Preparation method of hollow photonic crystal structural color glaze

Abstract

The application discloses a preparation method of hollow photonic crystal structural color glaze. The method uses monodisperse polystyrene latex balls as the main body, arranges the three-dimensional photonic crystal structure coating through a coating process, fills the gaps between the three-dimensional photonic crystal balls with inorganic materials and organic high-temperature-resistant materials as the main filling materials, and obtains the photonic crystal structural color glaze with a metallic visual effect after the photonic crystal coating after the filling is sintered at a high temperature of 350-1500 DEG C and a reverse opal three-dimensional photonic crystal structure is generated. The preparation method using the structural color principle to obtain the decoration effect can be applied to the existing ceramic, glass, metal and other product industries on a large scale, so that the products have better decoration effects.

Description

Technical Field

[0001] This invention belongs to the field of ceramic glaze preparation technology, specifically relating to a method for preparing hollow photonic crystal structure color glaze. Background Technology

[0002] Photonic crystals refer to a photonic bandgap effect formed by the periodic arrangement of materials with different dielectric constants (or refractive indices) in space. Opals, butterfly wings, and peacock feathers, all possessing photonic crystal structures in nature, exhibit vibrant colors. Therefore, by artificially synthesizing photonic crystal materials and constructing one-dimensional, two-dimensional, or three-dimensional photonic crystal structures, it is possible to obtain the colors characteristic of photonic crystal structures. Existing patented photonic crystal fabrications are mainly suitable for preparation and temperature tolerance below 300℃, while methods for preparing photonic crystal ceramics stable through high-temperature sintering are rarely reported. Summary of the Invention

[0003] The purpose of this invention is to provide an easy-to-implement and mass-producible method for preparing structural color glazes based on an inverse opal hollow photonic crystal structure. The prepared glaze exhibits variations in color and depth depending on the viewing angle. This invention is simple to manufacture and facilitates large-scale mass production. The sintered glaze, due to its inverse opal photonic crystal structure, displays color that changes with angle and possesses a distinct metallic luster. Therefore, it has a promising future in the market for ceramic overglaze decoration.

[0004] The preparation method of the hollow photonic crystal structure color glaze is as follows:

[0005] (1) Apply a monodisperse polystyrene emulsion to the surface of glass, metal or ceramic blank, let it dry naturally at room temperature until it is surface dry, and then heat-bake it at 80°C for 30 min to obtain a polystyrene photonic crystal coating.

[0006] (2) Nanoscale inorganic materials and fluid organic materials are blended and stirred. At the same time, a solvent is added to further reduce the viscosity of the system. After stirring for 2-10 hours, an inorganic and organic composite filler material is obtained.

[0007] (3) The filler material prepared in step (2) is coated onto the surface of the polystyrene photonic crystal coating prepared in step (1). After 2-30 min of penetration and drying, it is placed in an oven at 50-80℃ for 1 h and then taken out.

[0008] (4) Place the sample obtained in step (3) into a muffle furnace and heat it at a heating rate of 1-5℃ / min. When the temperature reaches 350-450℃, keep it at that temperature for 1-3 hours. Then continue heating it at a heating rate of 1-5℃ / min to 500-1500℃ and keep it at that temperature for 1-2 hours. After that, cool it to room temperature to obtain a sample with a photonic crystal structure.

[0009] The monodisperse polystyrene emulsion described in step (1) has a particle size of 150-800 nm, a monodispersity index ≤0.05, and a solid content of 5-55 wt%.

[0010] The thickness of the photonic crystal coating after heat drying in step (1) is 2-150 μm; preferably 5-25 μm.

[0011] The nanoscale inorganic material mentioned in step (2) is selected from one or more of titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, pearl powder, pearlescent powder, glass powder, and transparent glaze.

[0012] The organic material mentioned in step (2) is selected from one or more of phenolic resin, organosilicon resin, epoxy resin, polysiloxane, and polysilazane.

[0013] The mass ratio of inorganic material to organic material in step (2) is 0.05-1:1.

[0014] The heating environment of the muffle furnace in step (4) is an air, argon, ammonia or nitrogen atmosphere, preferably a nitrogen atmosphere.

[0015] In step (1), the photonic crystal coating is prepared by coating method, but vertical pulling method, vacuum deposition method, inkjet printing, spraying, dispensing and other processing methods can also be used.

[0016] The particle size D90 of the nano-inorganic particles is preferably below 100 nm, and optimally below 50 nm.

[0017] In the above technical solution, the filling method of the organic-inorganic composite material described in step (3) is not limited to direct coating, but can also be achieved by various means such as dip-coating, dispensing, spraying, inkjeting, and curtain coating. The transparency of the sample obtained after step (3) will be further improved, tending to be transparent or semi-transparent.

[0018] During high-temperature sintering, the PS microspheres are completely decomposed and vaporized, forming air microspheres. Simultaneously, the high-temperature resistant organic-inorganic composite material used as the main structural component is retained. Based on the bandgap theory of photonic crystals, the air refractive index in the final inverse opal structure obtained in this invention is approximately 1. The refractive index of the organic-inorganic filler material can be calculated based on the volume ratio of organic and inorganic materials. The significant difference in refractive indices between the two further enhances the photonic bandgap effect, resulting in a more aesthetically pleasing structural color.

[0019] This invention uses a one-step synthesized polystyrene emulsion as a base and fills the gaps in a photonic crystal coating with a composite material to prepare a structural color glaze suitable for high-temperature sintering. After sintering, an inverse opal photonic crystal structure with air spheres and filling material as the main components is obtained, achieving the effect of displaying the colors of a photonic crystal structure. Since the refractive index of the sintered air spheres is approximately 1, which differs significantly from the refractive index of organic-inorganic composite materials, a large photonic bandgap intensity can be obtained, giving the sintered inverse opal structure glaze a brilliant structural color. Furthermore, based on the short-range and long-range ordering characteristics exhibited by the air spheres, the structural color shows a clear angle dependence (the color changes with the angle). Therefore, this invention, as a simple and easily implemented preparation method, complements existing ceramic glaze technology and has excellent application prospects. Attached Figure Description

[0020] Figure 1 SEM (scanning electron microscope) image of the sintered blue hollow photonic crystal glaze. Detailed Implementation Example 1

[0021] A 290nm monodisperse polystyrene emulsion was used to coat the glass surface, which was then allowed to dry naturally at room temperature until it was surface dry. Finally, it was heated at 80°C for 30 minutes to obtain a polystyrene photonic crystal coating of a certain thickness.

[0022] Nanoscale silica (30nm) and fluid organosilicon resin were blended and stirred in a mass ratio of 1:1. At the same time, ethanol solution was added to further reduce the viscosity of the system. After stirring for 6 hours, an inorganic and organic composite filler material was obtained.

[0023] On the surface of the prepared PS photonic crystal coating, a filler material was coated onto its surface. After 30 minutes of penetration and drying, it was placed in an oven at 80°C for 1 hour and then removed.

[0024] The sample was then placed in a muffle furnace and heated at a rate of 3 °C / min until it reached 400 °C. It was then held at that temperature for 1 hour, and then heated at a rate of 3 °C / min until it reached 500 °C. It was then held at that temperature for 1 hour and then cooled to room temperature to obtain a sample with a blue photonic crystal structure. Example 2

[0025] A 420nm monodisperse polystyrene emulsion was used to coat the glass surface, which was then allowed to dry naturally at room temperature until it was surface dry. Finally, it was heated at 80°C for 30 minutes to obtain a polystyrene photonic crystal coating of a certain thickness.

[0026] Nanoscale silica (20nm) and fluid siloxane resin were blended and stirred at a mass ratio of 0.5:1. At the same time, ethanol solution was added to further reduce the viscosity of the system. After stirring for 6 hours, an inorganic and organic composite filler material was obtained.

[0027] On the surface of the prepared PS photonic crystal coating, a filler material was coated onto its surface. After 60 minutes of penetration and drying, it was placed in an oven at 80°C for 1 hour and then removed.

[0028] Then, the sample was placed in a muffle furnace and heated at a rate of 3℃ / min. When the temperature reached 400℃, it was held for 1 hour. Then, the temperature was increased to 500℃ at a rate of 3℃ / min and held for 1 hour. After that, it was cooled to room temperature to obtain a sample with a red photonic crystal structure. Example 3

[0029] A 353nm monodisperse polystyrene emulsion was used to coat the glass surface, which was then allowed to dry naturally at room temperature until it was surface dry. Finally, it was heated at 80°C for 30 minutes to obtain a polystyrene photonic crystal coating of a certain thickness.

[0030] Nanoscale silica (10nm) and fluid silazane resin were blended and stirred at a mass ratio of 0.5:1. At the same time, n-hexane solution was added to further reduce the viscosity of the system. After ultrasonic dispersion for half an hour, an inorganic and organic composite filler material was obtained.

[0031] On the surface of the prepared PS photonic crystal coating, a filler material was coated onto its surface. After 30 minutes of penetration and drying, it was placed in an oven at 80°C for 1 hour and then baked at 150°C for 1 hour before being removed.

[0032] Then, the sample was placed in a tube furnace and heated in a nitrogen atmosphere at a heating rate of 2 °C / min. When the temperature reached 170 °C, it was held for 1 hour. Then, the temperature was increased to 500 °C at a heating rate of 0.5 °C / min and held for 1 hour. After that, the temperature was cooled to room temperature at a rate of 1 °C / min to obtain a sample with a green photonic crystal structure. Example 4

[0033] A 420nm monodisperse polystyrene emulsion was used to coat the glass surface with a wire rod. The coating was allowed to dry naturally at room temperature until it was surface dry, and then heated at 80°C for 30 minutes to obtain a polystyrene photonic crystal coating of a certain thickness.

[0034] Nanoscale zinc oxide (20nm) and fluid phenolic resin were blended and stirred at a mass ratio of 0.3:1. At the same time, isopropanol solution was added to further reduce the viscosity of the system. After ultrasonic dispersion for half an hour, an inorganic and organic composite filler material was obtained.

[0035] On the surface of the prepared PS photonic crystal coating, the filler material was deposited on its surface by a microfluidic spray gun (flow rate 50 mL / min). After 40 min of penetration and drying, it was placed in an oven at 80℃ for 1 h, and then the oven temperature was raised to 120℃ for 2 hours before being taken out.

[0036] Then, the sample was placed in a tube furnace and heated in a nitrogen atmosphere at a heating rate of 2℃ / min. When the temperature reached 200℃, it was held for 1 hour. Then, the temperature was increased to 400℃ at a heating rate of 0.5℃ / min and held for 1 hour. After that, the temperature was cooled to room temperature at a rate of 1℃ / min to obtain a sample with a red photonic crystal structure. Example 5

[0037] Using a laboratory-made 45wt% 293nm polystyrene photonic crystal emulsion (PDI 0.04), it was coated on the surface of a flat high-temperature resistant quartz glass (resistant to 1000℃ without softening or deformation) with an RDS20 wire rod. It was allowed to air dry at room temperature until surface dry, and then heated in a forced-air drying oven at 80℃ for 30 minutes to obtain a polystyrene photonic crystal coating of a certain thickness (20 micrometers).

[0038] Nanoscale silica (15nm) and liquid phenolic resin were mixed and stirred at a mass ratio of 0.05:1. At the same time, n-butanol solution was added to further reduce the viscosity of the system (the overall solid content is not less than 50%), so that the viscosity is less than 100mPas. After stirring for 6 hours, the mixture was ultrasonically dispersed for 30 minutes to obtain a uniformly dispersed, transparent inorganic and organic composite filler material.

[0039] On the surface of the prepared polystyrene photonic crystal coating, the filler material was coated onto its surface using an RDS20 wire rod. After 30 minutes of penetration and drying, it was placed in an oven at 80°C for 1 hour, and then heated to 120°C for 1 hour. After the oven cooled naturally, the sample was removed and cured.

[0040] Then, a layer of commercially available low-temperature melting point glass powder (which can melt and flow at 400-450℃) was uniformly coated onto the surface of the sample on a flat high-temperature resistant glass plate and placed in a muffle furnace. The sample was heated at a rate of 1℃ / min until it reached 350℃, and then held at that temperature for 3 hours. The temperature was then increased to 500℃ at a rate of 1℃ / min and held for 3 hours. The temperature was then increased to 700℃ at a rate of 1℃ / min, and then cooled to room temperature to obtain a photonic crystal glaze sample with a glass coating on the surface. Example 6

[0041] Using a laboratory-made 10wt% 246nm polystyrene photonic crystal emulsion (PDI 0.04), it was sprayed onto the surface of a flat ceramic slab using an Iwata HP-CP (0.3mm) airbrush and a small pressure pump. At least three coats were applied. The first coat of photonic crystal emulsion dried quickly due to water absorption on the ceramic surface, failing to form an ordered arrangement of photonic crystals. After the first coat dried, the second and third coats were applied (controlling the flow rate for thin sprays). Each coat was allowed to air dry slowly, ultimately forming a polystyrene photonic crystal layer with structural color on the ceramic surface. Finally, it was dried in a forced-air drying oven at 80°C for 30 minutes.

[0042] Nano-sized titanium dioxide (30nm) and photosensitive modified polysilazane resin were mixed and stirred at a mass ratio of 0.2:1. After stirring for 6 hours in a light-protected environment using a high-speed disperser, a uniformly dispersed and transparent inorganic and organic composite filler material was obtained.

[0043] On the surface of the prepared polystyrene photonic crystal coating, the filler material was coated onto its surface using an RDS30 wire rod. After 30 minutes of penetration and drying, it was placed under a UVLED light source (405nm) for 2 minutes. After irradiation, the filler material hardened.

[0044] Then, a layer of commercially available low-temperature melting point glass powder (which can melt and flow at 400-450℃) was uniformly coated on the surface of the sample on the flat ceramic plate and placed in a tube furnace. Under an argon atmosphere, the sample was heated at a rate of 1℃ / min until it reached 300℃, and then held at that temperature for 3 hours. The temperature was then increased to 500℃ at a rate of 1℃ / min and held for 3 hours. The temperature was then increased to 1100℃ at a rate of 1℃ / min and then allowed to cool naturally to room temperature, resulting in a photonic crystal glaze sample with a glass coating on the surface.

[0045] The foregoing has described in detail the implementable method of the present invention; however, the present invention is not limited thereto. Simple modifications or combinations suitable for the method that fall within the scope of the inventive concept should be considered as part of the disclosure of the present invention and are all within the protection scope of the present invention.

[0046] Furthermore, the various embodiments of the present invention can be combined arbitrarily without contradiction, and as long as they do not violate the spirit of the present invention, they should all be regarded as the contents disclosed by the present invention.

Claims

1. A method for preparing a hollow photonic crystal structure color glaze, characterized in that, The implementation steps include the following: (1) Apply a monodisperse polystyrene emulsion to the surface of glass, metal or ceramic blank, let it dry naturally at room temperature until it is surface dry, and then heat-bake it at 80°C for 30 min to obtain a polystyrene photonic crystal coating. (2) Nanoscale inorganic materials and fluid organic materials are blended and stirred. At the same time, a solvent is added to further reduce the viscosity of the system. After stirring for 2-10 hours, an inorganic and organic composite filler material is obtained. (3) The filler material prepared in step (2) is coated onto the surface of the polystyrene photonic crystal coating prepared in step (1). After 2-30 min of penetration and drying, it is placed in an oven at 50-80℃ for 1 h and then taken out. (4) Place the sample obtained in step (3) into a muffle furnace and heat it at a heating rate of 1-5℃ / min. When the temperature reaches 350-450℃, keep it at that temperature for 1-3 hours. Then continue heating it at a heating rate of 1-5℃ / min to 500-1500℃ and keep it at that temperature for 1-2 hours. After that, cool it to room temperature to obtain a sample with a photonic crystal structure.

2. The method for preparing hollow photonic crystal structure glaze according to claim 1, characterized in that, The monodisperse polystyrene emulsion described in step (1) has a particle size of 150-800 nm, a monodispersity index ≤0.05, and a solid content of 5-55 wt%.

3. The method for preparing hollow photonic crystal structure colored glaze according to claim 1, characterized in that, The thickness of the photonic crystal coating after heat baking in step (1) is 2-150 μm.

4. The method for preparing hollow photonic crystal structure colored glaze according to claim 1, characterized in that, The nanoscale inorganic material mentioned in step (2) is selected from one or more of titanium dioxide, silicon dioxide, zinc oxide, aluminum oxide, pearl powder, pearlescent powder, glass powder, and transparent glaze.

5. The method for preparing hollow photonic crystal structure colored glaze according to claim 1, characterized in that, The organic material mentioned in step (2) is selected from one or more of phenolic resin, organosilicon resin, epoxy resin, polysiloxane, and polysilazane.

6. The method for preparing hollow photonic crystal structure colored glaze according to claim 1, characterized in that, The mass ratio of inorganic material to organic material in step (2) is 0.05-1:

1.

7. The method for preparing hollow photonic crystal structure colored glaze according to claim 1, characterized in that, The heating environment of the muffle furnace described in step (4) is an air, argon, ammonia or nitrogen atmosphere.

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