阅读说明：本技术 一种二氧化硅纳米银线减反射薄膜的制备方法 (Preparation method of silicon dioxide nano silver wire antireflection film ) 是由 王旭 田瑞岩 于 2019-04-08 设计创作，主要内容包括：本发明涉及了一种二氧化硅纳米银线减反射薄膜的制备方法,以乙二醇为还原剂和溶剂、硝酸银为根源,FeCL3·6H2O氯化铁为络合诱导剂,PVP活性引发剂结构调节、制备出直径10-30 nm的纳米银线,然后在乙醇中以二氧化硅为壳层包覆纳米银线制备出壳层结构的纳米复合材料AgSiO2,再次加入甲醇和超纯水溶液混合均匀后用孔径为减压抽滤,得到薄膜通过热压法转移至经过亲水改性的PET上丙酮洗去滤膜。(The invention relates to a preparation method of a silicon dioxide nano silver wire antireflection film, which takes ethylene glycol as a reducing agent and a solvent, silver nitrate as a root source, FeCl 3.6H2O ferric chloride as a complexing inducer, PVP active initiator structure adjustment and preparation of a nano silver wire with the diameter of 10-30 nm, then the nano silver wire is coated by silicon dioxide as a shell layer in ethanol to prepare a nano composite material AgSiO2 with a shell layer structure, methanol and an ultrapure aqueous solution are added again to be uniformly mixed, and then the mixture is subjected to vacuum filtration by using aperture under reduced pressure, so that the obtained film is transferred to hydrophilic modified PET by a hot pressing method and washed by acetone to remove a filter membrane.)

1. The method for preparing a silica nano silver wire antireflection film according to claim 1, characterized in that the preparation method comprises the steps of:

s1, performing hydrophilic treatment on the surface of the PET;

s2, pouring 5g of PVP into a magnetic stirrer filled with 200 mL of Ethylene Glycol (EG), when gel-like soft bodies are generated and attached to the wall of a beaker, flushing the gel-like soft bodies with a certain amount of EG, and pouring the gel-like soft bodies into a three-neck flask to obtain a solution A;

s3, after oil bath heating and stabilization, adding mixed solution of AgCI and AgNO3, adding glycol solution again, and finally mixing, stirring and dissolving the mixed solution and a certain amount of EG respectively to obtain solution B;

s4, slowly adding the solution B into the solution A drop by drop, gradually changing the solution from a colorless transparent state to a light blue colloid state, and stopping the reaction after continuously heating for 10min after the solution finally becomes a milky solution with metallic luster;

s5, standing and naturally cooling, taking out the supernatant, wherein the lower precipitate is the nano-silver wire, washing the precipitate for several times by using ethanol if the precipitate is complete, and dissolving the precipitate in the ethanol for later use, and after the precipitate is not complete, centrifuging the supernatant for 3-4 times to obtain the precipitate, cleaning and storing by using the ethanol;

s6, taking a proper amount of nano-silver wires into a three-neck flask by using a liquid-transferring gun, preparing silicon dioxide by using ethanol, ammonia water, Tetraethoxysilane (TEOS) and octodecamegaohm water according to a certain proportion, adding a nano-silver wire solution, placing the three-neck flask on a magnetic stirrer, and stirring for 1 hour at room temperature to obtain sol;

s7, centrifuging the product again to obtain nano Ag SiO2 with certain coating thickness; s8, carrying out reduced pressure suction filtration by using a mixed cellulose filter membrane with a nano aperture to obtain a film, transferring the film onto a treated PET substrate by a hot pressing method, and removing the filter membrane by using an acetone bath to realize transfer.

2. The method for preparing the silicon dioxide nano silver wire antireflection film according to claim 1, wherein the preparation method comprises the following steps, and is characterized in that the PET pretreatment in the step S1 comprises the steps of soaking in ethanol for 20 hours, ultrasonically cleaning for 10min, and airing; and then soaking the PET in 1moI/L NaOH solution, treating for a certain time at 50 ℃, rinsing with ultrapure water for 3 times by using 0.1mol/L HCI, placing in 60 ℃ saturated glutamic acid solution for reacting for 6 hours, and taking out and drying.

