CN106865990A - A kind of transparent glass ceramics and preparation method with high efficiency blue transmitting - Google Patents
A kind of transparent glass ceramics and preparation method with high efficiency blue transmitting Download PDFInfo
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- CN106865990A CN106865990A CN201710012843.7A CN201710012843A CN106865990A CN 106865990 A CN106865990 A CN 106865990A CN 201710012843 A CN201710012843 A CN 201710012843A CN 106865990 A CN106865990 A CN 106865990A
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- glass ceramics
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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
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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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- Geochemistry & Mineralogy (AREA)
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- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
It is a kind of with high efficiency blue transmitting transparent glass ceramics and preparation method, each component and mole be SiO2：79 89%, MgO：5 10%, Ga2O3：5 10%, Ce：1%.Preparation method：Raw material is weighed according to proportioning, by Ga2O3、Ce2O3Dilute nitric acid solution being dissolved in respectively, being heated and is obtained clear solution under magnetic agitation, mixed, it is 1 to add mol ratio:1:1 tetraethyl orthosilicate, ethanol, deionized water, is subsequently adding and is dissolved with MgCl2·6H2The ethanol solution of O, lasting stirring, obtains homogeneous mixed solution, stands dehydration and forms solid gel, then is placed in 95%N2And 5%H2In atmosphere tube type stove, 700 900oC sinters 3h, heating rate 2.5oC/min, is cooled to room temperature.Present invention process is simple, with low cost, nontoxic pollution-free, and product physical and chemical performance stabilization, annealing temperature is low.Glass ceramics is fixed easily, it is easy to device without encapsulation, luminous with efficient stable, ultraviolet with good absorption, can be used for white light LED part.
Description
Technical field
The invention belongs to solid luminescent material field.
Background technology
The abundant Absorption and emission spectra that transition of the 4f electronics of rare earth ion between different energy levels is produced, make its
Field of light emitting materials has a wide range of applications.Ce3+It is the most frequently used activator, is typical d → f transition, because 5d electronics is
Outer-shell electron, it is easily affected by the ambient, so Ce3+Luminous peak position do not fix, depending on chemical bond and part
Polarizability.Include AB2O4The nanocrystalline glass ceramics of spinel structure then possesses good chemical stability.MgGa2O4Due to
With self-excitation blue emission and can be applied to the potentiality of display and paid close attention to more and more widely.Additionally, gallium acid magnesium
Can be well embedded in glass matrix, simultaneously because ionic radius of rare earth and Ga3+Radius causes it close to identical electronegativity
Ga can be replaced3+The position of ion occupies the Ga of eight tetrahedrons and 16 octahedral sites3+.The MgGa of spinel structure2O4
Because it has good fire resistance, thermal-shock resistance, there is mechanical strength and good chemistry high in temperature course is raised
Stability and be widely used in ceramics, electronics and catalysis material.Based on this, rare earth ion Ce3+Adulterate the transparent of gallate
Glass ceramics has wide application prospect.
The content of the invention
The present invention seeks to propose a kind of transparent glass ceramics with high efficiency blue transmitting and preparation method thereof, one is prepared
Kind of transparent glass ceramics, is heat-treated in reducing atmosphere, by manipulate it is nanocrystalline in matrix realize blue emission, in this, as white
Light LED encapsulation materials.
The present invention is achieved by the following technical solutions.
A kind of transparent glass ceramics with high efficiency blue transmitting of the present invention, each component and its molar percentage
（mol%）It is SiO2：79-89%, MgO：5-10%, Ga2O3：5-10%, Ce：1%.
MgO of the present invention and Ga2O3Introducing so that MgGa is grown in glass system2O4It is nanocrystalline.
The preparation method of a kind of transparent glass ceramics with high efficiency blue transmitting of the present invention, using collosol and gel
Method+Technology for Heating Processing prepares transparent glass ceramics, nanocrystalline growth is controlled by controlling heat treatment temperature, in making as lighting
The rare earth ion of the heart is solid-solution in the crystalline phase of precipitation, is comprised the following steps.
（1）The mixing of glass ceramics dispensing.
Raw material is weighed according to proportioning, by Ga2O3, Ce2O3Dilute nitric acid solution is dissolved in respectively, is heated and is obtained under magnetic agitation
Clear solution, is well mixed it, adds tetraethyl orthosilicate, ethanol, wherein deionized water, tetraethyl orthosilicate:Ethanol:Deionization
Water=1:1:1（Mol ratio）, then will be dissolved with MgCl2·6H2The ethanol solution of O is added in above-mentioned solution, and gained mixing is molten
Liquid is persistently stirred, and obtains homogeneous mixed solution, is stood dehydration and is formed solid gel.
（2）The sintering of glass ceramics.
Solid gel is placed in 95%N2And 5%H2Atmosphere tube type stove in, heat treatment 700 DEG C -900 DEG C sinter 3 hours, rise
Warm speed 2.5oC/min, cools to room temperature with the furnace.
Oxide Ga of the present invention2O3, chloride MgCl2·6H2O is pure, the rare earth ion Ce of analysis3+Selection purity
It is 99.99% oxide Ce2O3。
The beneficial effects of the invention are as follows：(1) glass ceramics preparation process is simple of the invention, with low cost, nontoxic nothing
Pollution, product physical and chemical performance stabilization, annealing temperature is low；(2) glass ceramics of the invention is fixed easily, it is easy to device without encapsulation
Part.（3）The present invention is prepared for singly mixing Ce3+Transparent glass ceramics, this glass ceramics has the luminous of efficient stable, ultraviolet
With good absorption, white light LED part is expected to be widely applied to.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of fluorescent material sample in embodiment 1-3.
Fig. 2 is emission spectrum of the fluorescent material sample under 336 nanometers of burst of ultraviolel in embodiment 1-3.
Fig. 3 is emission spectrum chromaticity coordinates of the fluorescent material sample under 336 nanometers of burst of ultraviolel in embodiment 1-3.
Specific embodiment
The present invention will be described further by following examples.
Embodiment 1-3 is prepared use rare earth ion doped transparent glass ceramics as follows.
The selection of (a) raw material：
The primary raw material of the glass ceramics is analytically pure chloride MgCl2·6H2O, oxide Ga2O3With organic reagent just
Silester, ethanol, rare earth ion selection purity are 99.99% Ce2O3。
The mixing of (b) glass ceramics batch：
Raw material accurately is weighed according to proportioning, raw material is weighed according to proportioning, by Ga2O3, Ce2O3Dilute nitric acid solution is dissolved in respectively, plus
Clear solution is obtained under heat and magnetic agitation, it is well mixed, tetraethyl orthosilicate, ethanol, deionized water is added, wherein positive silicon
Acetoacetic ester：Ethanol：Deionized water：=1:1:1（Mol ratio）, secondly will be dissolved with MgCl2·6H2The ethanol solution of O is added to
State in solution, gained mixed solution is persistently stirred, obtain homogeneous mixed solution, stand dehydration and form solid gel.
（2）The sintering of glass ceramics
By solid gel as atmosphere（95%N2+5%H2）In tube furnace, heat treatment 700oC-900oC is sintered 3 hours, heating rate
2.5oC/min, cools to room temperature with the furnace.
Embodiment 1.
According to molar percentage（mol%）It is SiO：89%, MgO：5%, Ga2O3：5%, Ce3+:1% ratio weighs raw material and is total to
11.13g.As shown in table 1, the embodiment temperature is 700 to each material qualityoC.X-ray diffraction result（As shown in Figure 1）Show sample
Product are typical glassy structure.By grind into powder, with F-4600 fluorescence spectrophotometer measurements, its Emission at Room Temperature is composed（Such as
Shown in Fig. 2）.Under 336 nanometers of near ultraviolet excitations, Ce is detected3+：5d-4f stronger transmitting.Its emission spectra chromaticity coordinates position
It is set to x=0.16 y=0.0548, such as Fig. 3（a）, position is located at blue region, is observed visually glass ceramics and sends blue light.
The glass composition of the embodiment 1 of table 1
| Raw material | Tetraethyl orthosilicate | |||
| Embodiment 1 | 0.5411 | 0.4999 | 10 | 0.0875 |
Embodiment 2.
According to molar percentage（mol%）It is SiO：79%, MgO：10%, Ga2O3：10%, Ce3+:1% ratio weighs raw material,
Heat treatment temperature is set to 800oC.X-ray diffraction result（As shown in Figure 1）Show that sample starts MgGa occur2O4Spinelle
It is nanocrystalline.With F-4600 fluorescence spectrophotometer measurements, its Emission at Room Temperature is composed（As shown in Figure 2）Swash in 336 nanometers of black lights
Give, detect Ce3+：The transmitting of 5d-4f, its emission spectra chromaticity coordinates position is x=0.1603 y=0.0689, such as Fig. 3（b）, position
Setting in blue region.It is observed visually glass ceramics and sends strong blue light.
Embodiment 3.
According to molar percentage（mol%）It is SiO：79%, MgO：10%, Ga2O3：10%, Ce3+:1% ratio weighs raw material,
Heat treatment temperature is set to 900oC.X-ray diffraction result（As shown in Figure 1）Show that sample starts MgGa occur2O4Spinelle
It is nanocrystalline.With F-4600 fluorescence spectrophotometer measurements, its Emission at Room Temperature is composed（As shown in Figure 2）Swash in 336 nanometers of black lights
Give, detect Ce3+：The transmitting of 5d-4f, its emission spectra chromaticity coordinates position is x=0.1597 y=0.0851, such as Fig. 3（c）, position
Setting in blue region.It is observed visually glass ceramics and sends blue light.
Claims (2)
1. it is a kind of with high efficiency blue transmitting transparent glass ceramics, it is characterized in that each component and its molar percentage are：SiO2：
78-93%, MgO：2.5-10.5%, Ga2O3：2.5-10.5%, Ce：1-2%.
2. described in claim 1 with high efficiency blue transmitting transparent glass ceramics preparation method, it is characterized in that including such as
Lower step：
（1）The mixing of glass ceramics dispensing：
Raw material is weighed according to proportioning, by Ga2O3、Ce2O3Dilute nitric acid solution is dissolved in respectively, is heated and is obtained transparent molten under magnetic agitation
Liquid, is well mixed it, adds tetraethyl orthosilicate, ethanol, deionized water, wherein tetraethyl orthosilicate, ethanol, deionized water to rub
You are than being 1:1:1, then, MgCl will be dissolved with2·6H2The ethanol solution of O is added in above-mentioned solution, and gained mixed solution is held
Continuous stirring, obtains homogeneous mixed solution, stands dehydration and forms solid gel；
（2）The sintering of glass ceramics：
Solid gel is placed in 95%N2And 5%H2In the tube furnace of atmosphere, heat treatment 700oC-900oC is sintered 3 hours, heating rate
2.5oC/min, cools to room temperature with the furnace.
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| CN201710012843.7A CN106865990A (en) | 2017-01-09 | 2017-01-09 | A kind of transparent glass ceramics and preparation method with high efficiency blue transmitting |
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| CN201710012843.7A CN106865990A (en) | 2017-01-09 | 2017-01-09 | A kind of transparent glass ceramics and preparation method with high efficiency blue transmitting |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739153A (en) * | 2017-11-06 | 2018-02-27 | 南昌大学 | A kind of clear glass and preparation method with highly effective green light transmitting |
| US20210088716A1 (en) * | 2018-03-22 | 2021-03-25 | Centre National De La Recherche Scientifique | Optical element and associated manufacturing method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163572A (en) * | 2014-07-15 | 2014-11-26 | 南昌大学 | Transparent glass ceramic having high efficiency white light emission and preparation method thereof |
-
2017
- 2017-01-09 CN CN201710012843.7A patent/CN106865990A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104163572A (en) * | 2014-07-15 | 2014-11-26 | 南昌大学 | Transparent glass ceramic having high efficiency white light emission and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| D. JIA: "Enhanced Vk3+ center afterglow in MgAl2O4 by doping with Ce3+", 《JOURNAL OF LUMINESCENCE》 * |
| W.A.I.TABAZA: "Luminescence of Ce doped MgAl2O4 prepared by the combustion method", 《PHYSICA B》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739153A (en) * | 2017-11-06 | 2018-02-27 | 南昌大学 | A kind of clear glass and preparation method with highly effective green light transmitting |
| US20210088716A1 (en) * | 2018-03-22 | 2021-03-25 | Centre National De La Recherche Scientifique | Optical element and associated manufacturing method |
| US11880063B2 (en) * | 2018-03-22 | 2024-01-23 | Centre National De La Recherche Scientifique | Optical element and associated manufacturing method |
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Application publication date: 20170620 |