CN113548670B - Preparation method of inorganic structure color material - Google Patents
Preparation method of inorganic structure color material Download PDFInfo
- Publication number
- CN113548670B CN113548670B CN202110762157.8A CN202110762157A CN113548670B CN 113548670 B CN113548670 B CN 113548670B CN 202110762157 A CN202110762157 A CN 202110762157A CN 113548670 B CN113548670 B CN 113548670B
- Authority
- CN
- China
- Prior art keywords
- microspheres
- shell
- core
- inorganic
- poly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
The invention discloses a preparation method of an inorganic structural color material, and belongs to the technical field of preparation of structural color materials. The invention relates to a powder material consisting of hollow porous microspheres, which is prepared by taking organic polymer microspheres as cores and coating an inorganic shell layer to prepare core-shell microspheres, etching and forming pores by alkali to obtain porous core-shell colloidal microspheres, regulating and controlling the etching time to ensure that the pore diameter is in a mesoporous range, and finally removing the organic polymer in the porous core-shell colloidal microspheres by a high-temperature calcination method. The invention has the advantages that the inorganic structure color pigments with different colors can be obtained by the preparation method, and the color is bright. In addition, the pigment is stable in color, green and environment-friendly, can be used as a novel pigment, a dye and other pigments, and has wide application prospects in the fields of printing ink, printing and dyeing, paint and the like.
Description
Technical Field
The invention relates to an inorganic structural color material and a preparation method thereof, belonging to the technical field of structural color material preparation.
Background
The structural colors are the colors of blue sky, rainbow, butterfly wing, peacock feather, shell, soap bubble and opal with attractive light in nature, and are the visual effects generated by the interference, diffraction and scattering of the special physical structure of the object and the light. Compared with traditional chemical colorants such as dyes and pigments, the structural color has the advantages of high brightness, high saturation, fastness, environmental friendliness and the like, and has a wide application prospect.
As for the structural color, the color does not disappear as long as the microstructure of the material constituting the structural color is not destroyed. At present, structural color is mainly obtained by assembling colloid microspheres into periodically ordered photonic crystals, but the periodic microstructure formed by microsphere point contact has poor mechanical property and is easily damaged by external force, so that the structural color fades and even disappears. In recent years, powdered photonic pigments have been developed, but the color produced by the micron-sized photonic crystal structure is also discolored due to structural damage. Therefore, the development of a novel structural color pigment which is free from assembly, bright in color, never fades and environment-friendly has important significance.
The invention aims to develop an inorganic structure color material and a preparation method thereof. The structural color pigment is prepared by taking a polymer microsphere as a core, coating an inorganic shell layer to prepare a core-shell microsphere, performing alkali etching to form a porous core-shell colloid microsphere, regulating and controlling the etching time to enable the aperture to be in a mesoporous range, and removing an organic polymer in the porous core-shell colloid microsphere by adopting a high-temperature calcination method to prepare the hollow porous microsphere. Compared with the traditional organic pigment, dye and other coloring agents which have toxicity and can cause serious pollution to the ecological environment, the inorganic structure coloring material with different colors can be prepared by the method, the color is bright, in addition, the coloring material has stable color and environmental protection, can be used as a novel pigment, dye and other coloring agents, and has wide application prospect in the fields of printing ink, printing and dyeing, paint and the like.
Disclosure of Invention
The invention aims to provide a preparation method of an inorganic structural color material. The structural color pigment is prepared by taking a polymer microsphere as a core and coating an inorganic shell layer to prepare a core-shell microsphere, performing alkali etching to form a porous core-shell colloidal microsphere, regulating the etching time to ensure that the aperture is in a mesoporous range, and removing an organic polymer in the porous core-shell colloidal microsphere by adopting a high-temperature calcination method to prepare the hollow porous microsphere. Compared with the traditional organic pigment, dye and other coloring agents which have toxicity and can cause serious pollution to the ecological environment, the inorganic structure coloring material with different colors can be prepared by the method, the color is bright, in addition, the coloring material has stable color and environmental protection, can be used as a novel pigment, dye and other coloring agents, and has wide application prospect in the fields of printing ink, printing and dyeing, paint and the like. The invention provides a preparation method of an inorganic structure color material, which comprises the following steps:
(1) The polymer microsphere with good monodispersity is used as a core, and an inorganic shell layer is coated on the surface of the microsphere to form the microsphere with a core-shell structure; the polymer microsphere is any one of polystyrene, poly (styrene-acrylic acid), polymethyl methacrylate, poly (styrene-methyl methacrylate), poly (methyl methacrylate-acrylic acid), poly (styrene-acrylamide), poly (styrene-divinylbenzene) or polyurea; the inorganic shell layer is any one of silicon dioxide, titanium dioxide, zirconium dioxide, tin dioxide, cerium dioxide, zinc oxide, copper oxide or zinc sulfide;
(2) Performing alkali etching on the core-shell microspheres obtained in the step (1) to form pores, so as to obtain porous core-shell colloidal microspheres, and regulating and controlling etching time to enable the pore diameter to be in a mesoporous range of 2-50 nm;
(3) And (3) calcining the porous core-shell colloidal microspheres obtained in the step (2) in a muffle furnace by a high-temperature calcination method, and removing the organic polymer to prepare the hollow porous microspheres. The invention utilizes the Mie scattering effect of hollow and surface porous structures on light to generate structural color. In order to obtain better effect in high-temperature calcination, the porous core-shell colloidal microspheres are ground into fine powder before high-temperature calcination in a muffle furnace, so that the calcination is more uniform and the removal effect is better.
Preferably, in step (1) of the method for preparing an inorganic structural color material, the particle size of the polymer microspheres is 180 to 630nm.
Preferably, in the step (2) of the method for producing an inorganic structural color material, the base is any one of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia water, and ammonium bicarbonate.
Preferably, in step (2) of the above method for producing an inorganic structural coloring material, the time for the alkali etching is 15 to 180min, and the concentration of the alkali used is 0.1 to 1.0g/mL.
Preferably, in the step (3) of the above method for preparing an inorganic structural color material, the calcination temperature is 350 to 600 ℃ and the calcination time is 2 to 10 hours.
Advantageous effects
1. The inorganic structural color pigment prepared by the invention is directly obtained by calcination instead of photonic crystal assembly, and has the advantages of simple process, easy implementation, low preparation cost, mass preparation and strong universality.
2. The invention can prepare inorganic structure color pigments with different colors, and the colors are bright.
Drawings
FIG. 1 is an optical photograph of a hollow porous silica powder prepared in example 1;
FIG. 2 is a spectrum of the hollow porous silica powder obtained in example 1.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications can be made to the present invention by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
Example 1
The method comprises the following steps of (1) taking a polystyrene microsphere with good monodispersity and 180-630 nm as a core, and coating a silicon dioxide shell layer on the surface of the microsphere to obtain core-shell microspheres with different particle sizes; performing alkali etching on the core-shell microspheres in a sodium hydroxide solution with the concentration of 0.2g/mL to form porous core-shell colloidal microspheres, and regulating and controlling the etching time to be 30min to ensure that the pore diameter is in a mesoporous range; and finally, grinding the dried porous core-shell colloidal microspheres into powder in a mortar, then placing the powder into a porcelain ark, transferring the porcelain ark into a muffle furnace for calcination, heating at the rate of 3 ℃/min, calcining at the temperature of 450 ℃ for 3h, removing the organic polymer, and preparing the hollow porous silicon dioxide powder.
An optical photograph of the hollow porous silica powder prepared by using the polystyrene microspheres of 190 nm, 230 nm and 310nm as the cores in the example is shown in fig. 1, the structural color powder respectively shows bright blue, green and brown, and as shown in the spectrum of fig. 2, the corresponding reflection peaks are 444 nm, 529 nm and 624nm respectively.
Examples 2 to 9
Microspheres having a core-shell structure were prepared in the same manner as in example 1, except that the conditions were the same as in example 1, using poly (styrene-acrylic acid), polymethyl methacrylate, poly (styrene-methyl methacrylate), poly (methyl methacrylate-acrylic acid), poly (styrene-acrylamide), poly (styrene-divinylbenzene), and polyurea instead of the polystyrene microspheres in example 1, respectively, and the same effects were obtained as shown in fig. 1 and fig. 2.
Example 10
The method comprises the following steps of (1) taking a polystyrene microsphere with good monodispersity and 180-630 nm as a core, and coating a titanium dioxide shell layer on the surface of the microsphere to obtain core-shell microspheres with different particle sizes; performing alkali etching pore-forming on the core-shell microspheres in a sodium bicarbonate solution with the concentration of 0.3g/mL to obtain porous core-shell colloidal microspheres, and regulating and controlling the etching time to be 40min to ensure that the pore diameter is in a mesoporous range; and finally, grinding the dried porous core-shell colloidal microspheres into powder in a mortar, then placing the powder into a porcelain ark, transferring the porcelain ark into a muffle furnace for calcination, heating at the rate of 2 ℃/min, calcining at 550 ℃ for 2h, removing the organic polymer, and preparing the hollow porous titanium dioxide powder.
Examples 11 to 18
Different core materials, namely poly (styrene-acrylic acid), polymethyl methacrylate, poly (styrene-methyl methacrylate), poly (methyl methacrylate-acrylic acid), poly (styrene-acrylamide), poly (styrene-divinylbenzene) and polyurea are respectively taken to replace the polystyrene microspheres in the embodiment 10 to prepare the microspheres with the core-shell structure, and other conditions are consistent with the embodiment 10, so that better effects can be obtained.
Example 19
The method comprises the following steps of (1) taking a polystyrene microsphere with good monodispersity and 180-630 nm as a core, and coating a zirconium dioxide shell layer on the surface of the microsphere to obtain core-shell microspheres with different particle sizes; performing alkali etching pore-forming on the core-shell microspheres in a sodium carbonate solution with the concentration of 0.2g/mL to obtain porous core-shell colloidal microspheres, and regulating and controlling the etching time to be 40min to ensure that the pore diameter is in a mesoporous range; and finally, grinding the dried porous core-shell colloidal microspheres into powder in a mortar, then placing the powder into a porcelain ark, transferring the porcelain ark into a muffle furnace for calcination, heating at the rate of 3 ℃/min, calcining at the temperature of 400 ℃ for 5 hours, and removing the organic polymer to prepare the hollow porous zirconium dioxide powder.
Examples 20 to 27
Different core materials, namely poly (styrene-acrylic acid), polymethyl methacrylate, poly (styrene-methyl methacrylate), poly (methyl methacrylate-acrylic acid), poly (styrene-acrylamide), poly (styrene-divinylbenzene) and polyurea, are respectively taken to replace the polystyrene microspheres in the embodiment 19 to prepare the microspheres with the core-shell structure, and other conditions are consistent with the embodiment 19, so that better effects can be obtained.
Example 28
The preparation method comprises the following steps of (1) taking 180-630 nm polystyrene microspheres with good monodispersity as cores, and coating a tin dioxide shell layer on the surfaces of the microspheres to obtain core-shell microspheres with different particle sizes; performing alkali etching pore-forming on the core-shell microspheres in an ammonia water solution with the concentration of 0.4g/mL to obtain porous core-shell colloidal microspheres, and regulating and controlling the etching time to be 50min to ensure that the pore diameter is in a mesoporous range; and finally, grinding the dried porous core-shell colloidal microspheres into powder in a mortar, then putting the powder into a porcelain ark, transferring the porcelain ark into a muffle furnace for calcination, wherein the heating rate is 2 ℃/min, calcining the powder at 600 ℃ for 5h, removing the organic polymer, and preparing the hollow porous tin dioxide powder.
Examples 29 to 36
Different core materials, namely poly (styrene-acrylic acid), polymethyl methacrylate, poly (styrene-methyl methacrylate), poly (methyl methacrylate-acrylic acid), poly (styrene-acrylamide), poly (styrene-divinylbenzene) and polyurea, are respectively taken to replace the polystyrene microspheres in the embodiment 28 to prepare the microspheres with the core-shell structure, and other conditions are consistent with the embodiment 28, so that better effects can be obtained.
Example 37
The preparation method comprises the following steps of (1) taking 180-630 nm polystyrene microspheres with good monodispersity as cores, and coating a cerium dioxide shell layer on the surfaces of the microspheres to obtain core-shell microspheres with different particle sizes; performing alkali etching on the core-shell microspheres in an ammonium bicarbonate solution with the concentration of 0.5g/mL to form porous core-shell colloidal microspheres, and regulating and controlling the etching time to be 25min to ensure that the pore diameter is in a mesoporous range; and finally, grinding the dried porous core-shell colloidal microspheres into powder in a mortar, then placing the powder into a porcelain ark, transferring the porcelain ark into a muffle furnace for calcination, heating at the rate of 2 ℃/min, calcining at the temperature of 500 ℃ for 6h, removing the organic polymer, and preparing the hollow porous cerium dioxide powder.
Examples 38 to 45
Different core materials, namely poly (styrene-acrylic acid), polymethyl methacrylate, poly (styrene-methyl methacrylate), poly (methyl methacrylate-acrylic acid), poly (styrene-acrylamide), poly (styrene-divinylbenzene) and polyurea were respectively taken to replace the polystyrene microspheres in example 37 to prepare microspheres with a core-shell structure, and other conditions were consistent with example 37, so that the same good effects were obtained.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (6)
1. A preparation method of an inorganic structure color material is characterized by comprising the following steps:
(1) The polymer microsphere with good monodispersity is used as a core, and an inorganic shell layer is coated on the surface of the microsphere to form the microsphere with a core-shell structure; the polymer microsphere is any one of polystyrene, poly (styrene-acrylic acid), polymethyl methacrylate, poly (styrene-methyl methacrylate), poly (methyl methacrylate-acrylic acid), poly (styrene-acrylamide), poly (styrene-divinylbenzene) or polyurea; the inorganic shell layer is any one of silicon dioxide, titanium dioxide, zirconium dioxide, tin dioxide, cerium dioxide, zinc oxide, copper oxide or zinc sulfide;
(2) Performing alkali etching on the core-shell microspheres obtained in the step (1) to form pores, so as to obtain porous core-shell colloidal microspheres, and regulating and controlling etching time to enable the pore diameter to be in a mesoporous range of 2-50 nm;
(3) And (3) calcining the porous core-shell colloidal microspheres obtained in the step (2) in a muffle furnace by a high-temperature calcination method to remove the organic polymer, thus obtaining the hollow porous microspheres.
2. The method according to claim 1, wherein the polymer microspheres in step (1) have a particle size of 180 to 630nm.
3. The method for preparing an inorganic structural color material according to claim 1, wherein the base in the step (2) is any one of sodium carbonate, sodium bicarbonate, sodium hydroxide, ammonia water, or ammonium bicarbonate.
4. The method according to claim 1, wherein the etching time of the alkali in step (2) is 15-180 min, and the concentration of the alkali used is 0.1-1.0 g/mL.
5. The method for preparing an inorganic structural color material according to claim 1, wherein the calcination temperature in the step (3) is 350 to 600 ℃, and the calcination time is 2 to 10 hours.
6. The method for preparing an inorganic structural color material according to claim 1, wherein in the step (3), the porous core-shell colloidal microspheres are ground into fine powder before high-temperature calcination in a muffle furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110762157.8A CN113548670B (en) | 2021-07-06 | 2021-07-06 | Preparation method of inorganic structure color material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110762157.8A CN113548670B (en) | 2021-07-06 | 2021-07-06 | Preparation method of inorganic structure color material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113548670A CN113548670A (en) | 2021-10-26 |
| CN113548670B true CN113548670B (en) | 2023-03-17 |
Family
ID=78131361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110762157.8A Active CN113548670B (en) | 2021-07-06 | 2021-07-06 | Preparation method of inorganic structure color material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113548670B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114164483B (en) * | 2021-11-26 | 2022-09-09 | 大连理工大学 | Preparation method of microbubble-driven photonic pigment |
| CN114602452B (en) * | 2022-03-15 | 2023-10-17 | 中国科学院赣江创新研究院 | Self-template porous cerium-zirconium solid solution and preparation method thereof |
| CN114503949B (en) * | 2022-04-19 | 2022-07-05 | 无棣永利盐业有限公司 | Mariculture pond with high-efficient blowdown function |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491349B (en) * | 2011-12-08 | 2013-08-21 | 厦门大学 | Preparation method of hollow mesoporous silica nanospheres |
| CN105174301B (en) * | 2015-09-21 | 2017-03-22 | 陕西科技大学 | Low-angle-dependence green zinc-sulfide structural color pigment and preparing method thereof |
| JP6739071B2 (en) * | 2015-09-23 | 2020-08-12 | 国立大学法人千葉大学 | Membranes and articles containing core-shell particles |
| CN105439461B (en) * | 2015-12-02 | 2018-08-28 | 陕西科技大学 | A kind of hollow silica photonic crystal structure color film of blue-green and preparation method thereof |
| CN108325481A (en) * | 2018-01-22 | 2018-07-27 | 武汉理工大学 | Photonic crystal decorative coveringn of color tunable and preparation method thereof |
-
2021
- 2021-07-06 CN CN202110762157.8A patent/CN113548670B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113548670A (en) | 2021-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113548670B (en) | Preparation method of inorganic structure color material | |
| CN103288491B (en) | Preparation method of blue-green photonic crystal structure color film | |
| CN109031476B (en) | Preparation method of patterned photonic crystal structure chromogenic material with stable structure and bright color | |
| KR101541009B1 (en) | Colored glazed pigments using natural dye and method of manufacturing the same | |
| CN104233802A (en) | Preparation method of natural silk fabric with photonic crystal structure color | |
| CN108227055B (en) | Preparation method and application of visible light reflecting film | |
| CN104071839A (en) | Preparation method of green zirconium oxide superstructure toner | |
| CN114181694B (en) | Red fluorescent electrophoresis particle for electronic paper and preparation method and application thereof | |
| CN114940769B (en) | Angle-dependence-free electric response film based on structural color and preparation method and application thereof | |
| CN109486305B (en) | Special energy-saving eye-protecting brightening coating for classroom and preparation method and application thereof | |
| CN104817281A (en) | Preparation method of orange-yellow photonic crystal structure color thin film with photo-catalytic effect | |
| CN103257388A (en) | Nano-composite polarized lens | |
| CN109535771A (en) | Cobalt blue palygorskite nano composite pigment, preparation method and application | |
| CN112898825B (en) | Submicron-grade large red zirconium silicate coated pigment and preparation method thereof | |
| CN115058165A (en) | Structural color material with gas responsiveness and preparation method thereof | |
| CN112280353B (en) | Antibacterial and ultraviolet-resistant thermochromic wax color paint and preparation method thereof | |
| CN114892432A (en) | Method for preparing patterned photonic crystal structure color-generating fabric by ink-jet printing technology | |
| CN108946818B (en) | Preparation method of black inorganic ceramic pigment | |
| CN102729681B (en) | Photographic paper ink absorption layer material and preparation method thereof | |
| CN105439462A (en) | Purple hollow silicon oxide photonic crystal structure color thin film and preparation method thereof | |
| CN103257387A (en) | Method for manufacturing nano-composite polarized lens | |
| CN113429638A (en) | Method for preparing erasable rewritable medium with rapid color change and high cycle number | |
| JPH08314396A (en) | Magnetic recording body | |
| CN105714291A (en) | Preparation method for SiO2 colloidal crystal rainbow film with gorgeous colors | |
| CN105439461B (en) | A kind of hollow silica photonic crystal structure color film of blue-green and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |