CN105541122B - A kind of hollow silica photonic crystal structure color film of yellow green and preparation method thereof - Google Patents
A kind of hollow silica photonic crystal structure color film of yellow green and preparation method thereof Download PDFInfo
- Publication number
- CN105541122B CN105541122B CN201510872923.0A CN201510872923A CN105541122B CN 105541122 B CN105541122 B CN 105541122B CN 201510872923 A CN201510872923 A CN 201510872923A CN 105541122 B CN105541122 B CN 105541122B
- Authority
- CN
- China
- Prior art keywords
- crystal structure
- photonic crystal
- color film
- yellow green
- hollow silica
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Silicon Compounds (AREA)
Abstract
Hollow silica photonic crystal structure color film of a kind of yellow green disclosed by the invention and preparation method thereof, belongs to photonic crystal structure color film preparing technical field.For template, NH is modified on its surface with organic micro-spheres polystyrene (PS) first for the method for the present invention2, then utilize improvedMethod coats one layer of uniform silicon oxide layer on its surface, the photon crystal structure of opal structural is formed in glass baseplate surface finally by self assembly, PS microballoons are carbonized by the calcining under protection of reducing atmosphere again, since the atrament that the PS microballoons of carbonization are generated is present in inside each hollow silica shell to absorb most of incoherent scattering light, it is simple to obtain a kind of yellow green photonic crystal structure color film this method process assembled with high saturation silica hollow ball, raw material, which is easy to get, to be shown, printing, coating, cosmetics, photonic crystal etc. is widely used.
Description
Technical field
The invention belongs to photonic crystal structure color film preparing technical fields, and in particular to a kind of hollow silica of yellow green
Photonic crystal structure color film and preparation method thereof.
Background technology
Schemochrome is to be interfered by microstructure and the visible light of object, scattered or developed the color phenomena such as diffraction,
This is a kind of physics colour generation, has many advantages, such as bright-colored, will never fade, environmental-friendly, short preparation period.Wherein pass through glue
The orderly self-assembly method of body microballoon, the opal photonic crystal of the high low-refraction alternating variation of formation, it may have photon band gap
Feature, when incident light frequency is fallen in bandgap range, which will not pass through the photonic crystal, these cannot be after resuming
The visible light broadcast can be reflected by photonic crystal, finally form coherent diffraction in the photon crystal surface with periodic structure, and
Generate bright and colourful schemochrome.By in nature and the research of artificial preparation structure color, at present display, decoration,
There is good application in anti-fake equal fields.In recent years, the photonic crystal that hollow ball was assembled into is existed by the extensive of researcher, such as Deng
Synthesis of Monodisperse Polystyrene@Vinyl-SiO2Core-Shell Particles and
Hollow SiO2Spheres, Lu are in Synthesis and Crystallization of Hybrid Spherical
It is proposed that silica is hollow respectively in Colloids Composed of Polystyrene Cores and Silica Shells
The preparation method of ball photonic crystal structure color film mainly passes through PS@SiO2Self assembly of the nucleocapsid microballoon on substrate,
Then in glass baseplate surface assembling acquisition, which has the technology of calcining organics removal core under air
Preferable structure.However, in the above-mentioned methods, since the shell of the photonic crystal of silica hollow ball assembling is relatively thin, causing to have
Effect index modulation is smaller, to which the photonic crystal that hollow silica assembles all has the smaller disadvantage of reflected intensity, this
Application of the hollow ball photonic crystal in terms of schemochrome will seriously be limited.
Invention content
The purpose of the present invention is to provide a kind of hollow silica photonic crystal structure color film of yellow green and its preparation sides
Method, this method is simple and practicable, environmentally safe, and the hollow silica photonic crystal structure color film color of yellow green obtained is full
With degree height, not fugitive color.
