CN1071721C - High-refractive index transparent ceramic micro-bead and its manufacture method and use - Google Patents
High-refractive index transparent ceramic micro-bead and its manufacture method and use Download PDFInfo
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- CN1071721C CN1071721C CN97116915A CN97116915A CN1071721C CN 1071721 C CN1071721 C CN 1071721C CN 97116915 A CN97116915 A CN 97116915A CN 97116915 A CN97116915 A CN 97116915A CN 1071721 C CN1071721 C CN 1071721C
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Abstract
The present invention relates to a high-refractive index transparent ceramic micro-bead and a manufacturing method thereof and an application thereof. The high-refractive index transparent ceramic micro-bead comprises 50 to 99 wt% of barium titanate and 1 to 49 wt% of shaping auxiliary agent. In the method of the present invention, the barium titanate and the shaping auxiliary agents are prepared into fine ceramic slurry, the slurry is prepared into granules with a certain size range by an ordinary drying method, and then the granules are sintered at a high temperature of more than 1000 DEG C to obtain the high-refractive index transparent ceramic micro-bead. The transparent ceramic micro-bead can be used for manufacturing a series of regressive reflecting materials such as regressive reflecting films, regressive reflecting paint, etc.
Description
The present invention relates to a kind of high-refractive index transparent ceramic micro-bead and application thereof that can be used for the regression reflecting sign.
Up to now, the transparent ceramic micro-bead that is widely used in the regression reflecting sign is most made through pyroprocessing by the amorphous glass powder basically.The refractive index n of common glass powder has only about 1.5, and its main component is a silicon-dioxide.The main component of high refractive index (n is 1.8～2.3) glass powder is a kind of or several heavy metal oxides, and the molecular formula of these oxide compounds is: Al
2O
3, BaO, BeO, Bi
2O
3, CaO, La
2O
3, MgO, PbO, TiO
2, ZnO, ZrO
2The disclosed relevant technology of making this class material has three kinds, first melting method.This method is earlier the component raw material to be carried out high-temperature fusion to be processed into vitreum, then vitreum is ground into powder, again the powder pyroprocessing is become transparent ceramic micro-bead.It two is sol-gel methodes, as the Chinese patent publication number is CN87.100121A and CN1045407A (application number: 90102069.9) the described precursor dispersion thing (precursor) that is about to metal oxide, as colloidal sol, the water-sol or the aqueous solution, be transformed into gel earlier by hydrolysis and polycondensation process, carry out drying again, burn till processing at last.The third method is a powder metallurgic method; Described in United States Patent (USP) 4.192.576 (March 11,1980), this method is carried out high temperature high pressure process with raw material earlier and is become stock, with its pulverizing, grinds to form powder then, and further pyroprocessing becomes transparent ceramic micro-bead.
The existence that these three kinds of methods have needs high-temperature fusion to handle, and promptly has the big shortcoming of energy consumption, and there is preparation technology's more complicated in the method that perhaps has, the problem that technical process is long, and these shortcomings all strengthen production cost.
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, in order to omit the high-temperature fusion step, cut down the consumption of energy, simplify technology, shortened process, reduce production costs and improve the finished product physicochemical property, adopt the fine ceramics powder to make raw material directly to carry out high temperature and burn till transparent ceramic micro-bead of acquisition and preparation method thereof thereby provide a kind of.
The object of the present invention is achieved like this:
A kind of high-refractive index transparent ceramic micro-bead provided by the invention, this microballon have the granularity of 10 μ m～150 μ m: its specific refractory power is up to n=1.9～2.4: this microballon is by the method preparation that comprises the following steps:
(1) makes raw material with the fine ceramics slurries of handling gained through wet chemical method, this slurry component contains fine ceramics powder, shaping assistant, water-soluble polymer tackiness agent and water, wherein metatitanic acid barium salt fine ceramics powder content in slurry is 15～45% (weight), shaping assistant content is 0.5～25% (weight), the water-soluble polymer binder content is 0.1～3% (weight), and water-content is 30～60% (weight); Described shaping assistant is selected from boric acid or silicic acid; Described water-soluble polymer tackiness agent is selected from polyvinyl alcohol, polyoxyethylene glycol, polyoxyethylene, methylcellulose gum, carboxymethyl cellulose, carboxyethyl cellulose, ethyl cellulose or hydroxypropylcellulose; The slurry preparation step is as follows:
The water-soluble polymer tackiness agent that at first under fully stirring, in the barium titanate salt solution slurries that contain 15～45% (weight), adds the shaping assistant and 0.1～3% (weight) of 0.5～25% (weight), continue to stir 20 minutes, under 50 ℃～150 ℃ conditions, be processed into the fine ceramics slurries:
In order to obtain the solid microbeads body of highly transparent, when the preparation slurry, should improve the powder solid content of slurry as much as possible, make the good fluidity of slurry simultaneously again.If solid content is low, slurry is thickness again, and then powder will contain a large amount of spaces, causes powder to produce a large amount of spaces after high temperature burns till, and causes the transparency of microballon obviously to descend.So can add the mineral acid of 0.5～25% (weight) such as nitric acid, hydrochloric acid when slurrying, perhaps organic acid such as acetic acid etc. fully dissolve each other slurries and mix mutually;
(2) drying step with the drying means that is selected from air stream drying method, fluid-bed drying or spray-drying process, carries out drying to gained slurries in the step (1), and it is done the powder that 20 μ m～150 μ m are processed in refining;
(3) high temperature processing step 1000 ℃～1500 ℃ sintering 0.01～10 minute, promptly gets high-refractive index transparent ceramic micro-bead to the powder of gained in the above-mentioned steps (2).
High-refractive index transparent ceramic micro-bead provided by the invention can be used to prepare regression reflecting coating and regression reflecting film.About regression reflecting coating, can be with reference to the application for a patent for invention prospectus, application number: 96100080.5, publication number: CN1141323A.
Advantage of the present invention: 1. its microballon granularity of the high-refractive index transparent ceramic micro-bead of preparing is 10 μ m～120 μ m.Its specific refractory power is up to n=1.9～2.4; 2. preparation method of the present invention omits the high-temperature fusion step, and technical process is short and simple, and energy consumption is low, reduces cost widely and improves the physicochemical property of finished product.3. technology of the present invention is easy to serialization production, and the engineering equipment expense is few; 4. method technology of the present invention is suitable for producing other functional non-crystalline state microballon material equally.
Below in conjunction with embodiment the present invention is described in detail: but this this embodiment places restrictions on protection scope of the present invention absolutely not.Embodiment 1:
Under well-beaten situation, to containing 30% (by the slurries gross weight, down with) add 3.5% boric acid in the aqueous slurry of metatitanic acid barium salt, continuing under the stirring state then, in this solution, add 2.0% concentration again and be 40% the carboxyethyl cellulose powder aqueous solution.Continue to stir after 20 minutes, the spray-drying process that water-soluble serous warp is common is handled the powder that obtains the about 100 μ m of particle diameter.After these powder granule thorough dryings, in fluidizing furnace, be heated 1000 ℃～1200 ℃, just obtained the solid transparent spheres of ceramic of particle diameter up to 50 μ m.When shining observation from different perspectives with the torch light beam, these solid transparent ball-type powders can reflect extremely bright retroreflecting light under the viewing angle of broad range.Specific refractory power by the solid transparent ceramic fine bead of present embodiment preparation is n=1.9.
Embodiment 2:
The barium carbonate powder of adding 45% in the solution that contains 2% (by the slurries gross weight, down together) silicon sol.After fully stirring, add 0.5% methylcellulose gum again, and continued stir about 20 minutes.Under 120 ℃ of conditions, above-mentioned slurries are carried out air stream drying.Resulting powder after the drying after Temperature Treatment between 1200 ℃～1500 ℃, is examined under a microscope gained powder product, and they all are transparent solid sphere, and its diameter range is 20 μ m～100 μ m.It is milky opaque body that a few granules is wherein also arranged.The specific refractory power of measuring gained solid transparent spheroid is 2.2.
Claims (4)
1. high-refractive index transparent ceramic micro-bead, this microballon has the granularity of 10 μ m～150 μ m; Its specific refractory power is up to n=1.9～2.4; This microballon is prepared by the method that comprises the following steps:
(1) makes raw material, this slurry component with the fine ceramics slurries of handling gained through wet chemical method
Contain fine ceramics powder, shaping assistant, water-soluble polymer tackiness agent and water, wherein metatitanic acid barium salt essence
Fine ceramics powder content in slurry is 15～45WT%, and shaping assistant content is 0.5～25WT%,
The water-soluble polymer binder content is 0.1～3WT%, and water-content is 30～60WT%; Described
Shaping assistant is selected from boric acid or silicic acid; Described water-soluble polymer tackiness agent is selected from polyvinyl alcohol, poly-second
Glycol, polyoxyethylene, methylcellulose gum, carboxymethyl cellulose, carboxyethyl cellulose, ethyl fibre
Dimension element or hydroxypropylcellulose; The slurry preparation step is as follows:
At first under fully stirring, in the barium titanate salt solution slurries that contain 15～45WT%, add 0.5
The water-soluble polymer tackiness agent of the shaping assistant of～25WT% and 0.1～3WT% continues to stir 20
Minute, under 50 ℃～150 ℃ conditions, be processed into the fine ceramics slurries;
(2) drying step is with the drying that is selected from air stream drying method, fluid-bed drying or spray-drying process
Method is carried out drying to gained slurries in the step (1), and 20 μ m～150 μ m are processed in its dried refining
Powder;
(3) high temperature processing step, the powder of gained in the above-mentioned steps (2) at 1000 ℃～1500 ℃
Sintering 0.01～10 minute promptly gets high-refractive index transparent ceramic micro-bead.
2. by the transparent ceramic micro-bead of the described preparation high refractive index of claim 1, it is characterized in that: also be included in the mineral acid or the organic acid that add 0.5～25WT% in the fine ceramics slurries that step (1) makes.
3. by the transparent ceramic micro-bead of the described preparation high refractive index of claim 1, it is characterized in that: the mineral acid that adds 0.5～25WT% in the slurries of described step (1) is selected from nitric acid, hydrochloric acid, boric acid or silicic acid, perhaps comprises the organic acid of acetic acid.
4. the described high-refractive index transparent ceramic micro-bead of claim 1 is used to prepare the application of regression reflecting coating and regression reflecting film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116915A CN1071721C (en) | 1997-09-18 | 1997-09-18 | High-refractive index transparent ceramic micro-bead and its manufacture method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116915A CN1071721C (en) | 1997-09-18 | 1997-09-18 | High-refractive index transparent ceramic micro-bead and its manufacture method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1211558A CN1211558A (en) | 1999-03-24 |
| CN1071721C true CN1071721C (en) | 2001-09-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97116915A Expired - Fee Related CN1071721C (en) | 1997-09-18 | 1997-09-18 | High-refractive index transparent ceramic micro-bead and its manufacture method and use |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101608055B (en) * | 2008-06-16 | 2011-05-11 | 东莞市宝临塑胶有限公司 | Imitated ceramic plastic material |
| CN101792311B (en) * | 2010-03-09 | 2012-11-07 | 武汉理工大学 | Preparation method of barium dititanate target |
| RU2656660C1 (en) * | 2016-11-07 | 2018-06-06 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Томский государственный университет систем управления и радиоэлектроники" (ТУСУР) | THERMO STABILIZING RADIATION RESISTANT COATING BaTiZrO3 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4172576A (en) * | 1977-06-21 | 1979-10-30 | General Signal Corporation | Highway crossing system with motion detecting apparatus |
| CN87100121A (en) * | 1986-01-13 | 1987-08-05 | 明尼苏达州采矿制造公司 | The road sign that contains transparent non-vitreous ceramic microspheres |
| CN86106629A (en) * | 1986-09-27 | 1988-04-06 | 中国科学院上海光学精密机械研究所 | Glass of high refractive index |
| CN1045407A (en) * | 1986-01-13 | 1990-09-19 | 明尼苏达州采矿制造公司 | The road sign that contains transparent non-vitreous ceramic microspheres |
| CN1096019A (en) * | 1994-04-12 | 1994-12-07 | 南京化工学院陶瓷厂 | Ceramic fine bead and manufacture method thereof |
| CN1158321A (en) * | 1996-11-21 | 1997-09-03 | 中国建筑材料科学研究院 | Crystallized glass microball and its prodn. tech. |
-
1997
- 1997-09-18 CN CN97116915A patent/CN1071721C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4172576A (en) * | 1977-06-21 | 1979-10-30 | General Signal Corporation | Highway crossing system with motion detecting apparatus |
| CN87100121A (en) * | 1986-01-13 | 1987-08-05 | 明尼苏达州采矿制造公司 | The road sign that contains transparent non-vitreous ceramic microspheres |
| CN1045407A (en) * | 1986-01-13 | 1990-09-19 | 明尼苏达州采矿制造公司 | The road sign that contains transparent non-vitreous ceramic microspheres |
| CN86106629A (en) * | 1986-09-27 | 1988-04-06 | 中国科学院上海光学精密机械研究所 | Glass of high refractive index |
| CN1096019A (en) * | 1994-04-12 | 1994-12-07 | 南京化工学院陶瓷厂 | Ceramic fine bead and manufacture method thereof |
| CN1158321A (en) * | 1996-11-21 | 1997-09-03 | 中国建筑材料科学研究院 | Crystallized glass microball and its prodn. tech. |
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|---|---|
| CN1211558A (en) | 1999-03-24 |
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