CN106892564A - The preparation method of silica scintillation glass high - Google Patents
The preparation method of silica scintillation glass high Download PDFInfo
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- CN106892564A CN106892564A CN201710017505.2A CN201710017505A CN106892564A CN 106892564 A CN106892564 A CN 106892564A CN 201710017505 A CN201710017505 A CN 201710017505A CN 106892564 A CN106892564 A CN 106892564A
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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
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/005—Multi-cellular glass ; Porous or hollow glass or glass particles obtained by leaching after a phase separation step
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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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment
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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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0095—Solution impregnating; Solution doping; Molecular stuffing, e.g. of porous 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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Abstract
A kind of preparation method of silica scintillation glass high, belongs to the preparing technical field of glass.Luminescence queenching phenomenon is produced present invention aim to address the rare earth ion cluster adulterated in scintillation glass and causes the few problem of rare earth ion doped amount, rare earth ion is adsorbed onto the preparation method of the silica scintillation glass high of the inner surface in equally distributed hole.Step of the invention is：1. host glass is prepared；2. split-phase；3. prepared by cellular glass；4. it is rare earth ion doped；5. high temperature sintering.Be incorporated into rare earth ion in nano-porous glass using infusion process by the present invention, so that the glass Rare Earth Ion for preparing according to the method described above is presented equally distributed phenomenon by being adsorbed onto on the inner surface in hole, so as to reduce because of the luminescence queenching that rare earth ion is caused because of cluster, the doping of rare earth ion is improve, so as to improve the luminous intensity of rare earth ion.The present invention also have studied interparticle energy transmission by being co-doped with various rare earth ions.
Description
Technical field
The invention belongs to the preparing technical field of glass.
Background technology
With the fast development of the technologies such as high-energy physics, nuclear physics and industry detection, the research to high-performance nuclear detector
Become a kind of trend, in recent years, research is applied to the research institution of the novel high-density scintillation material in high-energy physics field
It is more and more, and scintillator has very important effect in the research of high energy particle.Scintillator is a kind of by high-energy photon
The ionization energy of (X-ray, gamma-rays) or particle (hadron, electronics, proton, alpha particle etc.) changes into the light of ultraviolet/visible light
Conductivity type luminescent material, is a kind of energy transfer medium.The discovery of the discriminating of particle, the measure of particle properties and new particle all from
High performance scintillator is not opened.
Crystalline material is existing scintillator material main in the application, but crystal have the shortcomings that it is very big, such as：It is produced into
This is very high, very high to production equipment requirement, and growth cycle is long, is very easy to be influenceed by external environment.Because light is visited
The development of survey technology and the urgent need of following small-sized medical imaging detection device, the X-ray excited polycrystalline structure scintillator of application is easy in the urgent need to research
Material, vitreum scintillation material arises at the historic moment like this, an important component of the scintillation glass into scintillation material.
The content of the invention
Produce luminescence queenching phenomenon and lead present invention aim to address the rare earth ion cluster adulterated in scintillation glass
The few problem of rare earth ion doped amount is caused, rare earth ion is adsorbed onto the silica scintillation glass high of the inner surface in equally distributed hole
Preparation method.
Step of the invention is：
1. host glass is prepared：SiO is constituted according to weight fraction2:B2O3:Na2O:Al2O3=50~70:20~40:5~15:1 ~ 5 makees
It is matrix, adds the fining agent Sb that above-mentioned matrix weight number is 1%2O3, uniform mixing is weighed according to the above ratio, coordinated
Material, is put into platinum or corundum crucible, and the high temperature furnace for being placed in 1400-1500 DEG C founds 30-200min, then 400-600
DEG C iron plate on cast cooling shaping be borosilicate glass, as host glass；
2. split-phase：Step host glass 1. is put into Muffle furnace, in split-phase heat treatment 12-72h at 500-650 DEG C, is separated
Sodium boron phase and silicon phase, obtain muddy devitrification split-phase glass sample；
3. prepared by cellular glass：
A, the borosilicate glass after split-phase is pre-processed, using the strong acid solution with corrosiveness, glass is carried out
Surface treatment, destroys the silicon phase of glass surface, will be taken out after 1-10min in glass-impregnated to strong acid solution, washing；
B, with one of hydrochloric acid or nitric acid it is configured to H with water again+Concentration is the acid solution of 0.03-l mol/L, then prepare 0.1-
The cushioning liquid of 1mol/L, the mixing that a step borosilicate glasses are immersed in the acid solution and cushioning liquid that mix in proportion is molten
In liquid, 12-48h in the thermostat water bath being placed at a temperature of 60-100 DEG C takes out and after natural cooling by glass deionization
Water is cleaned, drying；
4. it is rare earth ion doped：The rare earth ion for being adulterated is cerium ion, terbium ion, and cerium ion concentration is in the mixed solution
0.05 ~ 0.5mol%, terbium ion concentration is 0.1 ~ 0.5mol%；The rare-earth ion solution of various concentrations is prepared, cellular glass is soaked
Steep and realize doping in the rare-earth ion solution 12h for preparing, taken out after the completion of doping, washing, dry after, be stored in drier
It is interior；
5. high temperature sintering：The glass for having adulterated is carried out to be sintered according to following heating gradient, the intensification step of sintering process
Suddenly it is：A, from room temperature to 300 ~ 500 DEG C of intervals, heating rate be less than 2 DEG C/min, in 300 ~ 500 DEG C of temperature ranges at least
Kept for 60 minutes；
B, 700 ~ 900 DEG C of intervals are warmed up to from 300 ~ 500 DEG C of temperature ranges, heating rate is less than 2 DEG C/min, at 700 ~ 900 DEG C
Temperature range at least keeps 60min；
C, 900 ~ 1200 DEG C of intervals are warmed up to from 700 ~ 900 DEG C of intervals, heating rate is less than 2 DEG C/min, in 900 ~ 1200 DEG C of temperature
Degree interval at least keeps 60min；
D, under reducing atmosphere in 800-1200 DEG C sinter 3-13h, obtain transparent vagcor.
The strong acid solution of the pretreatment described in step of the present invention a steps 3. is hydrofluoric acid.
Be incorporated into rare earth ion in nano-porous glass using infusion process by the present invention so that is prepared according to the method described above
Glass Rare Earth Ion equally distributed phenomenon is presented by being adsorbed onto on the inner surface in hole, so as to reduce because rare earth
The luminescence queenching that ion is caused because of cluster, improves the doping of rare earth ion, so as to improve the luminous intensity of rare earth ion.
The present invention also have studied interparticle energy transmission by being co-doped with various rare earth ions.
Brief description of the drawings
Fig. 1 is spectrum and life test figure.
Specific embodiment
Step of the invention is：
1. host glass is prepared：SiO is constituted according to weight fraction2:B2O3:Na2O:Al2O3=50~70:20~40:5~15:1 ~ 5 makees
It is matrix, adds the fining agent Sb that above-mentioned matrix weight number is 1%2O3, uniform mixing is weighed according to the above ratio, coordinated
Material, is put into platinum or corundum crucible, and the high temperature furnace for being placed in 1400-1500 DEG C founds 30-200min, then 400-600
DEG C iron plate on cast cooling shaping be borosilicate glass, as host glass；
2. split-phase：Step host glass 1. is put into Muffle furnace, in split-phase heat treatment 12-72h at 500-650 DEG C, is separated
Sodium boron phase and silicon phase, obtain muddy devitrification split-phase glass sample；
3. prepared by cellular glass：
A, the borosilicate glass after split-phase is pre-processed, using the strong acid solution with corrosiveness, glass is carried out
Surface treatment, destroys the silicon phase of glass surface, will be taken out after 1-10min in glass-impregnated to strong acid solution, washing；
B, with one of hydrochloric acid or nitric acid it is configured to H with water again+Concentration is the acid solution of 0.03-l mol/L, then prepare 0.1-
The cushioning liquid of 1mol/L, the mixing that a step borosilicate glasses are immersed in the acid solution and cushioning liquid that mix in proportion is molten
In liquid, 12-48h in the thermostat water bath being placed at a temperature of 60-100 DEG C takes out and after natural cooling by glass deionization
Water is cleaned, drying；
4. it is rare earth ion doped：The rare earth ion for being adulterated is cerium ion, terbium ion, and cerium ion concentration is in the mixed solution
0.05 ~ 0.5mol%, terbium ion concentration is 0.1 ~ 0.5mol%；The rare-earth ion solution of various concentrations is prepared, cellular glass is soaked
Steep and realize doping in the rare-earth ion solution 12h for preparing, taken out after the completion of doping, washing, dry after, be stored in drier
It is interior；
5. high temperature sintering：The glass for having adulterated is carried out to be sintered according to following heating gradient, the intensification step of sintering process
Suddenly it is：A, from room temperature to 300 ~ 500 DEG C of intervals, heating rate be less than 2 DEG C/min, in 300 ~ 500 DEG C of temperature ranges at least
Kept for 60 minutes；
B, 700 ~ 900 DEG C of intervals are warmed up to from 300 ~ 500 DEG C of temperature ranges, heating rate is less than 2 DEG C/min, at 700 ~ 900 DEG C
Temperature range at least keeps 60min；
C, 900 ~ 1200 DEG C of intervals are warmed up to from 700 ~ 900 DEG C of intervals, heating rate is less than 2 DEG C/min, in 900 ~ 1200 DEG C of temperature
Degree interval at least keeps 60min；
D, under reducing atmosphere in 800-1200 DEG C sinter 3-13h, obtain transparent vagcor.
The strong acid solution of the pretreatment described in step of the present invention a steps 3. is hydrofluoric acid.
The present invention is described in further detail below：
Other scintillation materials are different from, scintillation glass has the advantages that very big：Easy-formation easy to make is homogeneous and shape is variable
Degree is very strong, disclosure satisfy that various size requirement, it is often more important that its cost can be on a large scale far below scintillation crystal
Using the different purposes of different glass formula correspondences, the formula that glass is adjusted on a large scale disclosure satisfy that different Requirement of Spectrum.
Glass is easy to draw flash fiber, and then flash fiber panel is obtained, and neutron is detected simultaneously if containing B component in glass.
The research urgent problem of current scintillation glass is exactly low its density and photoyield.Newest detection component is to a certain degree
On can be by the development shortcoming low to make up glass light output of Detection Techniques, that is to say, that the low problem of photoyield has been obtained
To solution.
Generally, in order to improve yield and simplify production process, what is commonly used now is high-temperature melting method, is used
The method can improve productivity ratio really, shorten the production cycle, but make the silica scintillation glass high being melting out in this way
In rare-earth dopant easily produce cluster and produce concentration quenching phenomena, can not effectively improve rare earth ion flicker effect
Rate and luminous efficiency.Silica scintillation glass high, silica porous high are prepared using nano-porous glass using the method for the present invention
Glass is a kind of excellent silicate glass matrix material, due to its SiO2Content more than 96%, its optically and mechanically performance and stone
English glass is very close to, in fact, the quartz glass product of early stage is exactly to be obtained using sintering high silica porous glass.Silicon high
Oxygen cellular glass causes active ions to be easier uniformly to be distributed in pore structure with specific surface area and porosity high very high
Surface, a kind of distribution of the people using physical method come dispersed active ions in cellular glass, so as to avoid activation
The cluster of ion and the concentration quenching of active ions excitation state, strengthen its luminous intensity.
The present invention uses Na20-B203-Si02 glass system, first founds host glass according to constant weight percentage, then preparing
Host glass be incubated a period of time at a certain temperature, be allowed to separate sodium boron phase and silicon phase, then the glass of split-phase in constant temperature
The molten treatment of acid is carried out in water-bath and the cellular glass that uniform pore diameter is distributed is formed（Aperture size integrated distribution is in 1-100nm）, so
It is dipped into again afterwards in the mixed solution of the solution of cerium terbium rare earth ion, rare earth ion is adsorbed onto hole by way of free diffusing
Inner surface so that rare earth ion is evenly distributed in host glass, removes physical absorption water and makes glass finally by sintering
Densification, obtains transparent glass sample.By contrast, although this method is slightly more cumbersome than high-temperature melting method, but can make
Rare-earth dopant is uniformly distributed without forming rare earth polymer, it is suppressed that concentration quenching phenomena, so as to improve scintillation glass
The doping of Rare Earth Ion, also improves the scintillation efficiency of rare earth ion.
Ce3+5d-4f transition be allowed electric dipole transition, the electron lifetime of its 5d configuration is very short（Generally 30 ~
100ns）, with energy transmission probability higher.Tb3+Doped silicate glasses have that excitation of X-rays photoyield is high, the transparency
It is good, and strong green glow, the features such as matching with the sensitive wave length of photoelectric device, as scintillation glass one are produced at 542nm
Individual study hotspot.Tb3+There is a weak linear absorption band at 350nm -370nm, and this spectral line is just and Ce3+365nm
Transmitting band overlaps, therefore Tb3+Can be by Ce3+Sensitization, and be energized into5D3On energy level, Tb3+'s5D3Energy level produces two kinds of transition, and one is
By5D3 directly transits to matrix, and another is5D3Relax towards5D4, then by5D4Transit to ground state and produce fluorescence.So using nanometer
Cellular glass is carrier, Tb3+It is light emitting ionic, Ce3+It is sensitized ions, the die-away time of material is reduced, using nanoporous glass
Micropore, big specific surface area that glass is evenly distributed, make rare earth ion obtain sufficient physical dispersion and the spy adsorbed in glass
Property, prepare the double-doped vagcor scintillation glass material of terbium cerium.So as to play the rare earth ion doped amount of increase, glass light is improved
The purpose of yield.
Embodiment 1：
1) by setting parent glass weight fraction SiO2: B2O3: Na2O：Al2O3=58:30:10:2, SiO2Use silicon dioxide powder
End introduces, B2O3Introduced with boric acid, Na2O is introduced with natrium carbonicum calcinatum, Al2O3Introduced with alumina powder, Sb2O3With three oxidations
Two antimony powders end is introduced, raw materials used to be analysis pure raw material, and raw material is weighed according to molar ratio conversion, and it is 1% to add weight fraction
Sb2O3, the SiO that will be weighed2, boric acid, natrium carbonicum calcinatum, aluminum oxide and antimony oxide ground and mixed it is uniform, coordinated
Material；
2）Batch corundum crucible is inserted in high temperature furnace, in high temperature melting 3h at 1450 DEG C, stainless steel mold is then cast in
It is molded in tool, obtains glass sample A；
3) glass sample A is put into Muffle furnace immediately, in split-phase heat treatment 30h at 580 DEG C, obtains milky
Devitrification split-phase glass sample；
4) gained milky devitrification split-phase glass sample is inserted into the dilute hydrochloric acid solution and 1mol/ equipped with mass concentration for 1mol/L
In the beaker of the ammonium chloride buffer of L, and it is put into thermostat water bath, solvable rich sodium boron is leached in leaching under 90 DEG C of constant temperature
Phase, it is as clear as crystal in the solution to glass sample, glass sample B is obtained,
5) the glass sample B after leaching is taken out, is soaked with deionized water, washed, dried；Obtain opaque porous silica high
Glass；
6) porous borosilicate glass is impregnated into 12h in the terbium nitrate solution of 0.2mol/L, is washed after the completion of dipping, done
It is dry, obtain vagcor；
7）Vagcor is put into high-temperature electric heat stove, is sintered under reducing atmosphere.Heating schedule is：Room temperature is to 400
DEG C 4h, insulation 1h, then 4h be warmed up to 800 DEG C, be warmed up to 1000 DEG C after 2h after insulation 1h, be incubated 1h, last natural cooling, i.e.,
Transparent vagcor can be obtained.
Spectrum and life test are carried out to embodiment 1, as a result as shown in Figure 1.
Embodiment 2：
1) by setting parent glass weight fraction SiO2: B2O3: Na2O：Al2O3=58:30:10:2, SiO2Use silicon dioxide powder
End introduces, B2O3Introduced with boric acid, Na2O is introduced with natrium carbonicum calcinatum, Al2O3Introduced with alumina powder, Sb2O3With three oxidations
Two antimony powders end is introduced, raw materials used to be analysis pure raw material, and raw material is weighed according to molar ratio conversion, and it is 1% to add weight fraction
Sb2O3, the SiO that will be weighed2, boric acid, natrium carbonicum calcinatum, aluminum oxide and antimony oxide ground and mixed it is uniform, obtain batch
2）Batch corundum crucible is inserted in high temperature furnace, in high temperature melting 3h at 1450 DEG C, stainless steel mold is then cast in
It is molded in tool, obtains glass sample A；
3) glass sample A is put into Muffle furnace immediately, in split-phase heat treatment 30h at 580 DEG C, obtains milky
Devitrification split-phase glass sample；
4) gained milky devitrification split-phase glass sample is inserted into the dilute hydrochloric acid solution and 1mol/ equipped with mass concentration for 1mol/L
In the beaker of the ammonium chloride buffer of L, and it is put into thermostat water bath, solvable rich sodium boron is leached in leaching under 90 DEG C of constant temperature
Phase, it is as clear as crystal in the solution to glass sample, glass sample B is obtained,
5) the glass sample B after leaching is taken out, is soaked with deionized water, washed, dried；Obtain the silica glass porous high of devitrification
Glass；
6) porous borosilicate glass is impregnated into 12 in the cerous nitrate solution of the terbium nitrate solution of 0.2mol/L and 0.05mol/L
Hour, washed after the completion of dipping, dried, obtain vagcor；
7）Vagcor is put into high-temperature electric heat stove, is sintered under reducing atmosphere.Heating schedule is：Room temperature is to 400
DEG C 4h, insulation 1h, then 4h be warmed up to 800 DEG C, be warmed up to 1000 DEG C after 2h after insulation 1h, be incubated 1h, last natural cooling, i.e.,
Transparent vagcor can be obtained.
Embodiment 3：
1) by setting parent glass weight fraction SiO2: B2O3: Na2O：Al2O3=58:30:10:2, SiO2Use silicon dioxide powder
End introduces, B2O3Introduced with boric acid, Na2O is introduced with natrium carbonicum calcinatum, Al2O3Introduced with alumina powder, Sb2O3With three oxidations
Two antimony powders end is introduced, raw materials used to be analysis pure raw material, and raw material is weighed according to molar ratio conversion, and it is 1% to add weight fraction
Sb2O3, the SiO that will be weighed2, boric acid, natrium carbonicum calcinatum, aluminum oxide and antimony oxide ground and mixed it is uniform, coordinated
Material；
2）Batch corundum crucible is inserted in high temperature furnace, in high temperature melting 3h at 1450 DEG C, stainless steel mold is then cast in
It is molded in tool, obtains glass sample A；
3) glass sample A is put into Muffle furnace immediately, in split-phase heat treatment 30h at 580 DEG C, obtains milky
Devitrification split-phase glass sample；
4) gained milky devitrification split-phase glass sample is inserted into the dilute hydrochloric acid solution and 1mol/ equipped with mass concentration for 1mol/L
In the beaker of the ammonium chloride buffer of L, and it is put into thermostat water bath, solvable rich sodium boron is leached in leaching under 90 DEG C of constant temperature
Phase, it is as clear as crystal in the solution to glass sample, glass sample B is obtained,
5) the glass sample B after leaching is taken out, is soaked with deionized water, washed, dried；Obtain opaque porous silica high
Glass；
6) porous borosilicate glass is impregnated into 12h in the cerous nitrate solution of the terbium nitrate solution of 0.2mol/L and 0.1mol/L,
Washed after the completion of dipping, dried, obtained vagcor；
7）Vagcor is put into high-temperature electric heat stove, is sintered under reducing atmosphere.Heating schedule is：Room temperature is to 400
DEG C 4h, insulation 1h, then 4h be warmed up to 800 DEG C, be warmed up to 1000 DEG C after 2h after insulation 1h, be incubated 1h, last natural cooling, i.e.,
Transparent vagcor can be obtained.
Embodiment 4：
1) by setting parent glass weight fraction SiO2: B2O3: Na2O：Al2O3=58:30:10:2, SiO2Use silicon dioxide powder
End introduces, B2O3Introduced with boric acid, Na2O is introduced with natrium carbonicum calcinatum, Al2O3Introduced with alumina powder, Sb2O3With three oxidations
Two antimony powders end is introduced, raw materials used to be analysis pure raw material, and raw material is weighed according to molar ratio conversion, and it is 1% to add weight fraction
Sb2O3, the SiO that will be weighed2, boric acid, natrium carbonicum calcinatum, aluminum oxide and antimony oxide ground and mixed it is uniform, coordinated
Material；
2）Batch corundum crucible is inserted in high temperature furnace, in high temperature melting 3h at 1450 DEG C, stainless steel mold is then cast in
It is molded in tool, obtains glass sample A；
3) glass sample A is put into Muffle furnace immediately, in split-phase heat treatment 30h at 580 DEG C, obtains milky
Devitrification split-phase glass sample；
4) gained milky devitrification split-phase glass sample is inserted into the dilute hydrochloric acid solution and 1mol/ equipped with mass concentration for 1mol/L
In the beaker of the ammonium chloride buffer of L, and it is put into thermostat water bath, solvable rich sodium boron is leached in leaching under 90 DEG C of constant temperature
Phase, it is as clear as crystal in the solution to glass sample, glass sample B is obtained,
5) the glass sample B after leaching is taken out, is soaked with deionized water, washed, dried；Obtain opaque porous silica high
Glass；
6) porous borosilicate glass is impregnated into 12 in the cerous nitrate solution of the terbium nitrate solution of 0.2mol/L and 0.15mol/L
Hour, washed after the completion of dipping, dried, obtain vagcor；
7）Vagcor is put into high-temperature electric heat stove, is sintered under reducing atmosphere.Heating schedule is：Room temperature is to 400
DEG C 4h, insulation 1h, then 4h be warmed up to 800 DEG C, be warmed up to 1000 DEG C after 2h after insulation 1h, be incubated 1h, last natural cooling, i.e.,
Transparent vagcor can be obtained.