The present invention is to be achieved through the following technical solutions：
A kind of preparation method of the hollow silica photonic crystal structure color film of yellow green, includes the following steps：
1) by grain size be 280 ± 5nm polystyrene microsphere powder ultrasonic disperse in the mixed liquor of ethyl alcohol and deionized water
In, ammonium hydroxide is then added, silicon source is added after mixing well into mixed system, after being stirred to react, centrifuging and taking precipitation is precipitated through washing
It washs, dry, PS@SiO obtained2Nucleocapsid microballoon；
2) by PS@SiO2Nucleocapsid microballoon is scattered in absolute ethyl alcohol, is made and is contained SiO2The emulsion of microballoon；
3) glass substrate is dipped vertically into containing SiO2In the emulsion of microballoon, dried at 40~50 DEG C to containing SiO2
After absolute ethyl alcohol volatilization completely in the emulsion of microballoon, nucleocapsid photon crystal film is made in glass substrate surface；
4) nucleocapsid photon crystal film is calcined 1~4 hour under 500~600 DEG C of reducing atmospheres, high color is made
The hollow silica photonic crystal structure color film of saturation degree yellow green.
The amount ratio of polystyrene microsphere powder, ethyl alcohol and deionized water is 0.03g in step 1)：(25~40) mL：(3
~5) mL.
The ammonium hydroxide that 0.3~0.5mL mass fractions are 30% is added in every 30~45mL ethyl alcohol and the mixed liquor of deionized water.
Step 1) the silicon source is that ethyl orthosilicate is added into mixed system, and addition is micro- per 0.03g polystyrene
250~300 μ L ethyl orthosilicates are added in ball powder.
Mixing well after step 1) addition ammonium hydroxide is to use 30~50min of magnetic agitation at room temperature；After silicon source is added
To be stirred to react be 7~10h of magnetic agitation at room temperature.
Centrifugation described in step 1) is carried out at 4000~8000r/min, centrifugation time 3-6min.
The washing of described pair of precipitation of step 1) is will to precipitate to first pass through deionization washing 2~4 times, clear using absolute ethyl alcohol
It washes 2~4 times.
PS@SiO in step 2)2The amount ratio of nucleocapsid microballoon and absolute ethyl alcohol is (0.1~0.25) g：10mL.
Glass substrate is before using through over cleaning：It is first to impregnate 10h in 30% hydrogen peroxide solution, then use in mass concentration
Deionized water and absolute ethyl alcohol respectively cleaning 2~3 times.
The invention also discloses adopt the hollow silica photonic crystal structure color film of yellow green obtained with the aforedescribed process.
Compared with prior art, the present invention has technique effect beneficial below：
The preparation method of the hollow silica photonic crystal structure color film of yellow green disclosed by the invention is with grain size first
Organic polystyrene (PS) microballoon powder of 280 ± 5nm is template, in its surface modification-NH first2, then utilize improvedMethod coats one layer of uniform silicon oxide layer on its surface, then forms albumen in glass substrate surface by self assembly
The photon crystal structure of stone structure, then PS microballoons are carbonized by the calcining under protection of reducing atmosphere, due to the PS microballoons of carbonization
The atrament generated is present in inside each hollow silica shell, to absorb most of incoherent scattering light, part
The PS of carbonization is present in hollow ball inside, greatly improves hollow ball color saturation, and photon is assembled into solve hollow ball
It is brilliant to obtain a kind of yellow green photon assembled with high saturation silica hollow ball for the low disadvantage of crystal color visibility
Body schemochrome film.Present invention process process is simple and practicable, environmentally safe, and energy large-scale industrial production has wide
Application prospect.
Through yellow green film color produced by the present invention is beautiful, saturation degree is high, not fugitive color, solves chemical organic compounds face
Expect fugitive color, harmful disadvantage.
Description of the drawings
Fig. 1, which is 1 gained of embodiment, has the hollow silica photonic crystal structure color film of high color saturation yellow green
Optical microscope photograph；
Fig. 2 is 1 gained PS@SiO of embodiment2The TEM photos of microballoon.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Embodiment 1
A kind of preparation method of the hollow silica photonic crystal structure color film of yellow green, includes the following steps：
(1) by polystyrene (PS) microballoon powder, ethyl alcohol and deionized water according to 0.03g:30mL:The amount ratio of 3mL claims
Take the PS microballoon powder ultrasonic disperses that grain size is 280 ± 5nm in absolute ethyl alcohol and the mixed liquor of deionized water, dispersion is complete
Afterwards, the ratio of 0.3mL ammonium hydroxide is added according to every 30mL mixed liquors, ammonium hydroxide is added into mixed liquor, magnetic agitation mixes at room temperature
30min, then 250 μ L ethyl orthosilicates are rapidly joined as silicon source into reaction system, it is passed through after magnetic agitation reaction 8h at room temperature
Cross washing, centrifugation, drying, you can obtain PS@SiO2Nucleocapsid microballoon.
