CN109721250A - The method for preparing luminescent glass ceramic with glass powder with low melting point - Google Patents
The method for preparing luminescent glass ceramic with glass powder with low melting point Download PDFInfo
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- CN109721250A CN109721250A CN201910116213.3A CN201910116213A CN109721250A CN 109721250 A CN109721250 A CN 109721250A CN 201910116213 A CN201910116213 A CN 201910116213A CN 109721250 A CN109721250 A CN 109721250A
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- melting point
- low melting
- phase transition
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- 239000011521 glass Substances 0.000 title claims abstract description 114
- 239000000843 powder Substances 0.000 title claims abstract description 95
- 238000002844 melting Methods 0.000 title claims abstract description 62
- 230000008018 melting Effects 0.000 title claims abstract description 59
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000007704 transition Effects 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000002419 bulk glass Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 claims description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- 230000005496 eutectics Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 238000005286 illumination Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000005538 encapsulation Methods 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 description 8
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910020617 PbO—B2O3—SiO2 Inorganic materials 0.000 description 1
- 229910020615 PbO—SiO2 Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012994 photoredox catalyst Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229960002799 stannous fluoride Drugs 0.000 description 1
- 229910019655 synthetic inorganic crystalline material Inorganic materials 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- C03C12/00—Powdered glass; Bead compositions
-
- 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
-
- 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
- C03C10/16—Halogen containing crystalline phase
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
- F21K9/00—Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
- F21K9/90—Methods of manufacture
-
- 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
- F21V19/00—Fastening of light sources or lamp holders
- F21V19/001—Fastening of light sources or lamp holders the light sources being semiconductors devices, e.g. LEDs
- F21V19/0015—Fastening arrangements intended to retain light sources
- F21V19/002—Fastening arrangements intended to retain light sources the fastening means engaging the encapsulation or the packaging of the semiconductor device
Abstract
The invention discloses a kind of method for preparing luminescent glass ceramic with glass powder with low melting point, the preparation method of glass powder with low melting point is uniformly to mix bulk pharmaceutical chemicals, 15-90 minutes melted at 300~700 DEG C, obtains glass metal；300~700 DEG C of the glass metal is subjected to quenching, cooled to room temperature obtains both bulk glasses；Both bulk glasses are crushed, it is put into ball mill ball milling, obtain glass powder with low melting point, glass powder with low melting point of the invention has lower glass phase transition temperature, and its glass phase transition temperature is adjusted within the scope of 200~500 DEG C, suitable for the production of seal glass and vacuum component and the encapsulation of LED, especially suitable for manufacturing luminescent glass ceramic with phosphor material powder, which is particularly suitable for laser lighting.Glass ceramics forming and sintering at a lower temperature, can effectively avoid the heat deterioration of fluorescent powder at high temperature, have important application value in field of laser illumination.
Description
The application is the divisional application of parent application " glass powder with low melting point and its laser lighting glass ceramics of manufacture ",
Parent application application No. is 2016110912313, the applying date is on December 01st, 2016.
Technical field
Special glass manufacturing technology of the present invention field relates in particular to a kind of prepared with glass powder with low melting point and shines
The method of glass ceramics.
Background technique
Low-melting glass refers to that glass transition temperature is substantially less than the special glass of simple glass, can be widely used as sealing
Connect the Binder Phase in glass and electric slurry.With the fast development of electronic industry, low-melting glass is widely used in electronics
The sealing-in and protection of element and display device, such as sealing-in vacuum fluorescent display screen (VFD), plasma panel (PDP) and yin
The vacuum devices such as extreme ray pipe (CRT).In terms of LED encapsulation and its white light adjusting, low-melting glass is needed to substitute organic matter
It is packaged.LED/ laser (LD) illuminating glass ceramics is badly in need of glass powder with low melting point also to reduce fluorescent powder in high temperature sintering
Heat deterioration in the process.Remote phosphor for LED/ laser illumination system is made of carrier material and luminous agent, is commonly used
Carrier material have the organic materials such as PC, epoxy resin, PMMA.But usually there is thermal stability and chemical stabilization in organic matter
Property difference disadvantage, especially under the laser irradiation of high-energy density, organic material deterioration is serious.And fluorescent glass Ceramic bond
The advantages of luminescent crystal and inorganic glass materials, there can be a good optical property, compared with organic resin, glass has heat
Stability is good, and chemical stability is high, and preparation method is simple, good in optical property, has many advantages, such as to coat protective effect to fluorescent powder.
The manufacture of fluorescent glass ceramics need to use glass powder with low melting point and phosphor material powder sinter molding at high temperature, excessively high sintering temperature
Degree will lead to the luminescent properties deterioration of fluorescent powder.Therefore, the exploitation of glass powder with low melting point is to manufacture laser lighting glass ceramics
It is most important.
Traditional glass powder with low melting point mostly contains PbO, and PbO has good adjustment effect to the structure and performance of glass.PbO
Presence not only act as reduce glass powder phase transition temperature effect, moreover it is possible to enhance the chemical stabilization and mobility of system.It is domestic
It is outer to prepare leaded sealing glass powder and often select PbO-SiO2、PbO-B2O3、PbO-B2O3-SiO2、PbO-ZnO-B2O3Etc. systems.Though
Right leaded glass powder with low melting point has many advantages, such as that softening temperature is low, chemical stability is high, still, lead to the health hazard of the mankind compared with
Greatly.For this purpose, related fields scientific research personnel has been devoted to the exploitation of lead-free glass powder with low melting point.
Well known lead-free glass powder with low melting point is Bi2O3-B2O3ZnO ternary and B2O3-BaO-SiO-Bi2O3Quaternary body
System, but their vitrifying phase transition temperature is higher than 550 DEG C, it is difficult to meet the application demand of some low-temperature sealing/dresses, sintering.
In terms of lead-free glass powder with low melting point exploitation, phosphate system is that Abroad in Recent Years studies more active one of system.The U.S.
Patent the 5021366th discloses a kind of phosphate low-melting-point point glass powder, and the softening temperature of the glass is 400~430 DEG C.The U.S.
Patent the P5153151st discloses a kind of phosphate seal glass, and the transition temperature of the glass is 300~340 DEG C, however should
The shortcomings that glass, is containing toxic very big Tl2O。
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of sides that luminescent glass ceramic is prepared with glass powder with low melting point
Method.
It is a further object of the present invention to provide the luminescent glass ceramics that the above method obtains.
The purpose of the present invention is what is be achieved by following technical proposals.
A kind of preparation method of glass powder with low melting point, comprising the following steps:
1) bulk pharmaceutical chemicals are uniformly mixed, it is 15-90 minutes melted at 300~700 DEG C, obtain glass metal；
2) 300~700 DEG C of the glass metal is subjected to quenching: the glass metal is poured into copper mold, it is naturally cold
But to 20~25 DEG C of room temperature, both bulk glasses are obtained；
3) both bulk glasses are crushed, is put into ball mill ball milling, obtains glass powder with low melting point；
Wherein, the bulk pharmaceutical chemicals by weight percentage, by 40~70% SnF2, 20~60% P2O5With 0~20%
Glass powder phase transition temperature adjusting group be grouped as, the glass powder phase transition temperature adjusting group is divided into B2O3、V2O5、Sb2O3、
Bi2O3、SiO2、Al2O3、ZnO、MgO、ZrO2With the mixture of one of CaO or more than one arbitrary proportions.
In the above-mentioned technical solutions, the bulk pharmaceutical chemicals by weight percentage, by 45~60% SnF2, 30~50%
P2O5Glass powder phase transition temperature adjusting group with 0~20% is grouped as.
In the above-mentioned technical solutions, in 1), glass melting temperature is 400~600 DEG C, and melting time is 20-60 minutes.
In the above-mentioned technical solutions, the SnF2And P2O5Mass parts ratio be (1.9~2): 1, the glass powder phase turn
Temperature adjusting group is divided into B2O。
In the above-mentioned technical solutions, the SnF2And P2O5Mass parts ratio be (1.4~1.5): 1, the glass powder phase
Transition temperature adjusting group is divided into V2O5、Sb2O3And Bi2O3Mixture, wherein V2O5、Sb2O3And Bi2O3Mass ratio be (1~
3): (1~2): 1.
In the above-mentioned technical solutions, the SnF2And P2O5Mass parts ratio be (1.1~1.2): 1, the glass powder phase
Transition temperature adjusting group is divided into B2O3、Bi2O3And SiO2Mixture, wherein B2O3、Bi2O3And SiO2Mass ratio be (1~
2): (1~3): 1.
In the above-mentioned technical solutions, the SnF2And P2O5Mass parts ratio be (1.4~1.5): 1, the glass powder phase
Transition temperature adjusting group is divided into SiO2, ZnO and MgO mixture, wherein SiO2, ZnO and MgO mass ratio be (1~4): (0.5
~2): 1.
In the above-mentioned technical solutions, the SnF2And P2O5Mass parts ratio be (1.5~2): 1, the glass powder phase turn
Temperature adjusting group is divided into B2O3、SiO2、Al2O3、ZrO2With the mixture of CaO, wherein B2O3、SiO2、Al2O3、ZrO2And CaO
Mass ratio be (0.7~1.5): (1~3): (0.5~2): 1.
A kind of glass powder with low melting point obtained with above-mentioned preparation method.
A method of luminescent glass ceramic is prepared with above-mentioned glass powder with low melting point, comprising the following steps: by low melting point glass
Glass powder and fluorescent powder uniformly mix, and are calcined；Wherein, calcination temperature be higher than glass powder with low melting point phase transition temperature 25~
35 DEG C, calcination time is 10~30 minutes.
In the above-mentioned technical solutions, the partial size of the glass powder with low melting point is 3~10 microns.
In the above-mentioned technical solutions, the phase transition temperature is measured by differential scanning calorimeter.
In the above-mentioned technical solutions, the calcination temperature is 200~500 DEG C.
In the above-mentioned technical solutions, the calcination temperature is higher than 30 DEG C of the phase transition temperature of glass powder with low melting point.
In the above-mentioned technical solutions, the glass powder with low melting point and fluorescent powder use ball milling to reach uniform mixing, with second
Alcohol is as ball-milling medium, Ball-milling Time at least two hour.
In the above-mentioned technical solutions, 4 hours of Ball-milling Time.
A kind of luminescent glass ceramic prepared in aforementioned manners.
A kind of application of the glass ceramics of above-mentioned glass powder with low melting point preparation as remote fluorescence illuminator in illumination, general
Glass powder with low melting point and fluorescent powder uniformly mix, and are pressed into the thin slice with a thickness of 1~5mm, are calcined；Wherein, calcination temperature
Higher than 25~35 DEG C of phase transition temperature, calcination time is 10~30 minutes.
In the above-mentioned technical solutions, the ratio of the mass parts of the glass powder with low melting point and fluorescent powder is (6~10): (1~
3)。
In the above-mentioned technical solutions, the calcination temperature is higher than 30 DEG C of phase transition temperature.
Compared with the prior art, glass powder with low melting point of the invention has lower glass phase transition temperature, and its glass
Phase transition temperature is adjusted within the scope of 200~500 DEG C, suitable for the production of seal glass and vacuum component and the envelope of LED
Dress, especially suitable for manufacturing luminescent glass ceramic with phosphor material powder, which is particularly suitable for laser lighting.Glass
Glass ceramics forming and sintering at a lower temperature, can effectively avoid the heat deterioration of fluorescent powder at high temperature, in field of laser illumination
With important application value.
Detailed description of the invention
Fig. 1 is the XRD diffracting spectrum for the glass powder with low melting point that embodiment 1 is prepared；
Fig. 2 is the YAG:Ce of glass powder with low melting point made from embodiment 1 and 20%3+The glass that yellow fluorescent powder is prepared
Emission spectrum of the ceramics under the excitation of 447nm blue laser；
Fig. 3 be embodiment 3 glass powder with low melting point and 10% CaAlSiN3: Eu2+The glass that red fluorescence powder is prepared
Emission spectrum of the glass ceramics under the excitation of 447nm blue laser, wherein wavelength 1 is excitation spectrum, and wavelength 2 is emission spectrum.
Specific embodiment
In a specific embodiment of the invention, SnF2It buys in Hubei Heng Lvyuan Science and Technology Ltd., purity is
99.5%；Other various drugs are bought from Shanghai Aladdin biochemical technology limited liability company, and purity is that analysis is pure.SnF2By
Stannous fluoride introduces, P2O5It is introduced by ammonium dihydrogen phosphate, glass powder phase transition temperature adjusts the B of component2O3It is introduced by boric acid, V2O5
It is introduced by ammonium metavanadate, other are all introduced by corresponding oxide.The model TA instrument companies of U.S. of differential scanning calorimeter
Q2000 type.YAG:Ce3+Yellow fluorescent powder is bought from emerging beautiful Science and Technology Ltd., Shenzhen.CaAlSiN3: Eu2+Red fluorescence
Powder is prepared according to following documents: the preparation and performance of the CaAlSiN_3 and YAG red fluorescence powder of [1] Pei Haoyu .Eu doping
Research [D] University Of Nanchang, 2015..Glass metal is forbidden at cooling and shaping (quenching) with water quenching method, otherwise glass ingredient meeting
It reacts with water.The test equipment of XRD is Shimadzu X-ray diffractometer XRD-6000, and the test equipment of emission spectrum is F-
4600 Fluorescence Spectrometer (Hitachi).
Technical solution of the present invention is further illustrated combined with specific embodiments below.
A kind of preparation method of glass powder with low melting point, comprising the following steps:
1) bulk pharmaceutical chemicals are uniformly mixed according to parameter described in table 1 and formula, it is molten in 300~700 DEG C of glass melting temperatures
It is 15-90 minutes processed, obtain glass metal；
2) 300~700 DEG C of glass metal is carried out quenching: glass metal is poured into copper mold, and (disc, mold inner-cavity are deep
Degree is 1cm, radius 5cm) in, 20~25 DEG C of cooled to room temperature, obtain both bulk glasses；
3) by the mechanical crushing of both bulk glasses, it is put into ball mill ball milling, obtains glass powder with low melting point；
Wherein, bulk pharmaceutical chemicals, the weight percent of bulk pharmaceutical chemicals, glass melting temperature and melting time are as shown in table 1.
Glass powder with low melting point each component weight proportion, glass melting temperature and the time of 1 embodiment 1-6 of table and its phase transition temperature
Fig. 1 is the XRD diffracting spectrum for the glass powder with low melting point that embodiment 1 is prepared, it can be seen that obtaining from XRD diagram
Sample 23 degree nearby have a very wide non-structure cell, illustrate SnF provided by the invention2-P2O5System is a kind of good
Glass system.
By weight percentage, the glass powder with low melting point of 80% embodiment 1 and 20% YAG:Ce3+Yellow fluorescent powder ball milling
4 hours after evenly mixing, are pressed into the thin slice of 2mm, are sintered in 230 DEG C of electric furnace and fluorescent glass pottery can be obtained within 20 minutes
Porcelain；White light emission can be obtained under the excitation of blue laser in the luminescent glass ceramic, and launching light spectrogram is as shown in Figure 2.
The ratio of % by weight meter, the glass powder with low melting point of 70% embodiment 2 and 30% YAG:Ce3+Yellow fluorescent powder ball milling 4
A hour after evenly mixing, is pressed into the thin slice of 3mm, and being sintered 20 minutes in 260 DEG C of electric furnace can be obtained luminescent glass ceramic；
White light emission can be obtained under the excitation of blue laser in the luminescent glass ceramic.
The ratio of % by weight meter, the glass powder with low melting point of 90% embodiment 3 and 10% CaAlSiN3: Eu2+Red fluorescence powder
4 hours of ball milling are pressed into the thin slice of 2.5mm after evenly mixing, and being sintered 30 minutes in 300 DEG C of electric furnace can be obtained luminous glass
Glass ceramics；Under the excitation of blue laser red blue light synchronized transmissions can be obtained, launching light spectrogram is such as in the luminescent glass ceramic
Shown in Fig. 3.
The ratio of % by weight meter, the glass powder with low melting point of 80% embodiment 4 and 20% CaAlSiN3: Eu2+Red fluorescence powder
4 hours of ball milling are pressed into the thin slice of 2mm after evenly mixing, and being sintered 30 minutes in 380 DEG C of electric furnace can be obtained fluorescent glass
Ceramics；Red blue light synchronized transmissions can be obtained under the excitation of blue laser in the luminescent glass ceramic.
The ratio of % by weight meter, the glass powder with low melting point of 70% embodiment 5 and 30% red, green, blue three-color phosphor ball milling 4
A hour after evenly mixing, is pressed into the thin slice of 2mm, and being sintered 20 minutes in 450 DEG C of electric furnace can be obtained luminescent glass ceramic；
White light emission can be obtained under the excitation of ultraviolet laser in the luminescent glass ceramic.
The ratio of % by weight meter, red that the glass powder with low melting point of 80% embodiment 6 and 20% blue light can excite, green are glimmering
The light sphere of powder grind 4 hours after evenly mixing, be pressed into the thin slice of 2mm, be sintered in 500 DEG C of electric furnace can be obtained within 20 minutes it is luminous
Glass ceramics；Under the excitation of the luminescent glass ceramic blue laser, white light emission can be obtained.
It is equal that phase transition temperature by adjusting the technical program adjusts component, basic components, glass melting temperature and melting time
The available and consistent property of above-described embodiment.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. a kind of method for preparing luminescent glass ceramic with glass powder with low melting point, which comprises the following steps: by eutectic
Point glass powder and fluorescent powder uniformly mix, and are calcined；Wherein, calcination temperature is higher than 25~35 DEG C of phase transition temperature, calcining
Time is 10~30 minutes；
The preparation method of the glass powder with low melting point the following steps are included:
1) bulk pharmaceutical chemicals are uniformly mixed, it is 15-90 minutes melted at 300~700 DEG C, obtain glass metal；
2) 300~700 DEG C of the glass metal is subjected to quenching: the glass metal is poured into copper mold, is naturally cooled to
20~25 DEG C of room temperature, obtain both bulk glasses；
3) both bulk glasses are crushed, are put into ball mill ball milling, obtain glass powder with low melting point,
Wherein, the raw material by weight percentage, by 40~70% SnF2, 30~50% P2O5With 0~20% glass
Powder phase transition temperature adjusting group is grouped as, and the glass powder phase transition temperature adjusting group is divided into B2O3、V2O5、Sb2O3、Bi2O3、
SiO2、Al2O3、ZnO、MgO、ZrO2With the mixture of one of CaO or more than one arbitrary proportions.
2. the method according to claim 1, wherein the ratio of the mass parts of the glass powder with low melting point and fluorescent powder
For (6~10): (1~3).
3. according to the method described in claim 2, it is characterized in that, the SnF2And P2O5Mass parts ratio be (1.9~2):
1, the glass powder phase transition temperature adjusting group is divided into B2O3；
Alternatively, the SnF2And P2O5The ratios of mass parts be (1.4~1.5): 1, the glass powder phase transition temperature adjusts component
For V2O5、Sb2O3And Bi2O3Mixture, wherein V2O5、Sb2O3And Bi2O3Mass ratio be (1~3): (1~2): 1；
Alternatively, the SnF2And P2O5The ratios of mass parts be (1.1~1.2): 1, the glass powder phase transition temperature adjusts component
For B2O3、Bi2O3And SiO2Mixture, wherein B2O3、Bi2O3And SiO2Mass ratio be (1~2): (1~3): 1；
Alternatively, the SnF2And P2O5The ratios of mass parts be (1.4~1.5): 1, the glass powder phase transition temperature adjusts component
For SiO2, ZnO and MgO mixture, wherein SiO2, ZnO and MgO mass ratio be (1~4): (0.5~2): 1；
Alternatively, the SnF2And P2O5Mass parts ratio be (1.5~2): 1, the glass powder phase transition temperature adjusting group is divided into
B2O3、SiO2、Al2O3、ZrO2With the mixture of CaO, wherein B2O3、SiO2、Al2O3、ZrO2With the mass ratio of CaO be (0.7~
1.5): (1~3): (0.5~2): 1.
4. according to the method described in claim 3, it is characterized in that, the raw material by weight percentage, by 45~60%
SnF2, 30~50% P2O5Glass powder phase transition temperature adjusting group with 0~20% is grouped as.
5. according to the method described in claim 4, it is characterized in that, it is described 1) in, glass melting temperature be 400~600 DEG C.
6. according to the method described in claim 5, it is characterized in that, it is described 1) in, melting time be 20-60 minutes.
7. according to the method described in claim 6, it is characterized in that, the glass powder with low melting point and fluorescent powder use ball milling to reach
To uniform mixing, using ethyl alcohol as ball-milling medium, Ball-milling Time at least two hour, preferably 4 hours.
8. the method according to the description of claim 7 is characterized in that the calcination temperature is 200~500 DEG C and is higher than phase transition
30 DEG C of temperature.
9. according to the method described in claim 8, it is characterized in that, the partial size of the glass powder with low melting point is 3~10 microns.
10. a kind of luminescent glass ceramic prepared with any one of claim 1~9 the method.
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| CN109721250B (en) | 2021-11-26 |
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