CN115108734A - Photonic glass structural color film with solvent response reversible color change performance, preparation method and application - Google Patents

Abstract

The invention provides a photonic glass structural color film with solvent-responsive reversible discoloration performance, a preparation method and use thereof, and relates to the technical field of photonic glass structural color materials, including a substrate on which a plurality of monoliths with different particle sizes are attached. Dispersing hollow MnO ₂ microspheres; the present invention obtains a structural color film by monodispersing hollow MnO ₂ microspheres. The high refractive index and light absorption properties of _MnO2 make it unnecessary to add an additional black background to the material for the visualization of structural colors. The synthesized photonic glass films have bright colors and are not affected by the viewing angle. Under the stimulation of external solvent, the material has obvious color change response effect, and the response is reversible, which has broad application prospects in optical information storage.

Description

A photonic glass structural color film with solvent-responsive reversible color change performance, preparation Preparation method and use

technical field

The invention relates to the technical field of photonic glass structural color materials, in particular to a photonic glass structural color film with solvent-responsive reversible color change performance, a preparation method and an application.

Background technique

Structural color is an alternative coloring mechanism that creates color through the interference of light with microstructures, which will not fade as long as the structure is not destroyed. It has a wide range of application prospects in the fields of anti-counterfeiting, color display, and sensors.

Typically, photonic crystal materials based on coherent Bragg diffraction have periodic structures with short-range order and long-range order. However, photonic crystals have iridescent colors that change with the viewing angle. This iridescent color with narrow viewing angle will limit its application in coloring and color rendering, and the periodic structure has high requirements on the preparation process, which limits its practical application. application. Photonic glass is a class of short-range ordered and long-range disordered materials that do not require tedious and time-consuming assembly processes. Through the action of Mie scattering, non-iridescent colors are produced whose color does not change with the viewing angle. According to the Bragg formula: λ∝dn _eff , it can be known that the wavelength of the color is proportional to the lattice spacing and the effective refractive index. Tuning the lattice spacing and effective refractive index parameters can further change the color of the material. Compared with photonic crystals with iridescent colors, the advantages of photonic glass in terms of assembly and angle dependence are more conducive to the application in color rendering, and it is worthy of further in-depth research.

However, due to the low refractive index of the currently ubiquitous photonic glass structural color materials and poor light absorption performance, the photonic glass structural color materials have the disadvantage of low color saturation, and additional black substances are often required to improve coloring. restrict its application.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a photonic glass structural color film with solvent-responsive reversible discoloration performance, a preparation method and application thereof, and a photonic glass structural color film with high color saturation can be obtained;

The invention provides a photonic glass structural color film with solvent-responsive reversible color changing properties, comprising a substrate on which a plurality of monodisperse hollow MnO ₂ microspheres with different particle sizes are attached.

Further, the substrate is a glass substrate.

Further, the films can display violet, blue and green structural colors under natural light.

The present invention also provides a method for preparing a photonic glass structural color film with solvent-responsive reversible color changing properties, comprising the following steps: S1, preparing monodisperse silica microspheres with different particle sizes; Resorcinol-formaldehyde resin is added to the monodisperse silica microspheres, and after the reaction is centrifuged and washed, the centrifuged product is dispersed in deionized water; S3, potassium permanganate is added to the system obtained in step S2, centrifuged and washed after the reaction, and centrifuged The product is dispersed in deionized water; S4, sodium hydroxide solution is added to the system obtained in step S3, after the reaction is centrifuged and washed, and the centrifuged product is dispersed in deionized water to obtain monodisperse hollow MnO ₂ microspheres; S5, the obtained in step S4 The dispersion of hollow MnO ₂ microspheres was dropped on the substrate, and the hollow MnO ₂ structural color film was prepared after drying.

Further, in step S1, the particle size of the monodisperse silica particles is 170 nm-230 nm, and the concentration is 30 mg/mL-60 mg/mL.

Further, in step S2, the concentration of resorcinol is 0.07wt%, the concentration of formaldehyde is 0.1wt%, the reaction temperature is 60-100°C, and the reaction time is 4 hours.

Further, in step S3, the concentration of potassium permanganate is 4 mg/mL, and the reaction time at room temperature is 3 hours.

Further, in step S4, the concentration of sodium hydroxide is 6 mol/L, and the reaction time is 3 hours at 70°C.

Further, in step S5, the concentration of the hollow MnO ₂ microspheres is 5 mg/mL, and the dispersed droplets of the hollow MnO ₂ microspheres are naturally air-dried on the substrate.

The invention also provides the use of a photonic glass structural color film with solvent-responsive reversible color change performance, and the film can be used for optical information storage.

The technical scheme of the present invention obtains the structural color film by monodisperse hollow MnO ₂ microspheres. The high refractive index and light absorption properties of _MnO2 make it unnecessary to add an additional black background to the material for the visualization of structural colors. The synthesized photonic glass films have bright colors and are not affected by the viewing angle. Under the stimulation of external solvent, the material has obvious color change response effect, and the response is reversible, which has broad application prospects in optical information storage.

Description of drawings

In order to illustrate the specific embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the specific embodiments or the prior art. Obviously, the accompanying drawings in the following description The drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative efforts.

Fig. 1 is the preparation method flow chart of the present invention;

Fig. 2 (a) is the transmission electron microscope picture of Example 1 of the present invention;

Fig. 2 (b) is the reflection spectrogram of Example 1 of the present invention;

Fig. 2(c) is the effect diagram of solvent reversible response of Example 1 of the present invention.

Fig. 3 (a) is the transmission electron microscope picture of Example 2 of the present invention;

Fig. 3 (b) is the reflection spectrogram of Example 2 of the present invention;

Fig. 3(c) is a solvent reversible response effect diagram of Example 2 of the present invention.

Fig. 4 (a) is the transmission electron microscope picture of Example 3 of the present invention;

Fig. 4 (b) is the reflection spectrogram of Example 3 of the present invention;

Fig. 4 (c) is the solvent reversible response effect diagram of Example 3 of the present invention;

Detailed ways

The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "top", "bottom", "front", " Or The positional relationship is based on the orientation or positional relationship shown in the accompanying drawings, which is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, Therefore, it should not be construed as a limitation of the present invention.

Furthermore, the terms "first" and "second" are only used for descriptive purposes, and should not be understood as indicating or implying relative importance or implying the number of indicated technical features. Thus, features defined as "first", "second" may expressly or implicitly include one or more of said features. In the description of the present invention, "plurality" means two or more, unless otherwise expressly and specifically defined. In addition, the terms "installed", "connected" and "connected" should be understood in a broad sense, for example, it may be a fixed connection, a detachable connection, or an integral connection; it may be a mechanical connection or an electrical connection; it may be It is directly connected, or it can be indirectly connected through an intermediate medium, and it can be the internal connection of two components. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood in specific situations.

Example 1, the film has solvent-responsive reversible discoloration properties:

When the monodisperse hollow _MnO2 microspheres are attached to the substrate, due to the high refractive index and light absorption properties of the _MnO2 microspheres, the synthesized photonic glass films can have no additional black background for the visualization of structural colors. Brighter colors that are not affected by viewing angle. When the particle sizes of the hollow MnO ₂ microspheres at different positions on the substrate are different, different positions of the film can display different structural colors such as purple, blue and green. When no solvent is stimulated, the film appears as the first structural color (such as purple), and when stimulated by a solvent (such as ethanol or isopropanol), the structural color changes to the second structural color due to the increase in the effective refractive index (such as blue), and when the solvent evaporates, the film can reversibly return to the first structural color.

Example 2, as shown in Figure 1, the preparation method of the film showing purple structural color:

S1, take 8 mL of tetraethyl orthosilicate, 7 mL of ammonia water, 210 mL of ethanol, and 20 mL of deionized water, and stir for 4 hours to prepare monodisperse silica microspheres with a diameter of 170 nm.

S2, take a monodispersed solution containing 50 mg of silicon dioxide, add 2 mL of PVP solution with a mass fraction of 5 wt % and 16 mL of deionized water, stir for 12 hours, and then centrifuge and separate.

S3, add 20 mg of resorcinol, 28 μL of formaldehyde solution, 100 μL of ammonia water with a mass fraction of 2.8 wt %, and 28 mL of deionized water into the system obtained in step S2, and heat to 60°C. After 2 hours of reaction, the temperature was raised to 100°C, and the reaction was continued for 2 hours. Centrifugation, separation.