(2) precise step (1) obtains PS@SiO2Nucleocapsid microballoon 0.1g, ultrasonic disperse is in 10ml absolute ethyl alcohols
In, it is made and contains SiO2The emulsion of microballoon, and vertical deposition method plated film on a glass substrate is utilized in 40 DEG C of baking ovens.
(3) the nucleocapsid photon crystal film of preparation is calcined into 2h under 500 DEG C of reducing atmospheres, organic micro-spheres are carbonized,
It can be obtained the hollow silica photonic crystal structure color film of yellow green of existing high color saturation.
Referring to Fig. 1, the structure color element after as can be seen from Figure 1 calcining is showed with the yellowish green of high saturation
Color, color are very beautiful.
Referring to Fig. 2, as can be seen from Figure 2 there is uniform grain using the hollow silicon oxide microsphere that this method is prepared
Diameter, and the state for the high degree of dispersion being in are conducive to the progress of self assembling process；It can be seen from the figure that after calcined, have
Machine layer has been removed, and hollow silicon oxide ball is successfully made.
Embodiment 2
A kind of preparation method of the hollow silica photonic crystal structure color film of yellow green, includes the following steps：
(1) by polystyrene (PS) microballoon powder, ethyl alcohol and deionized water according to 0.03g:35mL:The amount ratio of 4mL claims
Take the PS microballoon powder ultrasonic disperses that grain size is 280 ± 5nm in absolute ethyl alcohol and the mixed liquor of deionized water, dispersion is complete
Afterwards, the ratio of 0.4mL ammonium hydroxide is added according to every 35mL mixed liquors, ammonium hydroxide is added into mixed liquor, magnetic agitation mixes at room temperature
40min, then 300 μ L ethyl orthosilicates are rapidly joined as silicon source into reaction system, it is passed through after magnetic agitation reaction 10h at room temperature
Cross washing, centrifugation, drying, you can obtain PS@SiO2Nucleocapsid microballoon；
(2) precise step (1) obtains PS@SiO2Nucleocapsid microballoon 0.15g, ultrasonic disperse is in 10mL absolute ethyl alcohols
In, obtain SiO2The emulsion of microballoon, and vertical deposition method plated film on a glass substrate is utilized in 45 DEG C of baking ovens.
(3) the nucleocapsid photon crystal film of preparation is calcined into 3h under 550 DEG C of reducing atmospheres, because organic micro-spheres
Carbonization, you can obtain the hollow silica photonic crystal structure color film of yellow green of existing high color saturation.
Embodiment 3
A kind of preparation method of the hollow silica photonic crystal structure color film of yellow green, includes the following steps：
(1) by polystyrene (PS) microballoon powder, ethyl alcohol and deionized water according to 0.03g:40mL:The amount ratio of 5mL claims
Take the PS microballoon powder ultrasonic disperses that grain size is 280 ± 5nm in absolute ethyl alcohol and the mixed liquor of deionized water, dispersion is complete
Afterwards, ammonium hydroxide is added into mixed liquor for the ratio for 0.5mL ammonium hydroxide being added according to every 45ml mixed liquors, and magnetic agitation mixes at room temperature
30min, then 270 μ L ethyl orthosilicates are rapidly joined as silicon source into reaction system, it is passed through after magnetic agitation reaction 7h at room temperature
Cross washing, centrifugation, drying, you can obtain PS@SiO2Nucleocapsid microballoon；
(2) precise step (1) obtains PS@SiO2Nucleocapsid microballoon 0.18g, ultrasonic disperse is in 10mL absolute ethyl alcohols
In obtained SiO2The emulsion of microballoon, and vertical deposition method plated film on a glass substrate is utilized in 40~50 DEG C of baking ovens.
(3) the nucleocapsid photon crystal film of preparation is calcined into 2h under 600 DEG C of reducing atmospheres, because organic micro-spheres
Carbonization, you can obtain the hollow silica photonic crystal structure color film of yellow green of existing high color saturation.
In conclusion the present invention prepares the PS microballoons of 280 ± 5nm of uniform particle sizes first using no emulsion polymerization,
Again by improvedIt is PS@SiO that method can be obtained grain size in one layer of silica of its coated with uniform2Nucleocapsid is micro-
Ball can be obtained finally by the carbonization of organic PS under protection of reducing atmosphere with the hollow silica photon of high-brightness yellow-green color
Crystal film.This method solve the low problems of hollow ball photonic crystal color intensity, while this yellow green film color is bright
Beautiful, fugitive color, does not solve chemical organic compounds pigment fugitive color, harmful disadvantage.Present invention process process is simply easy
Row enormously simplifies experimentation, and the hollow silica photonic crystal structure color film of yellow green obtained with the method has
There is higher saturation degree, showing, print, coating, cosmetics, photonic crystal etc. is widely used.
Claims (6)
1. a kind of preparation method of the hollow silica photonic crystal structure color film of yellow green, which is characterized in that including following step
Suddenly：
1) by grain size be 280 ± 5nm polystyrene microsphere powder ultrasonic disperse in ethyl alcohol and the mixed liquor of deionized water, so
After ammonium hydroxide is added, silicon source is added after mixing well into mixed system, after being stirred to react, centrifuging and taking precipitation, precipitation it is washed, dry
It is dry, PS@SiO obtained2Nucleocapsid microballoon；
2) by PS@SiO2Nucleocapsid microballoon is scattered in absolute ethyl alcohol, is made and is contained SiO2The emulsion of microballoon；
3) glass substrate is dipped vertically into containing SiO2In the emulsion of microballoon, dried at 40~50 DEG C to containing SiO2Microballoon
Emulsion in absolute ethyl alcohol completely volatilization after, nucleocapsid photon crystal film is made in glass substrate surface；
4) nucleocapsid photon crystal film is calcined 1~4 hour under 500~600 DEG C of reducing atmospheres, it is hollow that yellow green is made
Silica photonic crystal structure color film；
Wherein, the amount ratio of polystyrene microsphere powder, ethyl alcohol and deionized water is 0.03g in step 1)：(25~40) mL：(3
~5) mL；PS@SiO in step 2)2The amount ratio of nucleocapsid microballoon and absolute ethyl alcohol is (0.1~0.25) g：10mL；
Wherein, 0.3~0.5mL mass fractions are added in step 1) in every 30~45mL ethyl alcohol and the mixed liquor of deionized water is
30% ammonium hydroxide；Step 1) the silicon source is that ethyl orthosilicate is added into mixed system, and addition is per 0.03g polystyrene
250~300 μ L ethyl orthosilicates are added in microballoon powder.
2. the preparation method of the hollow silica photonic crystal structure color film of yellow green according to claim 1, feature
It is, mixing well after step 1) addition ammonium hydroxide is to use 30~50min of magnetic agitation at room temperature；Stirring after silicon source is added
It is 7~10h of magnetic agitation at room temperature to mix reaction.
3. the preparation method of the hollow silica photonic crystal structure color film of yellow green according to claim 1, feature
It is, the centrifugation described in step 1) is carried out at 4000~8000r/min, and centrifugation time is 3~6min.
4. the preparation method of the hollow silica photonic crystal structure color film of yellow green according to claim 1, feature
It is, the washing of described pair of precipitation of step 1) is will to precipitate to first pass through deionization washing 2~4 times, using washes of absolute alcohol 2
~4 times.
5. the preparation method of the hollow silica photonic crystal structure color film of yellow green according to claim 1, feature
It is, glass substrate is before using through over cleaning：It is first to impregnate 10h in 30% hydrogen peroxide solution, then spend in mass concentration
Ionized water and absolute ethyl alcohol respectively cleaning 2~3 times.
6. using the hollow silica photon crystal structure of yellow green made from the method described in any one of Claims 1 to 5
Color film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510872923.0A CN105541122B (en) | 2015-12-02 | 2015-12-02 | A kind of hollow silica photonic crystal structure color film of yellow green and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510872923.0A CN105541122B (en) | 2015-12-02 | 2015-12-02 | A kind of hollow silica photonic crystal structure color film of yellow green and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105541122A CN105541122A (en) | 2016-05-04 |
| CN105541122B true CN105541122B (en) | 2018-08-28 |
Family
ID=55820748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510872923.0A Active CN105541122B (en) | 2015-12-02 | 2015-12-02 | A kind of hollow silica photonic crystal structure color film of yellow green and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105541122B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021481B (en) * | 2018-06-27 | 2021-01-15 | 大连理工大学 | Colored inverse opal structure photonic crystal plastic film with bright pearlescent color and luster, and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288492B (en) * | 2013-05-29 | 2014-10-01 | 陕西科技大学 | Preparation method of red photonic crystal structured colored glaze |
| CN103288491B (en) * | 2013-05-29 | 2014-06-04 | 陕西科技大学 | Preparation method of blue-green photonic crystal structure color film |
-
2015
- 2015-12-02 CN CN201510872923.0A patent/CN105541122B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105541122A (en) | 2016-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106115805B (en) | The preparation method of the sour nickel/mos2 microsphere of nanometer hierarchy cobalt | |
| CN109201438B (en) | Composite photon structure material with high color generation, high brightness and low angle dependence and preparation method thereof | |
| CN103738969B (en) | Mesoporous silica and preparation method thereof | |
| CN103288491B (en) | Preparation method of blue-green photonic crystal structure color film | |
| CN108529692B (en) | Preparation method of hollow spherical nickel oxide | |
| CN105271796B (en) | A kind of low angle dependence blueness zinc sulphide schemochrome film and preparation method thereof | |
| CN109928643B (en) | PS @ TiO with non-iridescent effect2Structural color film and preparation method and application thereof | |
| CN104607231A (en) | Carbon nitride photocatalyst with three-dimensional ordered macroporous structure and preparation method thereof | |
| CN105175015A (en) | Low-angle-dependence violet zinc-sulfide structural color film and preparing method thereof | |
| CN103949193A (en) | Universal method for preparing inorganic hollow microspheres | |
| CN107162047B (en) | A kind of preparation method of titanium dioxide hollow ball | |
| CN101767205A (en) | Preparation method of hollow nickel nanosphere | |
| CN113106759B (en) | Structural yarn dyed fabric based on caffeic acid and preparation method thereof | |
| CN102600773B (en) | Method for preparing shell fluorescent microsphere | |
| CN104386699B (en) | Double-template legal system is for the method for many shells mesoporous silicon oxide nanomaterial | |
| CN104860350B (en) | TiO2The solvent process for thermosynthesizing of nucleocapsid structure sub-micron ball | |
| CN105481264B (en) | A kind of WO of morphology controllable3The preparation method of film | |
| CN107879349A (en) | A kind of monodisperse mesoporous silica microballoon powder and preparation method thereof | |
| CN105174302B (en) | Red low-angle-dependence zinc sulfide structure color materials and preparation method thereof | |
| CN105439462B (en) | A kind of hollow silica photonic crystal structure color film of purple and preparation method thereof | |
| CN105541122B (en) | A kind of hollow silica photonic crystal structure color film of yellow green and preparation method thereof | |
| CN104817280A (en) | Preparation method of red photonic crystal structure color thin film with photo-catalytic effect | |
| CN105439461B (en) | A kind of hollow silica photonic crystal structure color film of blue-green and preparation method thereof | |
| CN105113006A (en) | Mono-dispersed spherical zinc sulfide photonic crystal with rough surface and preparation method thereof | |
| CN105152208B (en) | Synthetic method of colorful TiO2 microsphere and application of colorful TiO2 microsphere |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |