CN102174276A - Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper - Google Patents
Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper Download PDFInfo
- Publication number
- CN102174276A CN102174276A CN2011100560917A CN201110056091A CN102174276A CN 102174276 A CN102174276 A CN 102174276A CN 2011100560917 A CN2011100560917 A CN 2011100560917A CN 201110056091 A CN201110056091 A CN 201110056091A CN 102174276 A CN102174276 A CN 102174276A
- Authority
- CN
- China
- Prior art keywords
- polystyrene
- titanium dioxide
- cerium
- electronic paper
- preparation
- 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.)
- Granted
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a method for preparing a cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper, which comprises the following steps of: hydrolyzing titanate on the outer layers of polystyrene microspheres serving as a template in an alcohol/nitrile mixed solvent containing ammonia water and distilled water to prepare polystyrene and titanium dioxide composite particles; immersing and stirring the composite particles in a cerium sol for 4 to 12 hours, performing centrifugal separation, and drying at the temperature of between 60 and 100 DEG C; and roasting at the temperature of between 500 and 600 DEG C for 2 to 6 hours to prepare cerium-doped titanium dioxide pigment microspheres with a hollow structure, wherein the microspheres are yellow and have the particle size of 100 to 400nm and the relative density of 1.4 to 2.8g/cm<3>. The yield of the polystyrene and titanium dioxide composite particles is controlled by adjusting the addition amount of water, so that the yield of cerium-doped hollow nano titanium dioxide yellow pigment particles is improved, and the problem that the content of secondary particles in the polystyrene and titanium dioxide core-shell composite particles is high at present is solved. The yellow hollow microspheres prepared by the method have a regular shape and low relative density, and the particle size is easy to control. The invention has the advantages that: raw materials are readily available, and the method is environment-friendly.
Description
One, technical field
The invention belongs to the electronic paper technology field, particularly a kind of Electronic Paper is with the preparation method of cerium doping hollow nano titanium oxide yellow ultramarine.
Two, background technology
Electronic Paper is a kind of novel indicating meter, has less energy-consumption, flexible shows, characteristics such as ultra-thin light, high-contrast, high-res.The approach that realizes electronic paper technology at present mainly includes cholesterol liquid crystal technique of display, electrophoretic display technology (EPD) and electric wetting technique of display etc.Wherein be the most potential technological approaches with the micro encapsulation electrophoretic display technology.It will be coated among the microcapsule by the electrophoresis disclosing solution that electrophoresis particle, suspension, charge control agent and stablizer etc. are formed, and utilize electrophoresis particle to be subjected to electric field action in painted suspension and electrophoretic migration takes place realize showing.The colored demonstration is the main direction of present electronic paper technology research, adopts colored filter to realize usually.But spectral filter not only can reduce the brightness of reflection-type electric paper display, also can reduce the saturation ratio of color.Doing electrophoresis particle with colored organic pigments also is one of method that realizes full-color demonstration, but mineral dye size distribution commonly used is wide, surface irregularity and density are bigger, dispersion stabilization in suspension is poor, can reduce the contrast gradient of prepared electronic paper display device, shorten its work-ing life.
Utilizing metal ion mixing is one of method for preparing on the colored organic pigments particle, and metal ion commonly used at present mainly contains Cr
3+, Co
2+, Al
3+, Fe
3+Deng.But contain Cr
3+, contain Co
2+Pigment has certain toxicity, so its use is more and more restricted, simultaneously, transition metals such as Fe, Co cause the influence that chromatic effect is subjected to the character of change of coordination number and adjacent ions significantly, be difficult to reliably, stably control the color development effect.
In order to improve the density matching of electrophoresis particle and organic solvent, improve its dispersion stabilization in organic solvent, can adopt usually electrophoresis particle is carried out organic coating modification or it is prepared into the method for hollow microsphere.Template is a kind of common method of preparation hollow microsphere, and it at first is preparation nuclear (template)/shell (target wall) composite particles on the basis of selected template, by the method for physics or chemistry the kernel template is removed then, thereby is obtained the target hollow-particle.The key of this method is will prepare to coat complete, uniform particle diameter and do not have nuclear (template)/shell (target wall) composite particles that other disturb particles (as the secondary particle of spontaneous nucleation etc.).
Three, summary of the invention
Technical problem:
The object of the present invention is to provide the preparation method of a kind of eco-friendly Electronic Paper with cerium doping hollow nano titanium oxide yellow ultramarine.
The present invention adds the yield of the water yield with control polystyrene and titanium dioxide core-shell composite particles by regulating, thereby improve the yield of cerium doping hollow titanium dioxide yellow ultramarine particle, solve the many defectives of secondary particle in present polystyrene and titanium dioxide core-shell composite particles, simultaneously, by introducing Rare-Earth Ce
4+Ion is to give the hollow microsphere yellow nature, the preparation non-toxic pigment, simultaneously since rare earth element painted be the transition of electron that relies in the inner f shell, seldom be subjected to the influence of adjacent ions character, thereby solve the unmanageable defective of transition metal pigment color development effect that contains commonly used.Its technical scheme:
A kind of Electronic Paper of the present invention may further comprise the steps with the preparation method of cerium doping hollow nano titanium oxide yellow ultramarine:
1) be that alcohol/nitrile mixed solution of 2:1 ~ 4:1 mixes with ammoniacal liquor, distilled water and volume ratio, wherein ammoniacal liquor and distilled water account for 0.33% ~ 0.44% and 0.25% ~ 0.50% of ammoniacal liquor, distilled water and alcohol/nitrile mixed solution three total mass respectively, promptly obtain containing the alcohol/nitrile mixed solvent of ammoniacal liquor and distilled water
2) polystyrene microsphere is dispersed in the described mixed solvent, is mixed with mass percent and is 0.02% ~ 0.2% polystyrene dispersion liquid; The preparation mass percent is the ethanol solution of 3% ~ 7% titanic acid ester, stir down it is splashed in the described polystyrene dispersion liquid, and the quality of the titanic acid ester solution that is dripped accounts for 15% ~ 18% of titanic acid ester solution and polystyrene dispersion liquid total mass, 20 ~ 35 ℃ were reacted 2 ~ 12 hours down, centrifugation, oven dry obtains white spherical polystyrene and titanium dioxide complex particle behind the absolute ethanol washing
3) be to add ceric ammonium nitrate in the dehydrated alcohol of 7:1 and the distilled water mixed solvent in volume ratio, the ceric ammonium nitrate solution of preparation 0.1 ~ 0.2mmol/L, add 2 times of mol ratios then to the citric acid of ceric ammonium nitrate, the back adding volume that stirs accounts for the ethylene glycol or the polyoxyethylene glycol of described ceric ammonium nitrate solution 10% ~ 30%, reaction obtained yellow transparent cerium colloidal sol in 2 hours under 20 ℃ ~ 35 ℃
4) with step 2) spherical polystyrene that obtains and titanium dioxide complex particle be immersed in the cerium colloidal sol that step 3) obtains, wherein, the quality of the composite particles that adds accounts for 0.05% ~ 0.1% of composite particles and cerium colloidal sol total mass, stirred 4 ~ 12 hours, 60 ℃ ~ 100 ℃ oven dry, be prepared into cerium doped titanium dioxide yellow ultramarine microballoon in 2 ~ 6 hours 500 ℃ ~ 600 ℃ roastings at last after the centrifugation with hollow structure.
Polystyrene microsphere used in the present invention surface shows electronegativity.
Alcohol used in the present invention/nitrile mixed solvent is dehydrated alcohol/acetonitrile mixed solvent.
Titanic acid ester used in the present invention is isopropyl titanate or tetrabutyl titanate.
Raw material polystyrene used in the present invention, titanic acid ester and doping agent ceric ammonium nitrate all are nontoxic or low toxicity, environmental friendliness.
Beneficial effect:
React according to technique scheme: the starting material toxicological harmless, environmental friendliness, the reaction conditions gentleness, product postprocessing is simple; The yellow hollow pigment microballoon regular shape for preparing, any surface finish, relative density are at 1.4 ~ 2.8g/cm
3Between, median size is at 100 ~ 400nm.
