CN104743885A - Rare earth-doped oxyfluoride germanate microcrystalline glass and preparation method thereof - Google Patents

Rare earth-doped oxyfluoride germanate microcrystalline glass and preparation method thereof Download PDF

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Publication number
CN104743885A
CN104743885A CN201510123499.XA CN201510123499A CN104743885A CN 104743885 A CN104743885 A CN 104743885A CN 201510123499 A CN201510123499 A CN 201510123499A CN 104743885 A CN104743885 A CN 104743885A
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glass
germanate
rare earth
doped
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胡曰博
高源�
邱建备
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Abstract

The invention discloses rare earth-doped oxyfluoride germanate microcrystalline glass and a preparation method thereof, and belongs to the technical field of luminescent materials. The microcrystalline glass comprises the following components in percentage by mole: 39-55% of GeO2, 5-15% of ZnO, 5-15% of AlF3, 10-25% of BaF2, 1-10% of Na2O, 1-20% of NaF and 0.5-5% of RF2 (R is rare earth elements). The preparation method comprises the following steps: firstly preparing oxyfluoride germanate glass by using a melt quenching method; and then, carrying out micro-crystallization on matrix glass by virtue of a thermal treatment process to obtain transparent oxyfluoride germanate microcrystalline glass, wherein the prepared oxyfluoride germanate microcrystalline glass has good transmission of light in a range from near-infrared rays to visible light, and the up-conversion luminescence of rare earth ions is remarkably enhanced. The prepared rare earth-doped oxyfluoride germanate microcrystalline glass containing NaBaAlF6 nano-crystals is simple in preparation method, high in environmental-friendly safety and relatively low in production cost.

Description

A kind of rear-earth-doped fluorine oxygen germanate devitrified glass and preparation method thereof
Technical field
The present invention relates to a kind of rear-earth-doped fluorine oxygen germanate devitrified glass and preparation method thereof, devitrified glass up-conversion luminescent material that particularly a kind of rear-earth-doped fluoride is nanocrystalline and preparation method thereof, belongs to luminescent material technical field.
Background technology
Rear-earth-doped frequency inverted luminescence technology has huge potential using value in fields such as solid-state laser, data storage, general illumination, 3 D stereo display, micro-imaging, sensing technology, solar cell, anti-counterfeiting technology and military confrontations, therefore, extensive research has been carried out to rear-earth-doped luminous material both at home and abroad.
Result of study shows, heat-treats rare earth institute doped substrate glass, and after crystalline phase appears in inside glass, rare earth ion preferentially in the inner enrichment of precipitation crystalline phase, can improve the frequency inverted luminous efficiency of rare earth ion greatly.Based on this, rear-earth-doped oxy-fluoride glass obtains large quantifier elimination at visible ray to the up-conversion luminescence near infrared wavelength region, and achieves abundant meaningful achievement.But the preparation of oxy-fluoride glass generally needs the deadly poisonous compound such as plumbous fluoride and cadmium fluoride as nucleator, consider from environmental angle, this severely limits its practical application.Therefore, people have developed alkaline including earth metal fluorochemical and the nanocrystalline devitrified glass of heavy metal fluoride sodium salt, to solve above-mentioned environmental issue.
In addition, fluorine oxygen bismuth germanate glass combines the advantage of bismuth germanate glass and crystal of fluoride, and maximum phonon energy is low, near infrared to visible wavelength range, have good light transmission, makes this component glass become the hot-candidate material of the Application Areass such as laser.At present, the Hu of domestic Kunming University of Science and Technology is said and rich is waited people to have reported for work Tm 3+/ Er 3+/ Yb 3+three mix containing BaF 2the fluorine oxygen germanate microcrystal glass material of nanometer crystalline phase.In addition, the people such as Xu Shiqing of the China Measures Institute has reported for work and has comprised β-NaGdF 4: Er 3+the fluorine oxygen silicate glass-ceramics of nanometer crystalline phase.But the research of separating out alkaline-earth metal fluoride sodium salt nanometer crystalline phase in rear-earth-doped fluorine oxygen bismuth germanate glass is not yet seen in report.
Summary of the invention
The object of this invention is to provide a kind of transparent rear-earth-doped oxy-fluoride glass, this devitrified glass has excellent thermostability and Safety and Environmental Protection, in visible ray near infrared wavelength region, there is good light transmission, and rare earth luminescence intensity obtains large increase; This rear-earth-doped glass frequency inverted luminescent material is obtained by following raw material, and each raw material and molar percentage are: GeO 239 ~ 55 mol %, ZnO 5 ~ 15 mol %, AlF 35 ~ 15 mol %, BaF 210 ~ 25 mol %, Na 2o 1 ~ 10 mol %, NaF1 ~ 20 mol %, RF 30.5 ~ 5 mol %, wherein R is one or more in rare earth element y b, Er, Tm, Nb, Ho, Tb.
Another object of the present invention is to the preparation method that above-mentioned rear-earth-doped fluorine oxygen germanate devitrified glass is provided, specifically comprise the steps:
(1) raw material is fully mixed be placed in crucible with cover, 30 ~ 60 min are founded at 1350 ~ 1450 DEG C, raw material is made to be melting into glass melt, glass melt is cast to fast on the Stainless Molding Board being preheating to 300 ~ 400 DEG C, after shaping, insulation 4 ~ 8 h carry out annealing and naturally cooling to room temperature at lower than glass transformation temperature 20 ~ 50 DEG C, obtain the glass containing rare earth ion, and obtained glass is carried out cut, grind and polished finish;
(2) glass containing rare earth ion step (1) prepared carries out differential thermal analysis, according to differential thermal analysis experiment, the obtained glass containing rare earth ion is placed in annealing furnace and heat-treats 15 ~ 60 min within the scope of T ~ T-50 DEG C, wherein T is the second crystallization peak temperature, and namely high temperature taking-up obtains rear-earth-doped containing NaBaAlF 6nanocrystalline transparent fluorine oxygen germanate devitrified glass.
Beneficial effect of the present invention is:
(1) what prepared by the present invention is rear-earth-doped containing NaBaAlF 6nanocrystalline fluorine oxygen germanate devitrified glass luminescent properties is good, and the experiment proved that, the devitrified glass after thermal treatment significantly improves than the Up-conversion Intensity of host glass;
(2) what prepared by the present invention is rear-earth-doped containing NaBaAlF 6nanocrystalline fluorine oxygen germanate devitrified glass has good light transmission near infrared to visible wavelength range;
(3) what prepared by the present invention is rear-earth-doped containing NaBaAlF 6nanocrystalline fluorine oxygen germanate devitrified glass preparation method is simple, and environmental safety is high, and production cost is lower.
Accompanying drawing explanation
Fig. 1 is doped in fluorine oxygen germanate presoma glass and contains NaBaAlF in embodiment 2 6er in nanocrystalline fluorine oxygen germanate devitrified glass 3+the up-conversion luminescence spectrum comparison diagram of ion.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described, but protection scope of the present invention is not limited to described content.
Embodiment 1
By composition 39GeO 220BaF 210ZnO10AlF 310Na 2o10NaF0.2ErF 30.3TmF 30.5YbF 3(mol%) GeO needed for total mass 10 grams is taken 2, BaF 2, ZnO, AlF 3, Na 2cO 3, NaF, ErF 3, TmF 3and YbF 3powder stock, abundant mixing load afterwards be placed in 1450 DEG C in crucible with cover at found 60min, then glass melt is cast to fast on the Stainless Molding Board being preheating to 400 DEG C, at the temperature lower than glass transformation temperature 20 DEG C, 4 h are incubated after shaping, Temperature fall is to room temperature, obtain the glass containing rare earth ion, and obtained glass is carried out cut, grind and polished finish; By obtained glass thermal treatment 60 min at lower than the second crystallization peak temperature 50 DEG C, naturally cool to room temperature, namely obtain containing NaBaAlF 6nanocrystalline rear-earth-doped devitrified glass.
Embodiment 2
By composition 43.5GeO 225BaF 25ZnO5AlF 31Na 2o20NaF0.5ErF 3(mol%) GeO needed for total mass 10 grams is taken 2, BaF 2, ZnO, AlF 3, Na 2cO 3, NaF and ErF 3powder stock, abundant mixing load afterwards be placed in 1350 DEG C in crucible with cover at found 45min, then glass melt is cast to fast on the Stainless Molding Board being preheating to 300 DEG C, at the temperature lower than glass transformation temperature 50 DEG C, 8 h are incubated after shaping, Temperature fall is to room temperature, obtain the glass containing rare earth ion, and obtained glass is carried out cut, grind and polished finish; By obtained glass thermal treatment 15min under the second crystallization peak temperature, naturally cool to room temperature, namely obtain containing NaBaAlF 6nanocrystalline rear-earth-doped devitrified glass.
Er in the present embodiment 2 3+doped with fluorine oxygen bismuth germanate glass and containing NaBaAlF 6the up-conversion luminescence spectrum of nanocrystalline fluorine oxygen germanate devitrified glass as shown in Figure 1; As can be seen from the figure, with Er in host glass 3+up-conversion luminescence compare, Er that devitrified glass adulterates in the present embodiment 3+up-conversion Intensity been significantly enhanced.
Embodiment 3
By composition 55GeO 210BaF 215ZnO15AlF 35Na 2o5NaF0.2ErF 30.8TbF 34YbF 3(mol%) GeO needed for total mass 10 grams is taken 2, BaF 2, ZnO, AlF 3, Na 2cO 3, NaF, ErF 3, TbF 3and YbF 3powder stock, abundant mixing load afterwards be placed in 1400 DEG C in crucible with cover at found 30 min, then glass melt is cast to fast on the Stainless Molding Board being preheating to 350 DEG C, at the temperature lower than the second crystallization peak temperature 30 DEG C, 5 h are incubated after shaping, Temperature fall is to room temperature, obtain the glass containing rare earth ion, and obtained glass is carried out cut, grind and polished finish; By obtained glass thermal treatment 30 min at lower than devitrification of glass temperature 30 DEG C, naturally cool to room temperature, namely obtain containing NaBaAlF 6nanocrystalline rear-earth-doped devitrified glass.
Embodiment 4
By composition 48.5GeO 215BaF 212ZnO10AlF 310Na 2o1NaF0.5NbF 31HoF 32YbF 3(mol%) GeO needed for total mass 10 grams is taken 2, BaF 2, ZnO, AlF 3, Na 2cO 3, NaF, NbF 3, HoF 3and YbF 3powder stock, abundant mixing load afterwards be placed in 1380 DEG C in crucible with cover at found 40 min, then glass melt is cast to fast on the Stainless Molding Board being preheating to 380 DEG C, at the temperature lower than the second crystallization peak temperature 40 DEG C, 6 h are incubated after shaping, Temperature fall is to room temperature, obtain the glass containing rare earth ion, and obtained glass is carried out cut, grind and polished finish; By obtained glass thermal treatment 45 min at lower than devitrification of glass temperature 40 DEG C, naturally cool to room temperature, namely obtain containing NaBaAlF 6nanocrystalline rear-earth-doped devitrified glass.

Claims (2)

1. a rear-earth-doped fluorine oxygen germanate devitrified glass, is characterized in that: this rear-earth-doped glass frequency inverted luminescent material is obtained by following raw material, and each raw material and molar percentage are: GeO 239 ~ 55 mol %, ZnO 5 ~ 15 mol %, AlF 35 ~ 15 mol %, BaF 210 ~ 25 mol %, Na 2o 1 ~ 10 mol %, NaF1 ~ 20 mol %, RF 30.5 ~ 5 mol %, wherein R is one or more in rare earth element y b, Er, Tm, Nb, Ho, Tb.
2. the preparation method of rear-earth-doped fluorine oxygen germanate devitrified glass according to claim 1, is characterized in that, specifically comprise the steps:
(1) raw material is fully mixed be placed in crucible with cover, 30 ~ 60 min are founded at 1350 ~ 1450 DEG C, raw material is made to be melting into glass melt, glass melt is cast to fast on the Stainless Molding Board being preheating to 300 ~ 400 DEG C, after shaping, insulation 4 ~ 8 h carry out annealing and naturally cooling to room temperature at lower than glass transformation temperature 20 ~ 50 DEG C, obtain the glass containing rare earth ion, and obtained glass is carried out cut, grind and polished finish;
(2) glass containing rare earth ion step (1) prepared carries out differential thermal analysis, according to differential thermal analysis experiment, the obtained glass containing rare earth ion is placed in annealing furnace thermal treatment 15 ~ 60 min within the scope of T ~ T-50 DEG C, wherein T is the second crystallization peak temperature, and namely high temperature taking-up obtains rear-earth-doped containing NaBaAlF 6nanocrystalline transparent fluorine oxygen germanate devitrified glass.
CN201510123499.XA 2015-03-20 2015-03-20 Rare earth-doped oxyfluoride germanate microcrystalline glass and preparation method thereof Pending CN104743885A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107445478A (en) * 2017-08-31 2017-12-08 中国计量大学 A kind of tellurate luminous glass of environment-friendly type germanium of Tm sensitizations and preparation method thereof
CN107601869A (en) * 2017-08-31 2018-01-19 中国计量大学 A kind of tellurate luminous glass of environment-friendly type germanium of Yb sensitizations and preparation method thereof
CN108863087A (en) * 2018-07-30 2018-11-23 吉林工程技术师范学院 A kind of rear-earth-doped niobates transparent glass ceramics and preparation method thereof
CN112010564A (en) * 2020-08-25 2020-12-01 暨南大学 Rare earth ion in-situ crystallization-based fluorine-oxygen microcrystalline glass and preparation method and application thereof
CN116282928A (en) * 2022-12-07 2023-06-23 中国计量大学 Gallium/zinc aluminate doped near-infrared tellurium germanate nanocrystalline glass and preparation method thereof

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CN103666475A (en) * 2013-12-11 2014-03-26 昆明理工大学 Rare earth doped glass frequency conversion luminous material and preparation method thereof

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CN103073183A (en) * 2013-02-21 2013-05-01 浙江大学 Method for preparing up-conversion luminescence glass made of rare earth ion doped germanosilicate oxyfluoride
CN103666475A (en) * 2013-12-11 2014-03-26 昆明理工大学 Rare earth doped glass frequency conversion luminous material and preparation method thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107445478A (en) * 2017-08-31 2017-12-08 中国计量大学 A kind of tellurate luminous glass of environment-friendly type germanium of Tm sensitizations and preparation method thereof
CN107601869A (en) * 2017-08-31 2018-01-19 中国计量大学 A kind of tellurate luminous glass of environment-friendly type germanium of Yb sensitizations and preparation method thereof
CN107445478B (en) * 2017-08-31 2019-10-25 中国计量大学 A kind of tellurate luminous glass of environment-friendly type germanium and preparation method thereof of Tm sensitization
CN107601869B (en) * 2017-08-31 2019-10-25 中国计量大学 A kind of tellurate luminous glass of environment-friendly type germanium and preparation method thereof of Yb sensitization
CN108863087A (en) * 2018-07-30 2018-11-23 吉林工程技术师范学院 A kind of rear-earth-doped niobates transparent glass ceramics and preparation method thereof
CN112010564A (en) * 2020-08-25 2020-12-01 暨南大学 Rare earth ion in-situ crystallization-based fluorine-oxygen microcrystalline glass and preparation method and application thereof
CN112010564B (en) * 2020-08-25 2022-04-22 暨南大学 Rare earth ion in-situ crystallization-based fluorine-oxygen microcrystalline glass and preparation method and application thereof
CN116282928A (en) * 2022-12-07 2023-06-23 中国计量大学 Gallium/zinc aluminate doped near-infrared tellurium germanate nanocrystalline glass and preparation method thereof
CN116282928B (en) * 2022-12-07 2024-01-26 中国计量大学 Gallium/zinc aluminate doped near-infrared tellurium germanate nanocrystalline glass and preparation method thereof

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