S4, add 80 mg of potassium permanganate and 20 mL of deionized water to the system obtained in step S3, stir at room temperature for 3 hours, centrifuge and separate.

S5, add 80 mL of deionized water and 20 mL of sodium hydroxide solution with a concentration of 6 mol/L to the system obtained in step S4, stir at 70 ° C for 3 hours, wash to neutrality, and disperse in deionized water with a concentration of 5 mg/L mL.

S6, dropping the monodisperse solution obtained in step S5 on a glass substrate with a mask to obtain a photonic glass film with a purple structural color.

As shown in Figure 2a, it is the transmission electron microscope image of Example 1 of the present invention, which proves that the product has a hollow structure and a uniform size distribution; as shown in Figure 2b, it is the reflection spectrum of Example 1 of the present invention, the position of the reflection peak Located at 440nm, corresponding to purple; as shown in Figure 2c, which is the solvent response image of Example 1 of the present invention, when there is no solvent stimulation, the film presents a purple structural color, and under the stimulation of ethanol or isopropanol solvent, The structural color red-shifted to blue due to the increase in the effective refractive index, and the film was reversibly reverted to violet when the solvent evaporated. It can be used for color development, anti-counterfeiting, optical information storage and reading under solvent response.

Example 3, as shown in Figure 1, the preparation method of the film showing blue structural color:

S1, take 10 mL of tetraethyl orthosilicate, 8 mL of ammonia water, 210 mL of ethanol, and 20 mL of deionized water, and stir for 4 hours to prepare monodisperse silica microspheres with a diameter of 200 nm.

S2, take a monodispersed solution containing 50 mg of silicon dioxide, add 2 mL of PVP solution with a mass fraction of 5 wt % and 16 mL of deionized water, stir for 12 hours, and then centrifuge and separate.

S3, add 20 mg of resorcinol, 28 μL of formaldehyde solution, 100 μL of ammonia water with a mass fraction of 2.8 wt %, and 28 mL of deionized water into the system obtained in step S2, and heat to 60°C. After 2 hours of reaction, the temperature was raised to 100°C, and the reaction was continued for 2 hours. Centrifugation, separation.

S4, add 80 mg of potassium permanganate and 20 mL of deionized water to the system obtained in step S3, stir at room temperature for 3 hours, centrifuge and separate.

S5, add 80 mL of deionized water and 20 mL of sodium hydroxide solution with a concentration of 6 mol/L to the system obtained in step S4, stir at 70 ° C for 3 hours, wash to neutrality, and disperse in deionized water with a concentration of 5 mg/L mL.

S6, dropping the monodisperse solution obtained in step S5 on a glass substrate with a mask to obtain a photonic glass film with a blue structural color.

As shown in Figure 3a, it is the transmission electron microscope image of Example 2 of the present invention, which proves that the product has a hollow structure and a uniform size distribution; as shown in Figure 3b, it is the reflection spectrum of Example 2 of the present invention, the position of the reflection peak Located at 480nm, corresponding to blue; as shown in Figure 3c, which is the solvent response image of Example 2 of the present invention, when there is no solvent stimulation, the film presents a blue structural color, and under the stimulation of ethanol or isopropanol solvent , due to the increase of the effective refractive index, the structural color red-shifted to green, and when the solvent volatilized, the film could reversibly return to blue. It can be used for color development, anti-counterfeiting, optical information storage and reading under solvent response.

Example 4, as shown in Figure 1, the preparation method of the film showing green structural color:

S1, take 4.5 mL of tetraethyl orthosilicate, 9 mL of ammonia water, 62 mL of ethanol, and 25 mL of deionized water, and stir for 4 hours to prepare monodisperse silica microspheres with a diameter of 230 nm.

S2, take a monodispersed solution containing 50 mg of silicon dioxide, add 2 mL of PVP solution with a mass fraction of 5 wt % and 16 mL of deionized water, stir for 12 hours, and then centrifuge and separate.

S3, add 20 mg of resorcinol, 28 μL of formaldehyde solution, 100 μL of ammonia water with a mass fraction of 2.8 wt %, and 28 mL of deionized water into the system obtained in step S2, and heat to 60°C. After 2 hours of reaction, the temperature was raised to 100°C, and the reaction was continued for 2 hours. Centrifugation, separation.

S4, add 80 mg of potassium permanganate and 20 mL of deionized water to the system obtained in step S3, stir at room temperature for 3 hours, centrifuge and separate.

S5, add 80 mL of deionized water and 20 mL of sodium hydroxide solution with a concentration of 6 mol/L to the system obtained in step S4, stir at 70 ° C for 3 hours, wash to neutrality, and disperse in deionized water with a concentration of 5 mg/L mL.

S6, dropping the monodisperse solution obtained in step S5 on a glass substrate with a mask to obtain a photonic glass film with a green structural color.

As shown in Figure 4a, it is the transmission electron microscope image of Example 3 of the present invention, which proves that the product has a hollow structure and uniform size distribution; as shown in Figure 4b, it is the reflection spectrum of Example 3 of the present invention, the position of the reflection peak It is located at 550nm, corresponding to green; as shown in Figure 4c, it is the solvent response image of Example 3 of the present invention. When there is no solvent stimulation, the film presents a green structural color, and under the stimulation of ethanol or isopropanol solvent, Due to the increase in the effective refractive index, the structural color red-shifted to yellow, and the film could reversibly return to green when the solvent evaporated. It can be used for color development, anti-counterfeiting, optical information storage and reading under solvent response.

Example 5, thin films can be used for optical information storage:

Optical information storage can be formed by arranging and combining different structural colors in a certain area on the film, and optical information reading can be formed by reading the arrangement and combination of structural colors in the area. Specifically, for example, the reading and writing of the optical disc, etc., will not be repeated here.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (10)

1. The photon glass structure color film with the solvent response reversible color change performance is characterized by comprising a substrate, wherein a plurality of monodisperse hollow MnO with different particle sizes are attached to the substrate ₂ And (3) microspheres.

2. A preparation method of a photon glass structure color film with solvent response reversible color change performance is characterized by comprising the following steps:

s1, preparing monodisperse silicon dioxide microspheres with different particle sizes;

s2, adding resorcinol-formaldehyde resin into the monodisperse silicon dioxide microspheres obtained in the step S1, reacting, centrifuging and washing, and dispersing the centrifugal product in deionized water;

s3, adding potassium permanganate into the system obtained in the step S2, reacting, then centrifugally washing, and dispersing a centrifugal product into deionized water;

s4, adding a sodium hydroxide solution into the system obtained in the step S3, centrifugally washing after reaction, dispersing a centrifugal product into deionized water to obtain monodisperse hollow MnO ₂ Microspheres;

s5, preparing the hollow MnO obtained in the step S4 ₂ The dispersed liquid of the microspheres is dripped on a substrate and dried to prepare the hollow MnO ₂ A structural color film.

3. The method for preparing a photonic glass structure color film having a solvent-responsive reversible color change property according to claim 2, wherein in step S1, the monodisperse silica particles have a particle size of 170nm to 230nm and a concentration of 30mg/mL to 60 mg/mL.

4. The method for preparing a photonic glass structure color film having a solvent-responsive reversible discoloration property according to claim 2, wherein in step S2, the concentration of resorcinol is 0.07 wt%, the concentration of formaldehyde is 0.1 wt%, the reaction temperature is 60 to 100 ℃, and the reaction time is 4 hours.

5. The method for preparing a photonic glass structure color film with solvent-responsive reversible color change properties according to claim 2, wherein in step S3, the concentration of potassium permanganate is 4mg/mL, and the reaction time at room temperature is 3 hours.

6. The method for preparing a photonic glass structure color film having a solvent-responsive reversible color change property according to claim 2, wherein in step S4, the concentration of sodium hydroxide is 6mol/L, and the reaction time at 70 ℃ is 3 hours.

7. The method for preparing a photonic glass structure color film having a solvent-responsive reversible discoloration property according to claim 2, wherein in step S5, MnO is hollowed ₂ The concentration of the microspheres is 5mg/mL, and the microspheres are hollow MnO ₂ The dispersed droplets of microspheres were air dried naturally on the substrate.

8. The photonic glass structural color film having solvent-responsive reversible color change properties according to claim 1, wherein the substrate is a glass substrate.

9. The photonic glass structural color film having a solvent-responsive reversible color change property according to claim 1, wherein the film can exhibit structural colors of purple, blue and green under natural light.

10. Use of a photonic glass structured color film having solvent-responsive reversible color change properties, wherein the film is useful for optical information storage.

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