In the present invention, the adding of suitable quantity of water, can effectively be controlled at the polystyrene microsphere surface and carry out coated by titanium dioxide: be example with the tetrabutyl titanate, an amount of water can promote the hydrolysis of tetrabutyl titanate, produces (the C of capacity
4H
9O)
3TiOH monomer, itself and ammoniacal liquor further act on and produce electronegative (C
4H
9O)
3TiO
-,, can impel the NH in the mixed solvent because the polystyrene microsphere surface shows electronegativity
4+In a large amount of enrichments in its surface, thereby make electronegative (C
4H
9O)
3TiO
-Cause and NH
4+Interaction and be adsorbed to polystyrene microsphere surface fast and at NH
4+Catalysis under the original position condensation, thereby form polystyrene and titanic oxide composite microsphere.
In the present invention, select Rare-Earth Ce for use
4+Ion doping is to give the hollow microsphere yellow nature.Compare with transition metal such as Cr, Fe, Co, rare earth element is painted to be the transition of electron that relies in the inner f shell, seldom is subjected to the influence of adjacent ions character.Because the yellow nature of prepared hollow microsphere itself when therefore being used for the Electronic Paper demonstration, can not reduce the saturation ratio of its brightness and color.Simultaneously, compare with transition metal such as Cr, Co, the toxicity of Rare-Earth Ce is very little, and prepared yellow ultramarine is environmentally friendly.
In the present invention, select for use the styrene polymer microballoon to do template, can control the size of hollow microsphere inner chamber by the polystyrene microsphere of selecting different-grain diameter.Simultaneously, can regulate the wall thickness of final hollow microsphere by the consumption of control titanic acid ester.Thereby the yellow hollow microsphere pigment that can prepare the different size requirement is to satisfy the demand of Electronic Paper industry.
Four, description of drawings
Fig. 1 is the transmission electron microscope picture of the product that made by the present invention;
Fig. 2 is the wide-angle x-ray diffraction spectrogram of the product that made by the present invention;
Fig. 3 is the ultraviolet-visible of the product that made by the present invention spectrogram that diffuses;
Fig. 4 is polystyrene and the titanium dioxide complex particle that is made by the present invention;
Fig. 5 is polystyrene and the titanium dioxide complex particle for preparing when not adding distilled water in the preparation process;
Fig. 6 adds in the preparation process to account for polystyrene and the titanium dioxide complex particle for preparing when the mixed solvent mass percent is 0.70% distilled water.
Five, embodiment
Embodiment 1
A kind of Electronic Paper is with cerium doping hollow nano titanium oxide yellow ultramarine, and this pigment particle size is 100nm, 200nm, 300nm, 400nm, and relative density is 1.4g/cm
3, 1.6g/cm
3, 2.2g/cm
3, 2.8g/cm
3, its preparation method is to be template with the styrene polymer microballoon, prepares polystyrene and titanium dioxide complex particle in its outer hydrolysis titanic acid ester.The submergence in cerium colloidal sol of this composite particles was stirred 4 ~ 12 hours, drying after the centrifugation, roasting is prepared from.
Embodiment 2
A kind of Electronic Paper may further comprise the steps with the preparation method of cerium doping hollow nano titanium oxide yellow ultramarine:
1) be that alcohol/nitrile mixed solution of 2:1,3:1 or 4:1 mixes with ammoniacal liquor, distilled water and volume ratio, wherein ammoniacal liquor and distilled water account for 0.33% or 0.44% and 0.25%, 0.30% or 0.50% of ammoniacal liquor, distilled water and alcohol/nitrile mixed solution three total mass respectively, promptly obtain containing the alcohol/nitrile mixed solvent of ammoniacal liquor and distilled water
2) the styrene polymer microballoon is dispersed in the described mixed solvent, is mixed with mass percent and is 0.02%, 0.05%, 0.10%, 0.15% or 0.2% polystyrene dispersion liquid; The preparation mass percent is the ethanol solution of 3%, 5% or 7% titanic acid ester, stir down it is splashed in the described polystyrene dispersion liquid, and the quality of the titanic acid ester solution that is dripped accounts for 15%, 16%, 17% or 18% of titanic acid ester solution and polystyrene dispersion liquid total mass, 20 ℃, 25 ℃, 30 ℃ or 35 ℃ were reacted 2,6,10 or 12 hours down, centrifugation, oven dry obtains white spherical polystyrene and titanium dioxide complex particle behind the absolute ethanol washing
3) be to add ceric ammonium nitrate in the dehydrated alcohol of 7:1 and the distilled water mixed solvent in volume ratio, the ceric ammonium nitrate solution of preparation 0.1mmol/L, 0.15mmol/L or 0.2mmol/L, add 2 times of mol ratios then to the citric acid of ceric ammonium nitrate, the back adding volume that stirs accounts for the ethylene glycol or the polyoxyethylene glycol of described ceric ammonium nitrate solution 10%, 20% or 30%, reaction obtained yellow transparent cerium colloidal sol in 2 hours under 20 ℃, 25 ℃, 30 ℃ or 35 ℃
4) with step 2) spherical polystyrene that obtains and titanium dioxide complex particle be immersed in the cerium colloidal sol that step 3) obtains, wherein, the quality of the composite particles that adds accounts for 0.05%, 0.08% or 0.1% of composite particles and cerium colloidal sol total mass, stirred 4,8 or 12 hours, 60 ℃, 80 ℃ or 100 ℃ of oven dry, at last be prepared into cerium doped titanium dioxide yellow ultramarine microballoon in 2,4 or 6 hours after the centrifugation with hollow structure 500 ℃ or 600 ℃ of roastings.
In the present embodiment,
Employed polystyrene microsphere surface shows electronegativity.
Employed alcohol/nitrile mixed solvent is dehydrated alcohol/acetonitrile mixed solvent.
Employed titanic acid ester is isopropyl titanate or tetrabutyl titanate.
Comparative Examples 1
Adopt to prepare cerium doped titanium dioxide hollow Nano microsphere yellow ultramarine with the foregoing description 2 identical methods, difference is not add distilled water in the reaction.Measurement result is shown in Fig. 5.
Comparative Examples 2
Adopt to prepare cerium doped titanium dioxide hollow Nano microsphere yellow ultramarine with the foregoing description 2 identical methods, difference has added in being to react that to account for the mixed solvent mass percent be 0.70% distilled water.Measurement result is shown in Fig. 6.
With reference to Fig. 1, according to transmission electron microscope picture analysis revealed product of the present invention, its edge is obviously different with the contrast that the center is showed in the transmission electron microscope picture, and the color of edge is darker, and the center color is more shallow, proves that product has hollow structure.
With reference to Fig. 2, show that according to the wide-angle x-ray diffraction analysis product of the present invention has the crystallization phases of titanium dioxide and cerium dioxide, prove that product is the adulterated titanium dioxide hollow microballoon of cerium.
With reference to Fig. 3, according to ultraviolet-visible diffuse reflection spectrum analysis revealed product of the present invention visible light more than the 580nm there is strong reflection, prove that product can be used as yellow ultramarine.
With reference to Fig. 4, prepare by the present invention in the process of polystyrene and titanium dioxide complex particle according to transmission electron microscope picture analysis revealed, the adding of suitable quantity of water can promote the hydrolysis of tetrabutyl titanate, thereby produces more (C
4H
9O)
3TiOH monomer, itself and ammoniacal liquor further act on and produce electronegative (C
4H
9O)
3TiO
-, because polystyrene microsphere surface NH
4+A large amount of enrichments, electronegative (C
4H
9O)
3TiO
-Be adsorbed to polystyrene microsphere surface fast and at NH
4+Catalysis under the original position condensation, show polystyrene and the titanic oxide composite microsphere that coats evenly, do not have secondary TiO 2 particles thereby form.
Contrast Fig. 5 and Fig. 6, according to transmission electron microscope picture analysis revealed in the preparation process of polystyrene and titanium dioxide complex particle, if except that adding ammoniacal liquor, no longer add distilled water, then effectively hydrolysis of tetrabutyl titanate can not form obvious and effective coated by titanium dioxide layer at the outside surface of polystyrene moulding; Add too much distilled water and then can significantly reduce (C
4H
9O)
3The monomeric solubleness of TiOH, this just means that the nucleation rate of secondary TiO 2 particles improves greatly in the system, thereby influences the prepared polystyrene and the yield of titanium dioxide complex particle.
Claims (5)
1. an Electronic Paper is characterized in that it may further comprise the steps with the preparation method of cerium doping hollow nano titanium oxide yellow ultramarine:
With ammoniacal liquor, distilled water and volume ratio is that alcohol/nitrile mixed solution of 2:1 ~ 4:1 mixes, wherein ammoniacal liquor and distilled water account for 0.33% ~ 0.44% and 0.25% ~ 0.50% of ammoniacal liquor, distilled water and alcohol/nitrile mixed solution three total mass respectively, promptly obtain containing the alcohol/nitrile mixed solvent of ammoniacal liquor and distilled water
Polystyrene microsphere is dispersed in the described mixed solvent, is mixed with mass percent and is 0.02% ~ 0.2% polystyrene dispersion liquid; The preparation mass percent is the ethanol solution of 3% ~ 7% titanic acid ester, stir down it is splashed in the described polystyrene dispersion liquid, and the quality of the titanic acid ester solution that is dripped accounts for 15% ~ 18% of titanic acid ester solution and polystyrene dispersion liquid total mass, 20 ~ 35 ℃ were reacted 2 ~ 12 hours down, centrifugation, oven dry obtains white spherical polystyrene and titanium dioxide complex particle behind the absolute ethanol washing
In volume ratio is to add ceric ammonium nitrate in the dehydrated alcohol of 7:1 and the distilled water mixed solvent, the ceric ammonium nitrate solution of preparation 0.1 ~ 0.2mmol/L, add 2 times of mol ratios then to the citric acid of ceric ammonium nitrate, the back adding volume that stirs accounts for the ethylene glycol or the polyoxyethylene glycol of described ceric ammonium nitrate solution 10% ~ 30%, reaction obtained yellow transparent cerium colloidal sol in 2 hours under 20 ℃ ~ 35 ℃
With step 2) spherical polystyrene that obtains and titanium dioxide complex particle be immersed in the cerium colloidal sol that step 3) obtains, wherein, the quality of the composite particles that adds accounts for 0.05% ~ 0.1% of composite particles and cerium colloidal sol total mass, stirred 4 ~ 12 hours, 60 ℃ ~ 100 ℃ oven dry, be prepared into cerium doped titanium dioxide yellow ultramarine microballoon in 2 ~ 6 hours 500 ℃ ~ 600 ℃ roastings at last after the centrifugation with hollow structure.
2. Electronic Paper according to claim 1 is characterized in that with the preparation method of cerium doping hollow nano titanium oxide yellow ultramarine employed polystyrene microsphere surface shows electronegativity.
3. Electronic Paper according to claim 1 is characterized in that with the preparation method of cerium doping hollow nano titanium oxide yellow ultramarine employed alcohol/nitrile mixed solvent is dehydrated alcohol/acetonitrile mixed solvent.
4. Electronic Paper according to claim 1 is characterized in that with the preparation method of cerium doping hollow nano titanium oxide yellow ultramarine employed titanic acid ester is isopropyl titanate or tetrabutyl titanate.
5. Electronic Paper according to claim 1 is characterized in that employed raw material polystyrene, titanic acid ester and doping agent ceric ammonium nitrate all are nontoxic or low toxicity, environmental friendliness with the preparation method of cerium doping hollow nano titanium oxide yellow ultramarine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110056091 CN102174276B (en) | 2011-03-09 | 2011-03-09 | Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110056091 CN102174276B (en) | 2011-03-09 | 2011-03-09 | Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102174276A true CN102174276A (en) | 2011-09-07 |
| CN102174276B CN102174276B (en) | 2013-03-20 |
Family
ID=44517542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110056091 Expired - Fee Related CN102174276B (en) | 2011-03-09 | 2011-03-09 | Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102174276B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613958A (en) * | 2013-11-29 | 2014-03-05 | 深圳清华大学研究院 | Environment-friendly titanium pigment prepared by using complexation-precipitation process |
| CN105086518A (en) * | 2015-07-27 | 2015-11-25 | 安徽明珠颜料科技有限公司 | Black iron oxide pigment containing bamboo charcoal powder and preparation method thereof |
| CN105111794A (en) * | 2015-07-27 | 2015-12-02 | 安徽明珠颜料科技有限公司 | Black iron oxide pigment containing tourmalinite powder and preparation method thereof |
| CN106082317A (en) * | 2016-05-31 | 2016-11-09 | 陕西科技大学 | A kind of preparation method of hollow hemisphere titanium dioxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210120A (en) * | 2007-12-25 | 2008-07-02 | 天津大学 | Hollow titanium dioxide white electrophoresis ion for electrophoresis displaying and preparing method thereof |
-
2011
- 2011-03-09 CN CN 201110056091 patent/CN102174276B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210120A (en) * | 2007-12-25 | 2008-07-02 | 天津大学 | Hollow titanium dioxide white electrophoresis ion for electrophoresis displaying and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| KAI ZHANG ET AL: "Hollow titania spheres with movable silica spheres inside", 《LANGMUIR》 * |
| XIN DU ET AL: "Facile preparation of titania hollow spheres by combination of the mixed solvent method and the sol-gel process and post-calcination", 《MATERIALS RESEARCH BULLETIN》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613958A (en) * | 2013-11-29 | 2014-03-05 | 深圳清华大学研究院 | Environment-friendly titanium pigment prepared by using complexation-precipitation process |
| CN103613958B (en) * | 2013-11-29 | 2015-01-21 | 深圳清华大学研究院 | Environment-friendly titanium pigment prepared by using complexation-precipitation process |
| CN105086518A (en) * | 2015-07-27 | 2015-11-25 | 安徽明珠颜料科技有限公司 | Black iron oxide pigment containing bamboo charcoal powder and preparation method thereof |
| CN105111794A (en) * | 2015-07-27 | 2015-12-02 | 安徽明珠颜料科技有限公司 | Black iron oxide pigment containing tourmalinite powder and preparation method thereof |
| CN106082317A (en) * | 2016-05-31 | 2016-11-09 | 陕西科技大学 | A kind of preparation method of hollow hemisphere titanium dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102174276B (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102174276B (en) | Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper | |
| CN107162044B (en) | A kind of compound nuclear shell structure nano powder preparation method | |
| CN101767205B (en) | Preparation method of hollow nickel nanosphere | |
| CN105700265B (en) | Color electrophoretic display with electric field response photonic crystal properties and preparation method thereof and display methods | |
| US11512007B2 (en) | Process for preparing rodlike magnetiic ferroferric oxide material and use thereof | |
| CN112457499B (en) | Rare earth-based metal organic framework fluorescent nano material and preparation method and application thereof | |
| CN107689271A (en) | Preparation method, porous graphene film and the electronic product of porous graphene film | |
| CN102649907A (en) | Magnetic-control liquid crystal material, preparation method of liquid crystal display device and display device | |
| CN103484099A (en) | Color material under regulation and control of electric field, and preparation method of material | |
| CN114177893B (en) | Magnetic microsphere, preparation method and application | |
| CN102698756B (en) | Fe3O4/TiO2 nano magnetic compound and preparation method thereof | |
| Meng et al. | Monodisperse hollow tricolor pigment particles for electronic paper | |
| CN105384176A (en) | Prussian blue composite photonic crystal and preparing method and application thereof | |
| Yan et al. | Preparation of titanium dioxide compound pigments based on kaolin substrates | |
| CN113861965A (en) | Composite fluorescent material with multiple fluorescent characteristics and preparation method and application thereof | |
| CN107140687B (en) | A kind of compound nuclear shell structure nano powder | |
| Niu et al. | Preparation and characterization of novel yellow pigments: hollow TiO 2 spheres doped with cerium | |
| CN102832004A (en) | Fe3O4/TiO2 nano magnetic composition and in-situ growing preparation method thereof | |
| CN108502931B (en) | Preparation method of sea urchin-shaped FeOOH micron material | |
| CN103803639B (en) | Ionic liquid is utilized to prepare the method for nano-ITO powder | |
| CN109022837A (en) | The method for preparing rodlike rare earth oxalate powder based on reverse microemulsion process | |
| CN102762671A (en) | Titanium dioxide | |
| CN100383196C (en) | Method for preparing conducting particles for composite electrically-conducting paint using microemulsion technology | |
| CN101892047A (en) | Core-shell fluorescent material and preparation method thereof | |
| CN112280353B (en) | Antibacterial and ultraviolet-resistant thermochromic wax color paint and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130320 Termination date: 20160309 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |