CN102503139B - A kind of up-conversion luminous transparent glass ceramic and preparation method thereof - Google Patents
A kind of up-conversion luminous transparent glass ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of up-conversion luminous transparent glass ceramic.By up-conversion luminescence doping nanocrystalline dispersed in borate glass of Gadolinia., through steps such as dispensing, melted, molding, annealing, it is prepared for the up-conversion luminous transparent glass ceramic that technique is simple, production cost is low, luminous intensity is high.
Description
Technical field
The invention belongs to field of light emitting materials, especially relate to the preparation of a kind of up-conversion luminous transparent glass ceramic.
Background technology
Rare earth oxide is common fluorescent material matrix, and wherein Gadolinia. has visual field without energy level absorption, and refractive index is high, easily realizes rare earth ion doped excellent properties of Denging, is wide variety of rare earth luminescent material substrate.Doping Gadolinia. is also applied to up-conversion luminescent material, because of the luminescent properties (long wavelength light excites down and sends short-wavelength light) of its uniqueness, shows etc. that field is widely applied at solid state laser, sensor, solaode, 3 D stereo.But its monocrystal material or transparent ceramic material complicated process of preparation, relatively costly, exploitation substitution material has important practical and is worth.
Because of the potential application foreground that it is good, scientific worker is prepared for the luminescent glass ceramic of many function admirables: Fujian Inst. of Matter Structure, Chinese Academy of Sciences Wang Yuan life etc. uses melt supercooled method, it is prepared for the transparent oxyfluoride glass ceramic that er-doped barium Han yttrium fluoride is nanocrystalline, it is nanocrystalline has great erbium ion solid solubility, under infrared ray excited, Up-conversion Intensity (Chinese patent 200610135388.1) is greatly improved；Being prepared for down-conversion luminescent transparent glass ceramic, it is coupled with silicon solar cell, is expected to reduce the thermo effect of silicon solar cell, improves the photoelectric transformation efficiency (Chinese patent 200810071325.3) of battery；By melt supercooled method and two steps of follow-up Crystallizing treatment, it is prepared for a kind of tunable transparent glass ceramics of glow color, it launches the visible ray of colour tunable under near ultraviolet excitation, including strong white light, it is expected to be developed into novel solid three-dimensional light and show and backlight source material (Chinese patent 200910112947.0).The bright grade of University of Science & Technology, Beijing Wang Shu is through dispensing, melting；Molding, annealing；Glass-cutting；The processes such as glass heat process are prepared for a kind of rare earth ion doped Na2O-CaO-SiO2 system transparent glass ceramics, and compared with single crystal substrate, its production technology is simple, low cost, doping content are high；Compared with glass matrix, the precipitation of crystallite phase improves thermal conductivity and the thermal shock resistance (Chinese patent 200910210385.3) of material.The equality preparation of Fan elder generation of Zhejiang University uses high temperature melting and Technology for Heating Processing to be prepared for different semiconductor lighting glass ceramics, its method is simple, pollution-free, low cost, luminosity height and Heat stability is good (Chinese patent 200910154361.0,200710069422.4)；Use reducing atmosphere high temperature melting and crystallize Technology for Heating Processing, be prepared near ultraviolet excitated blue luminescent glass ceramic, blue-light-emitting (Chinese patent 200810122223.X) can be produced under black light LED excites.
