CN108275882A - A kind of polychrome light emitting glass of ultraviolet excitation and preparation method thereof - Google Patents
A kind of polychrome light emitting glass of ultraviolet excitation and preparation method thereof Download PDFInfo
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- CN108275882A CN108275882A CN201810023833.8A CN201810023833A CN108275882A CN 108275882 A CN108275882 A CN 108275882A CN 201810023833 A CN201810023833 A CN 201810023833A CN 108275882 A CN108275882 A CN 108275882A
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- ultraviolet excitation
- polychrome light
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to illuminate and display technology field, and in particular to a kind of polychrome light emitting glass of ultraviolet excitation and preparation method thereof；The host material of the glass includes the composition of following molar ratio：SiO2：70%, SnO：1.14%, Na2O：20%, CaO：X%, CaF2：(10 x) %, wherein x% is the molar ratio of CaO, and (10 x) % is CaF2Molar ratio；X is 5,3,7,2 or 8.The Re that also doping molar ratio is 0.1% 1.5%3+；Wherein Re3+For rare earth ion；Preparation method includes：(a) selection of raw material, (b) mixing of dispensing, (c) melted three steps of glass ceramics.Transparent glass ceramics prepared by the present invention has efficient ultraviolet to can see below conversion luminescent properties, and can realize polychrome light emitting, the suitable large area industrial production of this material.
Description
Technical field
The invention belongs to illuminate and display technology field, and in particular to a kind of polychrome light emitting glass of ultraviolet excitation and
Preparation method.
Background technology
In recent years, there is important application in the fields such as solid-state polychrome Three-dimensional Display and biological fluorescent labeling due to white light source
Foreground and cause extensive concern.Now widely used energy-saving lamp and white light LED part are all in a kind of irradiation of short-wavelength light
Under, white light emission is converted to by multigroup fluorophor mixed light.However, this method can still have, light intensity is weak, color is steady
The problems such as qualitative poor, complex process.Therefore, it finds one kind and emitting intense white light and ultraviolet resistance spoke under near ultraviolet excitation
It is very necessary according to the novel solid luminescent material of (properity stabilization).Fluorescent glass is a kind of important fluorescent material,
Have many advantages, such as to prepare simple, at low cost, favorable repeatability, transparent good, easily doping.Since rare earth ion has abundant electricity
Sub- energy level and the narrow spectral line of emission are very suitable for as lower switching emission center.Optical glass is set to have by doping with rare-earth ions
There is fluorescent characteristic more carefully, the features such as luminescent chromaticity is pure, physico-chemical property is stable, high conversion efficiency.
But rare earth ion has that absorption cross-section is narrow to ultraviolet light.
Invention content
For the deficiencies in the prior art, the present invention provide a kind of ultraviolet excitation polychrome light emitting glass and its
Preparation method, the present invention select Eu3+、Tb3+Rare earth ion is the centre of luminescence, is prepared for Eu3+、Tb3+Rare earth ion doped is transparent
Glass ceramics, the glass have a high translucency, high thermal stability (high temperature that 800 degree can be born) and it is high it is luminous by force
Degree；And it realizes from green light to white light again to the Color tunable of feux rouges.
In order to achieve the above-mentioned object of the invention, present invention employs following technical schemes：
A kind of polychrome light emitting glass of ultraviolet excitation, host material includes the composition of following molar ratio：SiO2：
70%, SnO：1.14%, Na2O：20%, CaO：X%, CaF2：(10-x) %, wherein x% is the molar ratio of CaO, (10-x) %
For CaF2Molar ratio；X is 5,3,7,2 or 8.
Preferably, the Re that also doping molar ratio is 0.1%-1.5%3+；Wherein Re3+For rare earth ion.
Preferably, the Re3+For Eu3+Or Tb3+。
A kind of preparation method of the polychrome light emitting glass of ultraviolet excitation, includes the following steps：
(a) selection of glass ceramics raw material；
(b) mixing of glass ceramics batch；Raw material is weighed according to proportioning, adds absolute ethyl alcohol milled processed；
(c) glass ceramics is melted；Glass ceramics is melted using corundum crucible, and glass melting temperature is 1550 DEG C, when being melted
Between 1 hour, be then quickly cooled to glass ceramics, using annealing, obtain the polychrome light emitting glass of ultraviolet excitation.
Preferably, the milled processed of the step (b) is 0.5 hour.
Preferably, the annealing time of the step (c) is 4 hours, and annealing temperature is 540 DEG C.
Compared with prior art, the present invention having the advantages that：
1. preparation method of the present invention is easy, colour temperature is relatively low, is suitble to industrial mass manufacture.
2. glass ceramics produced by the present invention has good thermal stability and chemical stability compared with fluorescent powder.
3. glass of the present invention is the new ultra-violet light conversion material that a kind of stability is good, coloration is good, Eu3+And Tb3+
Doping keep the transmitting light of glass adjustable to feux rouges by white light from green light.
4. the present invention is by doping with rare-earth ions come wide band absorption ultraviolet light；The present invention utilizes small-power (about 0.5Mw/
mm2) 266nm ultraviolet light be excitation light source, reduce the heat affecting of excitaton source itself.
Description of the drawings
Emission spectrum of the sample that Fig. 1 is embodiment 1-5 under 266nm excitations；
Emission spectrum of the sample that Fig. 2 is embodiment 6-12 under 266nm excitations；
Emission spectrum of the sample that Fig. 3 is embodiment 13-18 under 266nm excitations.
Specific implementation mode
Below by specific implementation mode, invention is further described in detail.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment
Art or condition person carry out to specifications according to technology described in document in the art or condition.Agents useful for same or instrument
Production firm person is not specified, being can be with conventional products that are commercially available.
Embodiment 1-5
The pure SiO of host material Analysis about Selection2, SnO, Na2O, CaO and CaF2, it is according to host material proportioning：70SiO2-
1.14SnO-20Na2O–xCaO-(10-x)CaF2, x=5,3,7,2,8.Each material quality is as shown in table 1.Preparation method be according to
Said ratio weighs raw material, is fully ground and is put into corundum crucible, and 1550 DEG C are heated 1 hour, and glass ceramics is then quickly cooled to,
540 DEG C of annealing increase the crystallinity of crystallite in 4 hours again, obtain the polychrome light emitting glass of ultraviolet excitation.
To obtained by embodiment 1-5 sample carry out spectrum test, obtain launching light spectrogram as shown in Figure 1, chromaticity coordinates such as
Shown in table 2.
The glass of 1 embodiment 1-5 of table forms (unit：Gram)
Experimental result：Embodiment 1-5 samples are excited using 266nm ultraviolet sources, obtain the emission spectrum of Fig. 1,
And Fig. 1 emission spectrum are analyzed using CIE1931 chromaticity coordinates software for calculation, chromaticity coordinates in table 2 is obtained, can be seen by table 2
Go out under the excitation of ultraviolet source, changes CaO and CaF2Ratio realize the white light emission of fluorescence intensity, optimal chromaticity coordinates is
(0.3201,0.3105) correspond to embodiment 4.
The chromaticity coordinates of 2 embodiment 1-5 of table
| Embodiment | CIEx | CIEy |
| Embodiment 1 | 0.3204 | 0.3546 |
| Embodiment 2 | 0.3201 | 0.3596 |
| Embodiment 3 | 0.2994 | 0.3342 |
| Embodiment 4 | 0.3201 | 0.3150 |
| Embodiment 5 | 0.3074 | 0.3425 |
Embodiment 6-12
The analytically pure SiO of material selection2, SnO, Na2O, CaO, CaF2, rare earth ion select purity for 99.99% fluorination
Object is primary raw material, is according to host material proportioning：70SiO2-1.14SnO-20Na2O–2CaO-8CaF2：Doped ions Eu3+,
The ratio that its molar ratio is y=0,0.1,0.3,0.5,0.8,1,1.5% weighs raw material；Each material quality is as shown in table 3；Fully
Grinding 0.5 hour；It is put into corundum crucible, 1550 DEG C are heated 1 hour, and glass ceramics, then 540 DEG C of annealing 4 are then quickly cooled to
Hour increases the crystallinity of crystallite, obtains the polychrome light emitting glass of ultraviolet excitation.
Spectrum test is carried out to embodiment 6-12 samples, obtains launching light spectrogram as shown in Fig. 2, chromaticity coordinates such as 4 institute of table
Show.
The glass of 3 embodiment 6-12 of table forms (unit：Gram)
Experimental result：Embodiment 6-12 samples are excited using 266nm ultraviolet sources, obtain the emission spectrum of Fig. 2,
And Fig. 2 emission spectrum are analyzed using CIE1931 chromaticity coordinates software for calculation, chromaticity coordinates in table 4 is obtained, can be seen by table 4
Go out under the excitation of ultraviolet source, changes rare earth ion Eu3+Concentration realize the adjustable white light emission of fluorescence intensity, optimal color
Coordinate is that (0.3234,0.3475) corresponds to embodiment 7.
The chromaticity coordinates of 4 embodiment 6-12 of table
| Embodiment | CIEx | CIEy |
| Embodiment 6 | 0.3191 | 0.3484 |
| Embodiment 7 | 0.3234 | 0.3475 |
| Embodiment 8 | 0.3583 | 0.3707 |
| Embodiment 9 | 0.3578 | 0.3561 |
| Embodiment 10 | 0.4050 | 0.3764 |
| Embodiment 11 | 0.3973 | 0.3617 |
| Embodiment 12 | 0.4407 | 0.3779 |
Embodiment 13-18
The pure SiO of material Analysis about Selection2, SnO, Na2O, CaO and CaF2, rare earth ion selects purity for 99.99%
Fluoride is primary raw material, is according to host material proportioning：70SiO2-1.14SnO-20Na2O–2CaO-8CaF2：Doped ions
Tb3+, the ratio of molar ratio y=0.1,0.3,0.5,0.8,1,1.5% weighs raw material.Raw material is mixed and is fully ground
0.5 hour；It is put into corundum crucible, 1550 DEG C are heated 1 hour, and glass ceramics is then quickly cooled to, then 540 DEG C are annealed 4 hours
Increase the crystallinity of crystallite, obtains the polychrome light emitting glass of ultraviolet excitation.Each material quality is as shown in table 5.To implementing
Example 13-18 samples carry out spectrum test, obtain launching light spectrogram as shown in figure 3, chromaticity coordinates is as shown in table 6.
The glass of 5 embodiment 13-18 of table forms (unit：Gram)
Experimental result：Embodiment 13-18 samples are excited using 266nm ultraviolet sources, obtain the transmitting light of Fig. 3
Spectrum, and analyzes Fig. 3 emission spectrum using CIE1931 chromaticity coordinates software for calculation, and chromaticity coordinates in table 6 is obtained, can be with by table 6
Find out under the excitation of ultraviolet source, changes rare earth ion Tb3+(te) concentration realizes the adjustable white light emission of fluorescence intensity,
Optimal chromaticity coordinates is that (0.3046,0.3420) corresponds to embodiment 13.
The chromaticity coordinates of 6 embodiment 13-18 of table
| Embodiment | CIEx | CIEy |
| Embodiment 13 | 0.3046 | 0.3420 |
| Embodiment 14 | 0.3184 | 0.3711 |
| Embodiment 15 | 0.3055 | 0.3888 |
| Embodiment 16 | 0.3055 | 0.4106 |
| Embodiment 17 | 0.3174 | 0.4379 |
| Embodiment 18 | 0.3081 | 0.4645 |
The above is only preferred embodiments of the present invention, is not intended to limit the scope of the present invention,
Therefore every any trickle amendment, equivalent variations and modification made to the above embodiment according to the technical essence of the invention, belong to
In the range of technical solution of the present invention.
Claims (6)
1. a kind of polychrome light emitting glass of ultraviolet excitation, which is characterized in that host material includes the composition of following molar ratio：
SiO2：70%, SnO：1.14%, Na2O：20%, CaO：X%, CaF2：(10-x) %, wherein x% is the molar ratio of CaO,
(10-x) % is CaF2Molar ratio；X is 5,3,7,2 or 8.
2. a kind of polychrome light emitting glass of ultraviolet excitation according to claim 1, which is characterized in that also doping mole
Than the Re for 0.1%-1.5%3+；Wherein Re3+For rare earth ion.
3. a kind of polychrome light emitting glass of ultraviolet excitation according to claim 1, which is characterized in that the Re3+For
Eu3+Or Tb3+。
4. a kind of preparation method of the polychrome light emitting glass of ultraviolet excitation described in claim 1, which is characterized in that including
Following steps：
(a) selection of raw material；
(b) mixing of glass ceramics batch；Raw material is weighed according to proportioning, adds absolute ethyl alcohol milled processed；
(c) glass ceramics is melted；Glass ceramics is melted using corundum crucible, and glass melting temperature is 1550 DEG C, 1 hour time,
Then it is quickly cooled to glass ceramics, using annealing, obtains the polychrome light emitting glass of ultraviolet excitation.
5. a kind of preparation method of the polychrome light emitting glass of ultraviolet excitation according to claim 4, the step (b)
Milled processed be 0.5 hour.
6. a kind of preparation method of the polychrome light emitting glass of ultraviolet excitation according to claim 5, the step (c)
The annealing time be 4 hours, annealing temperature be 540 DEG C.
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| CN201810023833.8A CN108275882B (en) | 2018-01-10 | 2018-01-10 | Ultraviolet light excited multicolor light emitting glass and preparation method thereof |
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| CN201810023833.8A CN108275882B (en) | 2018-01-10 | 2018-01-10 | Ultraviolet light excited multicolor light emitting glass and preparation method thereof |
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| CN108275882B CN108275882B (en) | 2020-11-06 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278636A (en) * | 2000-03-29 | 2001-10-10 | Koa Glass Kk | Ultraviolet light fluoroglass, product of ultraviolet light fluoroglass and manufacturing method of ultraviolet light fluoroglass |
| CN101238077A (en) * | 2005-01-21 | 2008-08-06 | 独立行政法人产业技术综合研究所 | Transparent white fluorescent glass |
| CN103395997A (en) * | 2013-07-23 | 2013-11-20 | 南京邮电大学 | Rare earth doped transparent glass ceramic for white-light LED (Light-emitting Diode) and preparation method thereof |
| CN103771710A (en) * | 2013-12-25 | 2014-05-07 | 石家庄经济学院 | Rare earth doped near-infrared luminescent glass and preparation method thereof |
| CN106565086A (en) * | 2016-10-25 | 2017-04-19 | 南京奥依菲光电科技有限公司 | High-color-rendering high-quantum-efficiency white fluorescent glass and preparation method thereof |
-
2018
- 2018-01-10 CN CN201810023833.8A patent/CN108275882B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001278636A (en) * | 2000-03-29 | 2001-10-10 | Koa Glass Kk | Ultraviolet light fluoroglass, product of ultraviolet light fluoroglass and manufacturing method of ultraviolet light fluoroglass |
| CN101238077A (en) * | 2005-01-21 | 2008-08-06 | 独立行政法人产业技术综合研究所 | Transparent white fluorescent glass |
| CN103395997A (en) * | 2013-07-23 | 2013-11-20 | 南京邮电大学 | Rare earth doped transparent glass ceramic for white-light LED (Light-emitting Diode) and preparation method thereof |
| CN103771710A (en) * | 2013-12-25 | 2014-05-07 | 石家庄经济学院 | Rare earth doped near-infrared luminescent glass and preparation method thereof |
| CN106565086A (en) * | 2016-10-25 | 2017-04-19 | 南京奥依菲光电科技有限公司 | High-color-rendering high-quantum-efficiency white fluorescent glass and preparation method thereof |
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