CN102503139A - Up-conversion luminescence transparent glass ceramics and preparation method thereof - Google Patents
Up-conversion luminescence transparent glass ceramics and preparation method thereof Download PDFInfo
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- CN102503139A CN102503139A CN2011103537575A CN201110353757A CN102503139A CN 102503139 A CN102503139 A CN 102503139A CN 2011103537575 A CN2011103537575 A CN 2011103537575A CN 201110353757 A CN201110353757 A CN 201110353757A CN 102503139 A CN102503139 A CN 102503139A
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Abstract
The invention provides a method for preparing up-conversion luminescence transparent glass ceramics. The method comprises the following steps of: dispersing up-conversion luminescence doping gadolinium oxide nanocrystals in borate glass uniformly, batching, melting, forming, annealing and the like. The prepared up-conversion luminescence transparent glass ceramics have a simple process, and are low in production cost and high in luminous intensity.
Description
Technical field
The invention belongs to field of light emitting materials, especially relate to a kind of preparation of up-conversion luminous transparent glass ceramic.
Background technology
Rare earth oxide is common fluorescent material matrix, and wherein gadolinium sesquioxide has the visible region and do not have the energy level absorption, and specific refractory power is high, is prone to realize the rare earth ion doped excellent properties that waits, and is the rare earth luminescent material matrix of widespread use.The doping gadolinium sesquioxide also is applied to up-conversion luminescent material, because of its unique luminescent properties (long wavelength light excites down and sends short-wavelength light), has obtained widespread use in fields such as solid statelaser, transmitter, solar cell, 3 D stereo demonstrations.But its monocrystal material or transparent ceramic material complicated process of preparation, cost is higher, and the exploitation equivalent material has important practical and is worth.
Because of its good potential application foreground; The scientific worker has prepared the luminescent glass ceramic of many excellent propertys: the Wang Yuan of Fujian Inst. of Matter Structure, Chinese Academy of Sciences gives birth to the melt supercooled method that adopts that waits; Prepared the nanocrystalline transparent oxyfluoride glass ceramic of er-doped fluorinated yttrium barium; It is nanocrystalline to have a great erbium ion solid solubility, infrared ray excited down, increased substantially up-conversion luminescence intensity (Chinese patent 200610135388.1); Prepared down-conversion luminescent transparent glass ceramic, itself and silicon solar cell are coupled, and are expected to reduce the thermalization effect of silicon solar cell, improve the photoelectric transformation efficiency (Chinese patent 200810071325.3) of battery; Handle two steps through melt supercooled method and follow-up crystallization; Prepared the tunable transparent glass ceramics of a kind of glow color; It launches the visible light of colour tunable under near ultraviolet excitation; Comprise the intensive white light, being expected exploitation becomes demonstration of new type of solid state three-dimensional light and backlight material (Chinese patent 200910112947.0).The Wang Shu of University of Science & Technology, Beijing is bright to be waited through batching, melting; Moulding, annealing; Glass cutting; It is transparent glass ceramics that processes such as glass heat processing have prepared a kind of rare earth ion doped Na2O-CaO-SiO2, compares with single crystal substrate, and its production technique is simple, cost is low, doping content is high; Compare with glass matrix, the crystallite phase separate out thermal conductivity and the thermal shock resistance (Chinese patent 200910210385.3) that has improved material.The equality preparation of Fan of Zhejiang University elder generation adopts high temperature melting to prepare different semiconductor lighting glass-ceramic with thermal treatment process; Its method is simple, pollution-free, cost is low; High and the Heat stability is good (Chinese patent 200910154361.0,200710069422.4) of luminosity; Adopt reducing atmosphere high temperature melting and heat of crystallization treatment process, prepared near ultraviolet excitated blue luminescent glass ceramic, under near-ultraviolet light LED excites, can produce blue-light-emitting (Chinese patent 200810122223.X).
Existing method all is to adopt the generation of heat treating method original position nanocrystalline, and uncontrollable dopant ion is enriched in nanocrystalline process, and all there are deficiency in accurate control, the uniform doping property of its composition.Glass-ceramic is the transparent block materials of glassy phase and crystallite phase composite, and when crystallite is uniformly distributed in the glass basis, and crystal particle scale can be realized high transmission rate when reaching nano level far below lambda1-wavelength.If at first prepare luminous oxide nanocrystalline, mix with the glass oxide component, high temperature sintering generates glass-ceramic, because of its crystal grain is nanoscale, far below lambda1-wavelength, can realize high transmission rate, is a kind of method for preparing the high quality light-emitting glass-ceramic.Therefore develop a kind ofly based on mixing up-conversion luminescence nanometer crystal, the method for preparing luminescent glass ceramic has actual value.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of up-conversion luminescence crystalline ceramics, this luminescent glass ceramic material has characteristics such as technology is simple, production cost is low, luminous intensity height.The present invention realizes through following technical scheme:
1. the feed composition and the content (molar percentage) of doping gadolinium sesquioxide luminescence transparent pottery are: Al
2O
310-14%; Na
2O 10-25%; B
2O
360-77%; Up-conversion luminescence Gd
2O
30-4%
2. the nanocrystalline preparation of doping gadolinium sesquioxide is that (mol ratio of doping with rare-earth ions and gadolinium ion is 0.1: 4-1: 4), be coprecipitator with urea, under hydrothermal condition, generate presoma, it is nanocrystalline to make the doping gadolinium sesquioxide through calcining for raw material with the inorganic salt of rare earth.
3. preparation method according to claim 2 is characterized in that, adopts Al
2O
3, Na
2CO
3, H
3BO
3, up-conversion luminescence Gd
2O
3As raw material, prepare burden by above-mentioned content, grind even post-heating to 900-1200 degree centigrade and be incubated 2-8 hour, then with melt directly cooling obtain transparent glass ceramics.
4. the glass-ceramic after the moulding is eliminated internal stress in 500-700 degree centigrade of insulation annealing in 2-4 hour, obtain luminescent transparent glass ceramic.
The invention provides a kind of luminescent transparent glass ceramic preparation method who directly mixes up-conversion luminescence nanometer crystal; Technology is simple, production cost is low, compare with glass matrix; Light emitting ionic directly crystallite mutually in; Have like the crystalline spectral signature, fluorescence intensity is stronger, can be used as novel up-conversion luminescent material.
Description of drawings
Accompanying drawing is the fluorescent emission curve (980nm excites) of glass-ceramic after the thermal treatment.
Embodiment
Instance 1: with analytically pure Al
2O
3, Na
2CO
3, H
3BO
3Gd with preparation
2O
3Nanocrystalline, press Al
2O
3: Na
2CO
3: H
3BO
3: Gd
2O
3=4: the accurate weighing of the proportioning of 4: 20: 1 (mol ratio) also mixes; In agate mortar, fully grind to form and mix powder; And be placed in the platinum crucible, in program control resistance furnace, be heated to 1100 ℃ and be incubated 3 hours, melting liquid is poured in the copper mold of preheating be shaped then; The glass-ceramic that obtains is put into program control resistance furnace again and is heated to 600 ℃ and be incubated 3 hours; Promptly obtain the adulterated transparent glass ceramics of gadolinium sesquioxide; Sample is handled through surface finish, can observe ruddiness up-conversion luminescence signal with the measurement of Horiba JY FL3 XRF.Accompanying drawing is the fluorescent emission curve that makes glass-ceramic, shows that it is red up-conversion luminescence.
Instance 2: with analytically pure Al
2O
3, Na
2CO
3, H
3BO
3Gd with preparation
2O
3Nanocrystalline, press Al
2O
3: Na
2CO
3: H
3BO
3: Gd
2O
3=4: the accurate weighing of the proportioning of 4: 30: 1 (mol ratio) also mixes; In agate mortar, fully grind to form and mix powder; And be placed in the platinum crucible, in program control resistance furnace, be heated to 1000 ℃ and be incubated 3 hours, melting liquid is poured in the copper mold of preheating be shaped then; The glass-ceramic that obtains is put into program control resistance furnace again and is heated to 600 ℃ and be incubated 3 hours; Promptly obtain the adulterated transparent glass ceramics of gadolinium sesquioxide; Sample is handled through surface finish, can observe the conversion red signal light with the measurement of Horiba JY FL3 XRF.
Instance 3: with analytically pure Al
2O
3, Na
2CO
3, H
3BO
3Gd with preparation
2O
3Nanocrystalline, press Al
2O
3: Na
2CO
3: H
3BO
3: Gd
2O
3=4: the accurate weighing of the proportioning of 8: 20: 1 (mol ratio) also mixes; In agate mortar, fully grind to form and mix powder; And be placed in the platinum crucible, in program control resistance furnace, be heated to 1200 ℃ and be incubated 3 hours, melting liquid is poured in the copper mold of preheating be shaped then; The glass-ceramic that obtains is put into program control resistance furnace again and is heated to 600 ℃ and be incubated 3 hours; Promptly obtain the adulterated transparent glass ceramics of gadolinium sesquioxide; Sample is handled through surface finish, can observe the conversion red signal light with the measurement of Horiba JY FL3 XRF.
Claims (5)
1. the preparation method of a up-conversion luminous transparent glass ceramic, its characteristic:,, make up-conversion luminous transparent glass ceramic through batch mixing, melting and annealing with the nanocrystalline borate glass system of mixing of up-conversion luminescence gadolinium sesquioxide.
2. preparation method according to claim 1 is characterized in that: the feed composition and the content (molar percentage) of described doping gadolinium sesquioxide luminescence transparent pottery are: Al
2O
310-14%; Na
2O 10-25%; B
2O
360-77%; Up-conversion luminescence Gd
2O
30-4%.
3. preparation method according to claim 1; It is characterized in that: the nanocrystalline preparation of described up-conversion luminescence gadolinium sesquioxide is raw material with the inorganic salt of rare earth; The mol ratio of doping with rare-earth ions and gadolinium ion is 0.1: 4-1: 4; Urea is coprecipitator, under hydrothermal condition, generates presoma, and it is nanocrystalline to make the doping gadolinium sesquioxide through calcining.
4. preparation method according to claim 1 is characterized in that: adopt Al
2O
3, Na
2CO
3, H
3BO
3, up-conversion luminescence Gd
2O
3As raw material, prepare burden by above-mentioned content, grind even post-heating to 900-1200 degree centigrade and be incubated 2-8 hour, then with melt directly cooling obtain transparent glass ceramics.
5. preparation method according to claim 1 is characterized in that: the glass-ceramic after the moulding is eliminated internal stress in 500-700 degree centigrade of insulation annealing in 2-4 hour, obtain luminescent transparent glass ceramic.
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| CN201110353757.5A CN102503139B (en) | 2011-11-10 | 2011-11-10 | A kind of up-conversion luminous transparent glass ceramic and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304142A (en) * | 2013-02-21 | 2013-09-18 | 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 |
| CN106396413A (en) * | 2016-09-08 | 2017-02-15 | 长春理工大学 | Erbium-ytterbium co-doped up-conversion luminescent glass ceramic containing barium tungstate crystalline phase 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 |
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| 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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2011
- 2011-11-10 CN CN201110353757.5A patent/CN102503139B/en active Active
Patent Citations (3)
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| 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 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304142A (en) * | 2013-02-21 | 2013-09-18 | 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 |
| 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 |
| CN106396413A (en) * | 2016-09-08 | 2017-02-15 | 长春理工大学 | Erbium-ytterbium co-doped up-conversion luminescent glass ceramic containing barium tungstate crystalline phase and preparation method thereof |
| 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 |
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| CN102503139B (en) | 2016-08-17 |
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Effective date of registration: 20180629 Address after: 350108 207, room 2, Chuang Chuang, hi tech Industrial Park, Fuzhou High-tech Zone, 8 Minhou Road, Minhou, Fujian. Patentee after: FUJIAN ZHONGKE XINYUAN OPTOELECTRONICS TECHNOLOGY CO., LTD. Address before: Fuzhou City, Fujian province 350002 Yangqiao Road No. 155 Patentee before: Fujian Institute of Research on the Structure of Matter, Chinese Academy of Scie |