The method of having is all to use heat treatment method in-situ preparation nanocrystalline, it is impossible to controls dopant ion and is enriched in nanocrystalline process, accurately control, uniform doping all Shortcomings of its composition.Glass ceramics is the transparent block materials of glass phase and crystallite phase composition, in crystallite is uniformly distributed in glass basis, and when crystal particle scale reaches nanoscale far below lambda1-wavelength, can realize high transmission rate.If first preparing luminous oxide nanocrystalline, mixing with glass oxide component, high temperature sintering generates glass ceramics, because its crystal grain is nanoscale, far below lambda1-wavelength, can realize high transmission rate, be a kind of method preparing high quality light-emitting glass ceramics.Therefore exploitation is a kind of based on mixing up-conversion luminescence nanometer crystal, and the method preparing luminescent glass ceramic has real value.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of up-conversion luminescence crystalline ceramics, this luminescent glass ceramic material has that technique is simple, production cost is low, luminous intensity high.The present invention is achieved through the following technical solutions:
1. raw material components and the content (molar percentage) of doping Gadolinia. luminescence transparent pottery is: Al2O310-14%；Na2O 10-25%；B2O360-77%；Up-conversion luminescence Gd2O30-4%
2. the preparation that doping Gadolinia. is nanocrystalline, with inorganic salt of rare earth as raw material (mol ratio of doping with rare-earth ions and gadolinium ion is as 0.1:4-1:4), with carbamide as coprecipitator, generate presoma under hydrothermal conditions, prepare doping Gadolinia. through calcining nanocrystalline.
3. according to above-mentioned preparation method, it is characterised in that use Al2O3、Na2CO3、H3BO3, up-conversion luminescence Gd2O3As raw material, carry out dispensing by above-mentioned content, grind uniform post-heating to 900-1200 degree Celsius and be incubated 2-8 hour, then melt is directly cooled down and obtain transparent glass ceramics.
4. the glass ceramics after molding is eliminated internal stress in 500-700 degree Celsius of insulation annealing in 2-4 hour, obtain luminescent transparent glass ceramic.
The invention provides a kind of luminescent transparent glass ceramic preparation method being directly incorporated into up-conversion luminescence nanometer crystal, technique is simple, production cost is low, compared with glass matrix, light emitting ionic directly crystallite mutually in, there is the spectral signature like crystal, fluorescence intensity is relatively strong, can be as novel up-conversion luminescent material.
Accompanying drawing explanation
Accompanying drawing is the fluorescence emission curves (980nm excites) of glass ceramics after heat treatment.
Detailed description of the invention
Example 1: by analytically pure Al2O3、Na2CO3、H3BO3Gd with preparation2O3Nanocrystalline, by Al2O3∶Na2CO3∶H3BO3∶Gd2O3The proportioning accurate weighing of=4: 4: 20: 1 (mol ratio) also mixes, mix homogeneously powder body it is fully ground in agate mortar, and be placed in platinum crucible, program-controlled resistor stove it is heated to 1100 DEG C and is incubated 3 hours, then melting liquid being poured in the copper mold of preheating and shape；The glass ceramics obtained places into and is heated to 600 DEG C in program-controlled resistor stove and is incubated 3 hours, i.e. obtain the transparent glass ceramics of Gadolinia. doping, sample processes through surface finish, can observe HONGGUANG up-conversion luminescence signal with Horiba JY FL3 fluorescence spectrophotometer measurement.Accompanying drawing is the fluorescence emission curves preparing glass ceramics, shows that it is red up-conversion luminescence.
Example 2: by analytically pure Al2O3、Na2CO3、H3BO3Gd with preparation2O3Nanocrystalline, by Al2O3∶Na2CO3∶H3BO3∶Gd2O3The proportioning accurate weighing of=4: 4: 30: 1 (mol ratio) also mixes, mix homogeneously powder body it is fully ground in agate mortar, and be placed in platinum crucible, program-controlled resistor stove it is heated to 1000 DEG C and is incubated 3 hours, then melting liquid being poured in the copper mold of preheating and shape；The glass ceramics obtained places into and is heated to 600 DEG C in program-controlled resistor stove and is incubated 3 hours, i.e. obtains the transparent glass ceramics of Gadolinia. doping, and sample processes through surface finish, can observe upper conversion red signal light with Horiba JY FL3 fluorescence spectrophotometer measurement.
Example 3: by analytically pure Al2O3、Na2CO3、H3BO3Gd with preparation2O3Nanocrystalline, by Al2O3∶Na2CO3∶H3BO3∶Gd2O3The proportioning accurate weighing of=4: 8: 20: 1 (mol ratio) also mixes, mix homogeneously powder body it is fully ground in agate mortar, and be placed in platinum crucible, program-controlled resistor stove it is heated to 1200 DEG C and is incubated 3 hours, then melting liquid being poured in the copper mold of preheating and shape；The glass ceramics obtained places into and is heated to 600 DEG C in program-controlled resistor stove and is incubated 3 hours, i.e. obtains the transparent glass ceramics of Gadolinia. doping, and sample processes through surface finish, can observe upper conversion red signal light with Horiba JY FL3 fluorescence spectrophotometer measurement.
Claims (4)
1. a preparation method for up-conversion luminous transparent glass ceramic, is characterized in that: by up-conversion luminescence oxygen
Change gadolinium nanocrystalline incorporation borate glass system, through batch mixing, melting and annealing, prepare up-conversion luminescence transparent
Glass ceramics；
The raw material components of the transparent glass ceramics that described doping up-conversion luminescence Gadolinia. is nanocrystalline and moles hundred
Point content is: Al2O310-14%；Na2O10-25%；B2O360-77%；Up-conversion luminescence Gd2O30-4%,
Wherein Gd2O3It is not 0.
Preparation method the most according to claim 1, is characterized in that: described up-conversion luminescence Gadolinia.
Nanocrystalline preparation is with inorganic salt of rare earth as raw material, and doping with rare-earth ions with the mol ratio of gadolinium ion is
0.1:4-1:4, carbamide is coprecipitator, generates presoma under hydrothermal conditions, prepares doping Gadolinia. through calcining
Nanocrystalline.
Preparation method the most according to claim 1, is characterized in that: use Al2O3、Na2CO3、H3BO3、
Up-conversion luminescence Gd2O3As raw material, carry out dispensing by above-mentioned content, grind uniform post-heating to 900-1200
Degree Celsius and be incubated 2-8 hour, then melt is directly cooled down and obtains transparent glass ceramics.
Preparation method the most according to claim 1, is characterized in that: the glass ceramics after molding existed
500-700 degree Celsius of insulation annealing in 2-4 hour eliminates internal stress, obtains up-conversion luminous transparent glass ceramic.
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| CN103304142B (en) * | 2013-02-21 | 2015-05-20 | 山东康友光电科技股份有限公司 | Manufacturing method of spontaneous crystallization type up-conversion luminescence transparent glass ceramics |
| CN106396413B (en) * | 2016-09-08 | 2018-11-09 | 长春理工大学 | Erbium and ytterbium codoping up-conversion luminescent glass ceramics of crystalline phase containing barium tungstate and preparation method thereof |
| CN109775988A (en) * | 2019-04-04 | 2019-05-21 | 长春理工大学 | One kind containing Na9YSi6O18Crystal phase transparent glass ceramics and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265026A (en) * | 2008-04-18 | 2008-09-17 | 中国计量学院 | Microcrystalline glass for precipitating La2O3 nano-crystalline and preparation method thereof |
| CN101456675A (en) * | 2007-12-11 | 2009-06-17 | 中国科学院福建物质结构研究所 | Glass-ceramics for emitting bright white light through up-conversion |
| CN101723591A (en) * | 2009-11-25 | 2010-06-09 | 海洋王照明科技股份有限公司 | Borate microcrystalline glass and method for preparing same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456675A (en) * | 2007-12-11 | 2009-06-17 | 中国科学院福建物质结构研究所 | Glass-ceramics for emitting bright white light through up-conversion |
| CN101265026A (en) * | 2008-04-18 | 2008-09-17 | 中国计量学院 | Microcrystalline glass for precipitating La2O3 nano-crystalline and preparation method thereof |
| CN101723591A (en) * | 2009-11-25 | 2010-06-09 | 海洋王照明科技股份有限公司 | Borate microcrystalline glass and method for preparing same |
Non-Patent Citations (1)
| Title |
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| Gd2O3:Tm3+-Yb3+纳米晶粉体的制备及其上转换发光;陈秋立等;《哈尔滨师范大学自然科学学报》;20101231;第26卷(第5期);第41-44,59页 * |
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