3. The method as claimed in claim 1, wherein the value PVP (MW = 24000-.

4. The method for preparing the silica nano silver wire antireflection film according to claim 1, wherein in the step S3, after the film is heated in oil bath at 170 ℃ for 1H for stabilization, 0.35g of Ag/H12Cl3FeO6 is added, and after 12min, 1.5g of AgNO3 is weighed and mixed with ethylene glycol solution, and the ethylene glycol solution and a certain amount of EG are mixed, stirred and dissolved respectively; the concentration of H12Cl3FeO6 is 8 mM, the reaction time is 40 min, and the dosage of the control agent is 5-7.

5. The method for preparing a silica nano silver wire antireflection film according to claim 1, wherein said step S5 is: and (3) centrifuging the silver wire precipitate according to the weighting measure, washing the precipitate for a plurality of times by using ethanol, centrifuging again, wherein the rotating speed of a rotor is 600-1200r/min in the reaction process, the reaction color is changed from yellow to orange, and finally to grey white, adding acetone agent which is 3-5 times of the reaction solution into the reaction solution, and carrying out ultrasonic cleaning.

6. The method for preparing a silica nano silver wire antireflection film according to claim 1; it is characterized in that, in the step S6, the absolute ethyl alcohol, the ammonia water, the Tetraethoxysilane (TEOS) and the eighteen megaohms water are added according to the ratio of 20: 1.5:0.8: and (3) blending by 30 proportion.

7. The method for preparing a silica nano silver wire antireflection film according to claim 1; the method is characterized in that in the step S7, the product can be separated for 45min by a centrifuge at the rotation speed of 5000-10000 r/as required, the organic solvent adhesion is removed, the nano AgSiO2 is dissolved in a certain amount of methanol solution and ultrapure water to be mixed to prepare nano silver wire solution with a certain concentration, and the coating thickness of the SiO2 can be increased by repeating the experiment.

8. The method for preparing a silica nano silver wire antireflection film according to claim 1; characterized in that in the step S8, the filtration membrane is subjected to reduced pressure filtration by using a mixed cellulose reverse osmosis membrane or ceramic membrane having a pore size of 0.010 to 0.040um, and the pressure for membrane filtration カ is O.2 atm and 50 atm.

9. The method for preparing a silica nano silver wire antireflection film according to claim 1, wherein said step S8 is: the coating is uniform through the shell layer, and the thickness of the shell layer structure is about 50 nm; if the thickness of the SiO2 shell is to be increased, the method can be realized by repeating the experimental method of claim 1 in which the steps S2, S3, S4, S5 and S6 are coated with SiO 2.

Technical Field

The invention relates to the technical field of preparation of more than two metal molecular elements deposited on a substrate in a liquid-solid state manner, in particular to a preparation method of a silicon dioxide nano silver wire antireflection film, belonging to a coating ion crystal nucleus synthesis technology.

Background

As is well known, silver and copper are metallic conductors having the best electrical conductivity at normal temperature, and lead wires in daily life are made of copper. When silver and copper are made to be of a nanowire size, they exhibit different optical and electrical properties. As can be seen from the ultraviolet and visible spectrum absorption spectrogram, the absorption peak of the nano silver wire is about 380nm and belongs to the ultraviolet region, and the nano silver wire has no absorption basically in the visible light range (400 nm-780 nm), so the nano silver wire is basically transparent. Some studies show that as the diameter of the nano silver wire is reduced, the aspect ratio is increased, the absorption peak at 380nm is blue-shifted to 370nto or even 365nm, and the purer the nano silver wire is, the lower the absorption value of the solution in the visible light region (400 rim-780 nm) is, and the higher the light transmittance of the obtained transparent conductive film is.

Research shows that the one-dimensional growth of the nano silver wire is influenced by anions more obviously. This depends mainly on the difference in solubility (solubility product constant) of the product obtained by combining the anion and the silver ion, i.e., Ksp (AgCl) < Ksp (Ag 2S good 4) < Ksp (AgN good 3). The smaller the value of Ksp, the slower the reduction rate of Ag +, and the more favorable the anisotropic one-dimensional growth of multiple plum seed crystal synthesized into nano silver wire.

In the aspect of electrical performance, the longer the nano silver wire is, the more the nano silver wire may be lapped with one nano silver wire, and the whole nano silver wire network has more contacts, so that the number of electron transmission paths is increased, and the electrical conductivity is improved. Meanwhile, the conduction rate of electrons in the nano silver wire is far greater than that of electrons at the lap joint, so that the conductivity of the long-length nano silver wire network is better under the condition that the number of lap joints is the same.

Research shows that in the field of nano silver wire two-dimensional materials, the problems of low optical transmission performance and high film reflection performance exist in the antireflection film prepared by common silver materials at present. The antireflection film prepared from two-dimensional and three-dimensional nano silver materials has the problems that the plasma resonance effect is weak due to the micro morphology, the film has large scattering on incident light and the like. The nano silver wire film has more light through holes W in the film and has better antireflection performance due to stronger plasma resonance effect of the nano silver wire.

In addition, the nano-silica is non-toxic, tasteless and pollution-free, the particle size is small, the specific surface area is large, a large number of unsaturated bonds and hydroxyl groups in different bonding states exist on the surface, and the coating of the nano-silver wire can form a silicon dioxide-based nano-silver coating body or crystal, so that the performances such as cohesiveness, high temperature resistance, film forming property, gel property and charge property of the silicon dioxide-based nano-silver coating body or crystal are obviously improved.

Disclosure of Invention

In view of the above, the present invention provides a method for preparing a silicon dioxide nano silver wire antireflection film; in order to realize the aim, the invention discloses a preparation method of a silicon dioxide nano silver wire antireflection film; which comprises the following steps:

s1, performing hydrophilic treatment on the surface of the PET;

s2, pouring 5g PVP (MW = 50000) into a magnetic stirring device filled with 200 mL of Ethylene Glycol (EG), when gel-like soft bodies are generated and attached to the wall of a beaker, washing the beaker with a certain amount of EG, pouring the beaker into a three-neck flask to obtain a solution A,

s3, after oil bath heating and stabilization, adding the mixed solution of AgCI and AgNO3, adding the glycol solution again, and finally mixing, stirring and dissolving the mixed solution and a certain amount of EG respectively to obtain solution B;

s4, slowly adding the solution B into the solution A drop by drop, gradually changing the solution from a colorless transparent state to a light blue colloid state, and stopping the reaction after continuously heating for 10min after the solution finally becomes a milky solution with metallic luster;

s5, standing and naturally cooling, taking out the supernatant, wherein the lower precipitate is the nano-silver wire, washing the precipitate for several times by using ethanol if the precipitate is complete, and dissolving the precipitate in the ethanol for later use, and after the precipitate is not complete, centrifuging the supernatant for 3-4 times to obtain the precipitate, cleaning and storing by using the ethanol;

s6, taking a proper amount of nano-silver wires into a three-neck flask by using a liquid-transferring gun, preparing silicon dioxide by using ethanol, ammonia water, Tetraethoxysilane (TEOS) and octodecamegaohm water according to a certain proportion, adding a nano-silver wire solution, placing the three-neck flask on a magnetic stirrer, and stirring for 1 hour at room temperature to obtain sol;

s7, centrifuging the product again to obtain nano Ag SiO2 with certain coating thickness; s8, carrying out reduced pressure suction filtration by using a mixed cellulose filter membrane with a nano aperture to obtain a film, transferring the film onto a treated PET substrate by a hot pressing method, and removing the filter membrane by using an acetone bath to realize transfer.

As a further improvement of the invention, the PET surface is hydrophilically treated.

As a further improvement of the invention, 40mL of Dimethylformamide (DMF) and 10g of PVP are added to the vessel and stirred magnetically until the temperature is constant after heating to the target temperature.

As a further improvement of the present invention, 5g of PVP (MW = 50000) was poured into a magnetic stirrer containing 200 mL of Ethylene Glycol (EG), and when gel-like soft bodies had formed and adhered to the walls of the beaker, the gel-like soft bodies were rinsed with a certain amount of EG and poured into a three-necked flask to obtain solution A.

As a further improvement of the invention, after the oil bath is heated stably, the mixed solution of AgCI and AgNO3 is added, the glycol solution is added again, and finally, the mixed solution is mixed with a certain amount of EG respectively and stirred to obtain solution B.

As a further improvement of the invention: and slowly adding the solution B into the solution A dropwise, gradually changing the solution from a colorless transparent state to a light blue colloid state, and stopping the reaction after continuously heating for 10min after finally changing the solution into a milky solution with metallic luster.

The method is further improved by taking out supernatant liquor after standing and naturally cooling the liquor, wherein the lower-layer sediment is the nano silver wires, washing the sediment for a plurality of times by using ethanol if the sediment is complete, dissolving the sediment in the ethanol for standby, and washing and storing the sediment by using the ethanol after centrifuging the supernatant liquor for 3-4 times if the sediment is incomplete.

As a further improvement of the invention, a proper amount of nano silver wires are taken by a liquid-transferring gun and put into a three-neck flask, and then ethanol, ammonia water, Tetraethoxysilane (TEOS) and eighteen megaohms of water in a certain proportion are prepared into silicon dioxide, and then nano silver wire solution is added, and then the three-neck flask is placed on a magnetic stirrer and stirred for 1 hour at room temperature, thus obtaining the sol.

As a further improvement of the invention, the product is centrifuged again, and the nano Ag-SiO 2 with certain coating thickness is obtained after centrifugation.

As a further improvement of the invention, the membrane obtained by carrying out vacuum filtration by using a mixed cellulose filter membrane with nano-aperture is transferred to a treated PET substrate by a hot pressing method, and then the filter membrane is removed by using an acetone bath to realize the transfer.

Compared with the prior art, the invention has the beneficial effects that: in the prior art, a preparation method of a nano silver wire is a physical method which mainly represents an atomization method and an evaporation and condensation method, and a physical method has high requirements, low efficiency, large investment and larger industrialization requirements, so that a chemical method is a method which is mostly adopted by the current entrepreneurs or small and medium-sized enterprises, and is represented by a polyol method, a photoelectrochemical reduction method and the like, and is feasible due to simple operation, easy control of process and cost. In the method, a polyol method is adopted to prepare the silicon dioxide nano silver wire powder, solution and film.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

Fig. 1 is a schematic method flow diagram of a specific embodiment of a method for preparing a silica nano silver wire antireflection film according to the present invention.

Detailed Description

The invention discloses a preparation method of a silicon dioxide nano silver wire antireflection film, which comprises the following steps:

s1, performing hydrophilic treatment on the surface of the PET;

s2, pouring 5g PVP (MW = 50000) into a magnetic stirring device filled with 200 mL of Ethylene Glycol (EG), when gel-like soft bodies are generated and attached to the wall of a beaker, washing the beaker with a certain amount of EG, pouring the beaker into a three-neck flask to obtain a solution A,

s3, after oil bath heating and stabilization, adding the mixed solution of AgCI and AgNO3, adding the glycol solution again, and finally mixing, stirring and dissolving the mixed solution and a certain amount of EG respectively to obtain solution B;

s4, slowly adding the solution B into the solution A drop by drop, gradually changing the solution from a colorless transparent state to a light blue colloid state, and stopping the reaction after continuously heating for 10min after the solution finally becomes a milky solution with metallic luster;

s5, standing and naturally cooling, taking out the supernatant, wherein the lower precipitate is the nano-silver wire, washing the precipitate for several times by using ethanol if the precipitate is complete, and dissolving the precipitate in the ethanol for later use, and after the precipitate is not complete, centrifuging the supernatant for 3-4 times to obtain the precipitate, cleaning and storing by using the ethanol;

s6, taking a proper amount of nano-silver wires into a three-neck flask by using a liquid-transferring gun, preparing silicon dioxide by using ethanol, ammonia water, Tetraethoxysilane (TEOS) and octodecamegaohm water according to a certain proportion, adding a nano-silver wire solution, placing the three-neck flask on a magnetic stirrer, and stirring for 1 hour at room temperature to obtain sol;

s7, centrifuging the product again to obtain nano Ag SiO2 with certain coating thickness; s8, carrying out reduced pressure suction filtration by using a mixed cellulose filter membrane with a nano aperture to obtain a film, transferring the film onto a treated PET substrate by a hot pressing method, and removing the filter membrane by using an acetone bath to realize transfer.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art will be able to make the description as a whole, and the embodiments may be appropriately combined to form other embodiments as will be apparent to those skilled in the art.