raw material gas, and the cleaning time is 120 s. And (3) carrying out ultrasonic spraying on the raw material liquid, continuously spraying for 7 times on a silicon wafer under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 60 ℃, and placing on a heating plate at 100 ℃ for 1h after the spraying is finished, drying and curing to prepare the structural color film.
And then treating the mixture in a muffle furnace at 500 ℃ for 60min to remove the surfactant component in the mixture, thus obtaining the pure nano-particle structural color material.
Example 8
Weighing 0.5g of zirconium dioxide nano powder, adding deionized water to 100g, dispersing for 30min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyethylene glycol, adding deionized water to 100g, and dispersing and dissolving for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of zirconium dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyethylene glycol dilute solution, adding the zirconium dioxide nano dispersion liquid and the polyethylene glycol dilute solution into a beaker, adding deionized water to dilute the zirconium dioxide nano dispersion liquid to 100g, and performing ultrasonic dispersion for 30min to obtain a raw material liquid, wherein the mass ratio of the inorganic nano particles to the surfactant is 5: 1.
The substrate material used in the experiment is subjected to hydrophilic treatment in a plasma cleaning machine by using nitrogen as raw material gas, and the cleaning time is 120 s. And (3) carrying out ultrasonic spraying on the raw material liquid, continuously spraying 8 times on a silicon wafer under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 60 ℃, and drying and curing the silicon wafer on a heating plate at 100 ℃ for 30min after the spraying is finished to prepare the structural color film.
And then treating the mixture in a muffle furnace at 400 ℃ for 60min to remove the surfactant component in the mixture, thus obtaining the pure nano-particle structural color material.
Example 9
Weighing 0.5g of titanium dioxide nano powder, adding deionized water to 100g, dispersing for 30min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyvinylpyrrolidone, adding deionized water to 100g, and dispersing and dissolving for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of titanium dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyvinylpyrrolidone dilute solution, adding the titanium dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the titanium dioxide nano dispersion liquid to 100g, and performing ultrasonic dispersion for 30min to obtain a raw material liquid T, wherein the mass ratio of inorganic nano particles to a surfactant is 5: 1.
Weighing 1g of concentrated solution of silicon dioxide nano dispersion liquid (mass fraction is 30%), adding deionized water until the total mass is 60g, and dispersing for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of silicon dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyvinylpyrrolidone dilute solution, adding the silicon dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the mixture to 100g, ultrasonically dispersing the mixture for 30min, and filtering the mixture by using a 220nm filter membrane to obtain a raw material liquid S, wherein the mass ratio of inorganic nano particles to a surfactant is 5: 1.
The substrate material used in the experiment is subjected to hydrophilic treatment in a plasma cleaning machine by using nitrogen as raw material gas, and the cleaning time is 120 s. And (2) spraying the raw material liquid T on a substrate for 5 times by ultrasonic spraying under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 35 ℃, then heating and drying on a heating plate at 100 ℃ for 5min, then spraying the raw material liquid S by using the same operation conditions, alternately stacking TS for 1, 2 and 3 stacks, and after the spraying is finished, placing on the heating plate at 90 ℃ for 1h, drying and curing to prepare the structural color film.
Example 10
Weighing 0.5g of titanium dioxide nano powder, adding deionized water to 100g, dispersing for 30min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyvinylpyrrolidone, adding deionized water to 100g, and dispersing and dissolving for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of titanium dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyvinylpyrrolidone dilute solution, adding the titanium dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the titanium dioxide nano dispersion liquid to 100g, and performing ultrasonic dispersion for 30min to obtain a raw material liquid T, wherein the mass ratio of inorganic nano particles to a surfactant is 5: 1.
Weighing 1g of concentrated solution of silicon dioxide nano dispersion liquid (mass fraction is 30%), adding deionized water until the total mass is 60g, and dispersing for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of silicon dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyvinylpyrrolidone dilute solution, adding the silicon dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the mixture to 100g, ultrasonically dispersing the mixture for 30min, and filtering the mixture by using a 220nm filter membrane to obtain a raw material liquid S, wherein the mass ratio of inorganic nano particles to a surfactant is 5: 1.
The substrate material used in the experiment is subjected to hydrophilic treatment in a plasma cleaning machine by using nitrogen as raw material gas, and the cleaning time is 120 s. And (3) spraying the raw material liquid T on a substrate for 5 times by ultrasonic spraying under the spraying conditions of liquid inlet speed of 0.1mL/min, ultrasonic frequency of 120kHz and substrate temperature of 35 ℃, then heating and drying on a heating plate at 100 ℃ for 5min, adding a patterned mask on the sprayed sample, then spraying the raw material liquid S by using the same operation conditions, and after the spraying is finished, placing on the heating plate at 110 ℃ for 5min, drying and curing to prepare the structural color film with patterns.
Example 11
Weighing 0.5g of titanium dioxide nano powder, adding deionized water to 100g, dispersing for 30min by an ultrasonic cleaning machine, and filtering by using a 220nm filter membrane for later use.
Weighing 0.1g of polyvinylpyrrolidone, adding deionized water to 100g, and dispersing and dissolving for 30min by an ultrasonic cleaning machine for later use.
Weighing 10g of titanium dioxide nano dispersion liquid with the mass fraction of 0.5 wt% and 10g of the polyvinylpyrrolidone dilute solution, adding the titanium dioxide nano dispersion liquid and the polyvinylpyrrolidone dilute solution into a beaker, adding deionized water to dilute the titanium dioxide nano dispersion liquid to 100g, and performing ultrasonic dispersion for 30min to obtain a raw material liquid, wherein the mass ratio of the inorganic nano particles to the surfactant is 5: 1.
Carrying out hydrophilic treatment on a substrate material used for an experiment in a plasma cleaning machine by using nitrogen as a raw material gas, wherein the cleaning time is 120s, attaching a part of area of the obtained substrate by using a high-temperature resistant adhesive tape, carrying out ultrasonic spraying on the raw material liquid, continuously spraying for 5 times on a silicon wafer under the spraying conditions of a liquid inlet speed of 0.1mL/min, an ultrasonic frequency of 120kHz and a substrate temperature of 60 ℃, tearing off the high-temperature resistant adhesive tape after the spraying is finished, and placing a sample on a heating plate at 100 ℃ for 1h for drying and curing to prepare a structural color film with patterns.
Claims (5)
1. A method for preparing a structural color material by ultrasonic spraying is characterized by comprising the following steps:
step 1) preparation of inorganic nanoparticle dispersion
Diluting the inorganic nano-particle dispersion liquid stock solution or the inorganic nano-particle powder by using deionized water, performing ultrasonic dispersion for 10-30 min, and filtering to remove particles with the particle size of more than 220nm to obtain diluted inorganic nano-particle dispersion liquid;
step 2) preparing a dilute surfactant solution
Diluting surfactant powder with deionized water, and performing ultrasonic dispersion for 10-30 min to obtain a dilute surfactant solution;
step 3) preparing structural color material by ultrasonic spraying
Mixing the diluted inorganic nano dispersion liquid obtained in the step 1) with the surfactant diluent obtained in the step 2), adding deionized water for dilution, and performing ultrasonic dispersion for 10-30 min to obtain a raw material liquid; in the raw material liquid, the mass percentage concentration of the inorganic nanoparticles is 0.01-0.4 wt%, the mass percentage concentration of the surfactant is 0.001-0.1 wt%, and the mass ratio of the inorganic nanoparticles to the surfactant is 10: 1-1: 1;
adopting a silicon wafer as a substrate, and carrying out plasma cleaning treatment on the substrate, wherein the cleaning time is 30-300 s; the cleaning time is 60-120 s;
then, assembling on the substrate by adopting an ultrasonic spraying method, which comprises the following steps: spraying the raw material liquid on a substrate by an ultrasonic spraying machine, controlling the temperature of the substrate to be 35-60 ℃, and the spraying times to be 1-20; independently assembling one inorganic nanoparticle layer on a substrate or alternately assembling two different inorganic nanoparticle layers, drying a sample at 25-150 ℃ for 1-60 min after each group is assembled for one layer, then performing next layer assembly, and drying and curing at 90-110 ℃ for 5-60 min on a heating plate after all the layers are assembled to obtain a structural color material; when the single assembly is carried out, after the complete assembly is finished, the surface active agent is removed after the drying and curing, and the surface active agent is processed for 30min to 180min at the temperature of 300 ℃ to 1000 ℃.
2. The method for preparing the structural color material by ultrasonic spraying according to claim 1, wherein the inorganic nanoparticles are titanium dioxide, silicon dioxide, zirconium dioxide or zinc oxide; the surfactant is polyvinylpyrrolidone, polyethylene glycol, sodium dodecyl benzene sulfonate, stearic acid, alkyl glucoside, fatty glyceride, sorbitan fatty acid ester or polysorbate.
3. The method for preparing the structural color material by ultrasonic spraying according to claim 1 or 2, wherein the mass percent concentration of the inorganic nanoparticles in the raw material liquid is 0.05 wt% to 0.2 wt%, and the mass percent concentration of the surfactant is 0.005 wt% to 0.05 wt%.
4. The method for preparing structural color material by ultrasonic spraying according to claim 1 or 2,
carrying out plasma cleaning treatment on the substrate, wherein the cleaning gas is nitrogen, ammonia or air, and the cleaning time is 60-120 s;
when the substrate is assembled by adopting an ultrasonic spraying method, the number of spraying times is 5-15; after assembling one layer, drying the sample at 90-110 ℃ for 5-10 min; when the single assembly is carried out, after the complete assembly is finished, the surface active agent component is removed by processing for 60min to 120min at the temperature of 400 ℃ to 500 ℃ after drying and curing.
5. The method for preparing structural color material by ultrasonic spraying according to claim 3,
carrying out plasma cleaning treatment on the substrate, wherein the cleaning gas is nitrogen, ammonia or air, and the cleaning time is 60-120 s;
when the substrate is assembled by adopting an ultrasonic spraying method, the number of spraying times is 5-15; after assembling one layer, drying the sample at 90-110 ℃ for 5-10 min; when the single assembly is carried out, after the complete assembly is finished, the surface active agent component is removed by processing for 60min to 120min at the temperature of 400 ℃ to 500 ℃ after drying and curing.
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