CN107056070A - A kind of transparent Ce：YAG glass ceramics and preparation method thereof - Google Patents
A kind of transparent Ce：YAG glass ceramics and preparation method thereof Download PDFInfo
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- CN107056070A CN107056070A CN201710211676.9A CN201710211676A CN107056070A CN 107056070 A CN107056070 A CN 107056070A CN 201710211676 A CN201710211676 A CN 201710211676A CN 107056070 A CN107056070 A CN 107056070A
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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
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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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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
- C03B5/235—Heating the glass
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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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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
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- F21V9/30—Elements containing photoluminescent material distinct from or spaced from the light source
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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
- C03C2204/00—Glasses, glazes or enamels with special properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The present invention relates to a kind of transparent Ce:YAG glass ceramics and preparation method thereof, the glass ceramics is with Ce：YAG fluorescent powder prepares for raw material.Its preparation technology includes frit mixing, frit tabletting, frit pre-burning, prepares without container method glass and be heat-treated five steps of crystallization.The present invention is with Ce：YAG fluorescent powder is raw material, by the way that clear glass is made without container freezing method, clear glass is heat-treated under Tg temperature, the spontaneous precipitation Ce on the premise of not devitrification is ensured：YAG crystallites, effectively reduce the formation of defect, it is possessed the high grade of transparency and excellent optical property, while solving Ce：YAG crystallites and the unmatched problem of host glass refractive index.
Description
Technical field
The present invention relates to technical field of inorganic material, more particularly, to a kind of transparent Ce:YAG glass ceramics and its preparation side
Method.
Background technology
White light LEDs have that small volume, caloric value are low, power consumption is small, long lifespan, reaction speed are fast, environmental protection, can plane envelope
Dress, easy exploiting into frivolous compact product the advantages of, be described as by surmount incandescent lamp, fluorescent lamp " forth generation lighting source ", should
It is very wide with prospect.At present, commercialization white light LEDs product is led using chip and amorphous phosphor combination formation white light as development
Stream, Ce:YAG fluorescent powder is mixed in epoxy resin or silica gel and is coated on InGaN chips, the blue light that InGaN chips are sent
Part is absorbed by fluorescent material, makes it be excited to send gold-tinted, and unabsorbed blue light is mixed with the gold-tinted that fluorescent material is sent, and is just produced
Raw white light.But, because epoxy resin Polymer material thermal conductivity and chemical stability are poor, irradiated in high-power die
Aging, yellow easily occur under hot environment, LED colour casts are caused, in addition, Ce:High refractive index (the n=of YAG fluorescent powder particle
1.83) mismatched with the low refractive index (n=1.45-1.55) such as epoxy resin, higher light scattering loss will be caused and relatively low
Luminous efficiency, the service life of serious curtailment LED component.Therefore, thermal conductivity is high, chemically stable novel solid lights for research and development
Material, is the newest direction for developing White light LED technology in the world.
Glass ceramics, is, by the parent glass of specific composition, to pass through one class prepared by controlling crystallizing in heating process
Polycrystalline solids ceramic material containing a large amount of crystallite phases and glass phase, its existing glass material preparation method is simple, heat endurance
The high advantage with chemical stability, the polycrystalline feature with ceramics, compared with epoxy resin, its thermal conductivity is much bigger, in addition,
Devitrified glass is also easy to be processed into tabular or hollow bulb-shaped is directly overlayed on chip, therefore, it can new for building
Type white light LEDs avoid using epoxy resin or silica gel.Compared with conventional LED device, this new device has photochromic stabilization, made
With the remarkable advantage of long lifespan.
The common method for preparing devitrified glass has two kinds：One kind is to be initially formed forerunner's glass to be heat-treated again, from glass
Crystallization separates out crystallite in glass matrix, but crystallization rate is not high；Another is directly by Ce:YAG fluorescent powder is mixed with low-melting glass
Low temperature co-fired knot forms devitrified glass.
Using first method application and preparation in the patent of the devitrified glass of white light LEDs, such as Wenzhou University Jin Huaidong Shens
Patent of invention CN 102040337A please, it is " rear-earth-doped to recall aluminium garnet microcrystal glass material and its answering in white light LEDs
With ", disclose containing Ce in the patent:The preparation method of the devitrified glass of YAG crystalline phases, but obtained Ce:YAG devitrified glasses are transparent
Property is not fine.And in chemical composition introduce rare earth compound after can to melt cooling when crystallization initial viscosity, crystal type,
Crystalline size and transparency produce important influence, and then influence luminescent properties.
Nippon Electric Glass Co., Ltd is special with the PCT Publication WO2005/097938A1's of Kyoto University's joint application
Profit " is also disclosed that containing Ce in fluorescent material and LED ", the patent:The devitrified glass of YAG crystalline phases, but due to glass basis component master
To be sieve and silica-sesquioxide, material transparent is poor, the crystallite lattice defect (light the broken central role that goes out) that high temperature crystallization is separated out is more
Etc. reason, cause its luminous efficiency not high (referring to Setsuhisa Tanabe et al, " YAG glass-ceramic
phosphor for white LED(ⅠⅠ)：Luminescence characteristics ", Proc of SPIE, 2005,
Vol.5941,594112).
And second method application and preparation is used in the patent of the devitrified glass of white light LEDs, such as Chinese patent
A kind of entitled " the Ce of CN105198224A:YAG devitrified glasses and its preparation method and application ", disclose a kind of Ce:YAG disperses
Devitrified glass in host glass, glass basis component is SiO2-B2O3- PbO-ZnO, the transparency of glass is poor, and with
Ce：There is refractive index in YAG crystallites.Contain toxic component PbO in the raw material of glass ingredient, do not meet current
The theme of environmental protection.
In short, the disclosed patent of invention for being directed to the devitrified glass applied to white light LEDs is existing both at home and abroad so far,
But all introduced except Y mainly due to material composition2O3And Al2O3Outer other components, so that Ce:The surface defect of YAG crystallites
Increase, cause the reduction of its luminous efficiency.Meanwhile, Ce:The high refractive index of YAG microcrystal grains and the low refractive index of host glass are not
Match somebody with somebody, cause the transparency of devitrified glass low, poor optical properties.
The content of the invention
The technical problems to be solved by the invention are that there is provided one kind is transparent for above shortcomings in the prior art
Ce:YAG glass ceramics and preparation method thereof, the transparent glass ceramics is only with Ce：YAG fluorescent powder is that raw material or raw material remove Ce：
Al has been only introduced outside YAG fluorescent powder2O3, it is that a kind of thermal conductivity is high, transparency is high, chemically stable by being made without container freezing method
Novel solid luminescent material.
In order to solve the above technical problems, the technical scheme that the present invention is provided is：
A kind of transparent Ce is provided:YAG glass ceramics, the glass ceramics is with Ce：YAG fluorescent powder, Al2O3Prepared for raw material
Obtain.
By such scheme, the Ce：YAG fluorescent powder, Al2O3Mol ratio is 25-75：25-75.
The present invention also provides above-mentioned transparent Ce:The preparation method of YAG glass ceramics, its step is as follows：
1) frit is mixed：Raw material is weighed in proportion, and then raw material is placed in mortar or ball grinder and is fully ground mixing,
Obtain homogeneous glass mixture；
2) frit tabletting：By step 1) gained glass mixture be placed in mould, using electronic table tabletting machine,
Obtain foliated glass compound；
3) frit pre-burning：By step 2) gained sheet glass mixture loads crucible, then crucible is placed in Muffle furnace
Pre-burning, obtains block shape glass mixture；
4) glass is prepared without container method：By step 3) gained block shape glass mixture is placed in the nozzle of pneumatic suspension stove
On, it is suspended in the air, is not come in contact with any utensil with high-purity gas, after suspending stabilized, with laser to block
Shape glass mixture, which carries out heating, melts it, and after liquid glass material is well mixed, laser is closed, and stopping adds to it
Heat, cooling obtains glass to liquid glass material rapidly；
5) it is heat-treated crystallization：By step 4) gained glass be placed in Muffle furnace be heat-treated, heat treatment terminate rear furnace cooling
Transparent Ce is obtained to room temperature：YAG glass ceramics.
By such scheme, step 2) pressure of the tablet press machine is set to 10-30Mpa.
By such scheme, step 3) process conditions of the pre-burning are：It is warming up to from room temperature with 5 DEG C/min speed
1200-1600 DEG C, then insulation 1-6 hours, finally cool to room temperature with the furnace.
By such scheme, step 4) time heated with laser to block shape glass mixture is 1-
3min。
By such scheme, step 5) heat treatment condition is：0.5-4h is incubated at 800-1200 DEG C.
Present invention additionally comprises above-mentioned transparent Ce:Application of the YAG glass ceramics in white light LEDs.
Present invention additionally comprises above-mentioned transparent Ce:Application of the YAG glass ceramics in laser lighting.
The present invention by using without container freezing method, enabling that glass can not be formed into the component of glass using conventional method,
Its uniform crystallization is made by follow-up heat treatment, by change heat treatment temperature and duration, can obtain excitation peak widen and
Highest launches the glass ceramics of Dependent Red Shift.Because the devitrified glass is only with Ce：YAG fluorescent powder is that raw material or raw material remove Ce：
Al has been only introduced outside YAG fluorescent powder2O3, make that its crystallization rate is greatly improved and defect is significantly reduced, so as to be effectively improved Ce：
The luminous efficiency of YAG glass ceramics, this can not be realized using conventional melt cooling method.Host glass and Ce：YAG folding
The rate of penetrating matches, and reduces the scattering caused by refractive index is mismatched.In addition, introducing Al2O3In the case of, Al in matrix2O3
Thermal conductivity be higher than Ce：YAG, therefore host glass is conducive to Ce:YAG radiating, so that overall improve Ce:YAG glass ceramics
Thermal conductivity.
The present invention by sample without container freezing method by suspending, without adding any other component directly by frit
Simultaneously glass is made in air-cooled lower rapid cooling in melting sources, and cooldown rate reaches 400k/s.
Ce prepared by the present invention：YAG glass ceramics sends bright gold-tinted under 460nm or so blue light exciting light, yellow
Light is combined with blue light produces strong white light, can be applied to prepare white light LEDs and high power laser illumination.
The beneficial effects of the present invention are：Compared with prior art, the present invention is only with Ce：YAG fluorescent powder is prepared for raw material
Ce：YAG glass ceramics or raw material remove Ce：Al has been only introduced outside YAG fluorescent powder2O3, so as to be effectively reduced the formation of defect
And greatly improve the homogeneity of crystallization degree and crystallite dimension.Such component is that can not form glass using conventional melt cooling
Glass, raw material is mixed into merga pass without the obtained clear glass of container freezing method, then carried out clear glass under Tg temperature
Heat treatment, the spontaneous precipitation Ce on the premise of not devitrification is ensured：YAG crystallites, make it possess the high grade of transparency and excellent optical
Can, while solving Ce：YAG crystallites and the unmatched problem of host glass refractive index.Introducing Al2O3In the case of, due to base
Al in matter glass2O3Thermal conductivity be higher than Ce：YAG, therefore host glass is conducive to Ce:YAG radiating, so that overall improve Ce:
The thermal conductivity of YAG glass ceramics, gained glass ceramics product sends bright gold-tinted in the case where 460nm or so blue lights are excited, application
In white light LEDs, LED encapsulation structure can be optimized, and in the absence of the problem of aging for the resin for being packaged with fluorescent material, it is possible to increase it is white
Light LED light is imitated, and its excellent heat conductivility makes it be expected to apply in high power laser lighting apparatus.
Brief description of the drawings
Fig. 1 is the Ce prepared by the embodiment of the present invention 1：YAG GC XRD spectrum；
Fig. 2 is the Ce prepared by embodiment 1：YAG GC transmitance figure；
Fig. 3 is the Ce prepared by embodiment 1：YAG GC PL collection of illustrative plates；
Fig. 4 is the Ce prepared by embodiment 1：YAG GC photo；
Fig. 5 is the Ce prepared by embodiment 1：The white light LEDs photo that YAG GC are built；
Fig. 6 is the Ce prepared by embodiment 1：The illuminated diagram that YAG GC are excited by blue laser；
Fig. 7 is the Ce prepared by embodiment 6：YAG GC transmitance figure；
Fig. 8 is the Ce prepared by embodiment 6：YAG GC PL collection of illustrative plates；
Fig. 9 is the Ce prepared by embodiment 6：YAG GC photo；
Figure 10 is the Ce prepared by embodiment 6：The illuminated diagram that YAG GC are excited by blue laser.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Embodiment 1
Prepare transparent Ce:YAG glass ceramics, is comprised the following steps that：
(1) frit is mixed：By analytically pure Ce:YAG fluorescent powder and Al2O3According to 25Ce:YAG fluorescent powder：75Al2O3
It is placed in after the proportioning accurate weighing of (mol ratio) in mortar, mixing is fully ground in agate mortar, is obtained homogeneous glass and mix
Close material；
(2) frit tabletting：Glass mixture is placed in mould, using electronic table tabletting machine, pressure is set
10Mpa, obtains foliated glass compound；
(3) frit pre-burning：Foliated glass compound loads crucible, then crucible is placed in into pre-burning in Muffle furnace, from room temperature
1600 DEG C are warming up to 5 DEG C/min speed, 1 hour is incubated, finally cools to room temperature with the furnace and obtain block shape glass mixture；
(4) glass is prepared without container method：Block shape glass mixture is placed on the nozzle of pneumatic suspension stove, high-purity Ar is used
Sample is suspended in the air by gas, is not come in contact with any utensil；After suspending stabilized, CO is used2Laser is added to sample
Heat simultaneously melts it, and keeps 1min, after liquid glass material is well mixed, laser is closed, stopping is heated to it；In wind
Liquid glass material is cooled down rapidly in the presence of cold, and glass is made；
(5) it is heat-treated crystallization：Obtained glass is placed in Muffle furnace and is heat-treated, it is 1200 DEG C to set muffle furnace,
Soaking time is 0.5h, and insulation cools to the transparent Ce that room temperature obtains spontaneous crystallization with the furnace after terminating：YAG glass ceramics.
It is the transparent Ce prepared by the embodiment of the present invention 1 as shown in Figure 1：The XRD spectrum of YAG glass ceramics, shows in glass
YAG nanometers of crystalline phases have been separated out in glass matrix.Sample surfaces measure its transmitance by polishing with ultraviolet-visible spectrophotometer
(transmitance figure is as shown in Figure 2), it is seen that in 550-800nm wave bands, its transmitance is more than 45% to sample, and has by force in 430-480nm
It is strong to absorb, it is corresponding with excitation peak.Transparent Ce obtained by the present embodiment is measured with XRF：YAG glass ceramics sample room temperatures
Excite and emission spectra.In monitoring Ce3+On the PLE of ion 538nm transmittings, detect corresponding to Ce3+：The indigo plant of 4f → 5d transition
Optical band (400-500 nanometers of excitation bands) (PL collection of illustrative plates is as shown in Figure 3)；In 469 nanometers and 457 nanometers of emission spectras excited
On, occur corresponding to Ce3+：The strong yellow emission (centre wavelength is 538 nanometers) (as shown in Figure 3) of 5d → 4f transition.Ce：YAG
Glass ceramics photo is as shown in figure 4, it is as shown in Figure 5 with the white light LEDs photo that blue-ray LED is built.The Ce：YAG glass ceramics
Lower transmitting gold-tinted is excited in 465 nm blu-ray lasers, gold-tinted is combined with blue light produces bright white light, Ce：YAG GC are blue
The illuminated diagram of laser excitation is as shown in Figure 6.
Embodiment 2
Prepare transparent Ce:YAG glass ceramics, is comprised the following steps that：
(1) frit is mixed：By analytically pure Ce:YAG fluorescent powder and Al2O3According to 50Ce:YAG fluorescent powder：50Al2O3
It is placed in after the proportioning accurate weighing of (mol ratio) in mortar, mixing is fully ground in agate mortar, is obtained homogeneous glass and mix
Close material；
(2) frit tabletting：Glass mixture is placed in mould, using electronic table tabletting machine, pressure is set
30Mpa, obtains foliated glass compound；
(3) frit pre-burning：Foliated glass compound loads crucible, then crucible is placed in into pre-burning in Muffle furnace, from room temperature
1200 DEG C are warming up to 5 DEG C/min speed, 6 hours is incubated, finally cools to room temperature with the furnace and obtain block shape glass mixture；
(4) glass is prepared without container method：Block shape glass mixture is placed on the nozzle of pneumatic suspension stove, high-purity O is used2
Sample is suspended in the air by gas, is not come in contact with any utensil；After suspending stabilized, CO is used2Laser is added to sample
Heat simultaneously melts it, and keeps 1.5min, after liquid glass material is well mixed, laser is closed, stopping is heated to it；Liquid
State frit is cooled down rapidly, and glass is made；
(5) it is heat-treated crystallization：Obtained glass is placed in Muffle furnace and is heat-treated, it is 1130 DEG C to set muffle furnace,
Soaking time is 1h, and insulation cools to the transparent Ce that room temperature obtains spontaneous crystallization with the furnace after terminating：YAG glass ceramics.
Embodiment 3
Prepare transparent Ce:YAG glass ceramics, is comprised the following steps that：
(1) frit is mixed：By analytically pure Ce:YAG fluorescent powder and Al2O3According to 64Ce:YAG fluorescent powder：36Al2O3
It is placed in after the proportioning accurate weighing of (mol ratio) in mortar, mixing is fully ground in agate mortar, is obtained homogeneous glass and mix
Close material；
(2) frit tabletting：Glass mixture is placed in mould, using electronic table tabletting machine, pressure is set
30Mpa, obtains foliated glass compound；
(3) frit pre-burning：Foliated glass compound loads crucible, then crucible is placed in into pre-burning in Muffle furnace, from room temperature
1500 DEG C are warming up to 5 DEG C/min speed, 3 hours is incubated, finally cools to room temperature with the furnace and obtain block shape glass mixture；
(4) glass is prepared without container method：Block shape glass mixture is placed on the nozzle of pneumatic suspension stove, high-purity N is used2
Sample is suspended in the air by gas, is not come in contact with any utensil；After suspending stabilized, CO is used2Laser is added to sample
Heat simultaneously melts it, and keeps 1.5min, after liquid glass material is well mixed, laser is closed, stopping is heated to it；Liquid
State frit is cooled down rapidly, and glass is made；
(5) it is heat-treated crystallization：Obtained glass is placed in Muffle furnace and is heat-treated, it is 870 DEG C to set muffle furnace, is protected
The warm time is 2h, and insulation cools to the transparent Ce that room temperature obtains spontaneous crystallization with the furnace after terminating：YAG glass ceramics.
Embodiment 4
Prepare transparent Ce:YAG glass ceramics, is comprised the following steps that：
(1) frit is mixed：By analytically pure Ce:YAG fluorescent powder and Al2O3According to 75Ce:YAG fluorescent powder：25Al2O3
It is placed in after the proportioning accurate weighing of (mol ratio) in mortar, mixing is fully ground in agate mortar, is obtained homogeneous glass and mix
Close material；
(2) frit tabletting：Glass mixture is placed in mould, using electronic table tabletting machine, pressure is set
20Mpa, obtains foliated glass compound；
(3) frit pre-burning：Foliated glass compound loads crucible, then crucible is placed in into pre-burning in Muffle furnace, from room temperature
1500 DEG C are warming up to 5 DEG C/min speed, 2 hours is incubated, finally cools to room temperature with the furnace and obtain block shape glass mixture；
(4) glass is prepared without container method：Block shape glass mixture is placed on the nozzle of pneumatic suspension stove, high-purity N is used2
Sample is suspended in the air by gas, is not come in contact with any utensil；After suspending stabilized, CO is used2Laser is added to sample
Heat simultaneously melts it, and keeps 2min, after liquid glass material is well mixed, laser is closed, stopping is heated to it；Liquid
Frit is cooled down rapidly, and glass is made；
(5) it is heat-treated crystallization：Obtained glass is placed in Muffle furnace and is heat-treated, it is 860 DEG C to set muffle furnace, is protected
The warm time is 2h, and insulation cools to the transparent Ce that room temperature obtains spontaneous crystallization with the furnace after terminating：YAG glass ceramics.
Embodiment 5
Prepare transparent Ce:YAG glass ceramics, is comprised the following steps that：：
(1) frit is weighed：By analytically pure Ce:It is placed in after YAG fluorescent powder accurate weighing in mortar, in agate mortar
Mixing is fully ground, homogeneous glass mixture is obtained；
(2) frit tabletting：Glass mixture is placed in mould, using electronic table tabletting machine, pressure is set
20Mpa, obtains foliated glass compound；
(3) frit pre-burning：Foliated glass compound loads crucible, then crucible is placed in into pre-burning in Muffle furnace, from room temperature
1500 DEG C are warming up to 5 DEG C/min speed, 3 hours is incubated, finally cools to room temperature with the furnace and obtain block shape glass mixture；
(4) glass is prepared without container method：Block shape glass mixture is placed on the nozzle of pneumatic suspension stove, high-purity Ar is used
Sample is suspended in the air by gas, is not come in contact with any utensil；After suspending stabilized, CO is used2Laser is added to sample
Heat simultaneously melts it, and keeps 2.5min, after liquid glass material is well mixed, laser is closed, stopping is heated to it；Liquid
State frit is cooled down rapidly, and glass is made；
(5) it is heat-treated crystallization：Obtained glass is placed in Muffle furnace and is heat-treated, it is 1100 DEG C to set muffle furnace,
Soaking time is 1h, and insulation cools to the transparent Ce that room temperature obtains spontaneous crystallization with the furnace after terminating：YAG glass ceramics.
Embodiment 6
Prepare transparent Ce:YAG glass ceramics, is comprised the following steps that：
(1) frit is mixed：By analytically pure Ce:It is placed in after YAG fluorescent powder accurate weighing in mortar, in agate mortar
Mixing is fully ground, homogeneous glass mixture is obtained；
(2) frit tabletting：Glass mixture is placed in mould, using electronic table tabletting machine, pressure is set
30Mpa, obtains foliated glass compound；
(3) frit pre-burning：Foliated glass compound loads crucible, then crucible is placed in into pre-burning in Muffle furnace, from room temperature
1500 DEG C are warming up to 5 DEG C/min speed, 3 hours is incubated, finally cools to room temperature with the furnace and obtain block shape glass mixture；
(4) glass is prepared without container method：Block shape glass mixture is placed on the nozzle of pneumatic suspension stove, high-purity Ar is used
Sample is suspended in the air by gas, is not come in contact with any utensil；After suspending stabilized, CO is used2Laser is added to sample
Heat simultaneously melts it, and keeps 3min, after liquid glass material is well mixed, laser is closed, stopping is heated to it；Liquid
Frit is cooled down rapidly, and glass is made；
(5) it is heat-treated crystallization：Obtained glass is placed in Muffle furnace and is heat-treated, it is 980 DEG C to set muffle furnace, is protected
The warm time is 2h, and insulation cools to the transparent Ce that room temperature obtains spontaneous crystallization with the furnace after terminating：YAG glass ceramics.
Transparent Ce prepared by the present embodiment：YAG glass ceramics sample surfaces are by polishing, with ultraviolet-visible light splitting light
Degree instrument measure its transmitance (transmitance figure is as shown in Figure 7), it is seen that sample 550-800nm wave bands transmitance be more than 40%, and
There is strong absorption in 430-480nm, it is corresponding with excitation peak.Its room temperature is measured with XRF to excite and emission spectra.In prison
Survey Ce3+On the PLE of ion 557nm transmittings, detect corresponding to Ce3+：(400-500 receives the blue wave band of 4f → 5d transition
The excitation band of rice)；On 494 nanometers, 485 nanometers, the 447 nanometers and 451 nanometers emission spectras excited, occur corresponding to Ce3+：
The strong yellow emission (centre wavelength is 557 nanometers) (PL collection of illustrative plates is as shown in Figure 8) of 5d → 4f transition；Ce：YAG glass ceramics photos
As shown in figure 9, it excites lower transmitting gold-tinted in 465 nm blu-ray lasers, the illuminated diagram excited by blue laser is as shown in Figure 10.
Claims (9)
1. a kind of transparent Ce:YAG glass ceramics, it is characterised in that：The glass ceramics is with Ce：YAG fluorescent powder is prepared for raw material
Obtain.
2. transparent Ce according to claim 1:YAG glass ceramics, it is characterised in that：The raw material also includes Al2O3, institute
State Ce：YAG fluorescent powder, Al2O3Mol ratio is 25-75：25-75.
3. the transparent Ce described in a kind of claim 1 or 2:The preparation method of YAG glass ceramics, it is characterised in that step is as follows：
1) frit is mixed：Raw material is weighed in proportion, and then raw material is placed in mortar or ball grinder and is fully ground mixing, is obtained
Homogeneous glass mixture；
2) frit tabletting：By step 1) gained glass mixture be placed in mould, using electronic table tabletting machine, obtain
Foliated glass compound；
3) frit pre-burning：By step 2) gained sheet glass mixture loads crucible, then crucible is placed in pre-burning in Muffle furnace,
Obtain block shape glass mixture；
4) glass is prepared without container method：By step 3) gained block shape glass mixture be placed on the nozzle of pneumatic suspension stove, use
High-purity gas is suspended in the air, is not come in contact with any utensil, after suspending stabilized, with laser to block shape glass
Compound, which carries out heating, melts it, and after liquid glass material is well mixed, laser is closed, and stopping is heated to it, liquid
Cooling obtains glass to frit rapidly；
5) it is heat-treated crystallization：By step 4) gained glass be placed in Muffle furnace be heat-treated, heat treatment terminate after cool to room with the furnace
Temperature obtains transparent Ce：YAG glass ceramics.
4. preparation method according to claim 3, it is characterised in that step 2) pressure of the tablet press machine is set to 10-
30Mpa。
5. preparation method according to claim 3, it is characterised in that step 3) process conditions of the pre-burning are：From room temperature
1200-1600 DEG C is warming up to 5 DEG C/min speed, then insulation 1-6 hours, finally cool to room temperature with the furnace.
6. preparation method according to claim 3, it is characterised in that step 4) it is described mixed to block shape glass with laser
It is 1-3min to close the time for expecting to be heated.
7. preparation method according to claim 3, it is characterised in that step 5) heat treatment condition is：800-
0.5-4h is incubated at 1200 DEG C.
8. the transparent Ce described in a kind of claim 1 or 2:Application of the YAG glass ceramics in white light LEDs.
9. the transparent Ce described in a kind of claim 1 or 2:Application of the YAG glass ceramics in laser lighting.
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