Embodiment 5：
1) by setting parent glass weight fraction SiO2: B2O3: Na2O：Al2O3=58:30:10:2, SiO2Use silicon dioxide powder
End introduces, B2O3Introduced with boric acid, Na2O is introduced with natrium carbonicum calcinatum, Al2O3Introduced with alumina powder, Sb2O3With three oxidations
Two antimony powders end is introduced, raw materials used to be analysis pure raw material, and raw material is weighed according to molar ratio conversion, and it is 1% to add weight fraction
Sb2O3, the SiO that will be weighed2, boric acid, natrium carbonicum calcinatum, aluminum oxide and antimony oxide ground and mixed it is uniform, coordinated
Material；
2）Batch corundum crucible is inserted in high temperature furnace, in high temperature melting 3h at 1450 DEG C, stainless steel mold is then cast in
It is molded in tool, obtains glass sample A；
3) glass sample A is put into Muffle furnace immediately, in split-phase heat treatment 30h at 580 DEG C, obtains milky
Devitrification split-phase glass sample；
4) gained milky devitrification split-phase glass sample is inserted into the dilute hydrochloric acid solution and 1mol/ equipped with mass concentration for 1mol/L
In the beaker of the ammonium chloride buffer of L, and it is put into thermostat water bath, solvable rich sodium boron is leached in leaching under 90 DEG C of constant temperature
Phase, it is as clear as crystal in the solution to glass sample, glass sample B is obtained,
5) the glass sample B after leaching is taken out, is soaked with deionized water, washed, dried；Obtain opaque porous silica high
Glass；
6) porous borosilicate glass is impregnated into 12 in the cerous nitrate solution of the terbium nitrate solution of 0.2mol/L and 0.2mol/L
Hour, washed after the completion of dipping, dried, obtain vagcor；
7）Vagcor is put into high-temperature electric heat stove, is sintered under reducing atmosphere.Heating schedule is：Room temperature is to 400
DEG C 4h, insulation 1h, then 4h be warmed up to 800 DEG C, be warmed up to 1000 DEG C after 2h after insulation 1h, be incubated 1h, last natural cooling, i.e.,
Transparent vagcor can be obtained.
Claims (2)
1. a kind of preparation method of silica scintillation glass high, it is characterised in that：
1. host glass is prepared：SiO is constituted according to weight fraction2:B2O3:Na2O:Al2O3=50~70:20~40:5~15:1 ~ 5 makees
It is matrix, adds the fining agent Sb that above-mentioned matrix weight number is 1%2O3, uniform mixing is weighed according to the above ratio, coordinated
Material, is put into platinum or corundum crucible, and the high temperature furnace for being placed in 1400-1500 DEG C founds 30-200min, then 400-600
DEG C iron plate on cast cooling shaping be borosilicate glass, as host glass；
2. split-phase：Step host glass 1. is put into Muffle furnace, in split-phase heat treatment 12-72h at 500-650 DEG C, is separated
Sodium boron phase and silicon phase, obtain muddy devitrification split-phase glass sample；
3. prepared by cellular glass：
A, the borosilicate glass after split-phase is pre-processed, using the strong acid solution with corrosiveness, glass is carried out
Surface treatment, destroys the silicon phase of glass surface, will be taken out after 1-10min in glass-impregnated to strong acid solution, washing；
B, with one of hydrochloric acid or nitric acid it is configured to H with water again+Concentration is the acid solution of 0.03-l mol/L, then prepare 0.1-
The cushioning liquid of 1mol/L, the mixing that a step borosilicate glasses are immersed in the acid solution and cushioning liquid that mix in proportion is molten
In liquid, 12-48h in the thermostat water bath being placed at a temperature of 60-100 DEG C takes out and after natural cooling by glass deionization
Water is cleaned, drying；
4. it is rare earth ion doped：The rare earth ion for being adulterated is cerium ion, terbium ion, and cerium ion concentration is in the mixed solution
0.05 ~ 0.5mol%, terbium ion concentration is 0.1 ~ 0.5mol%；The rare-earth ion solution of various concentrations is prepared, cellular glass is soaked
Steep and realize doping in the rare-earth ion solution 12h for preparing, taken out after the completion of doping, washing, dry after, be stored in drier
It is interior；
5. high temperature sintering：The glass for having adulterated is carried out to be sintered according to following heating gradient, the intensification step of sintering process
Suddenly it is：A, from room temperature to 300 ~ 500 DEG C of intervals, heating rate be less than 2 DEG C/min, in 300 ~ 500 DEG C of temperature ranges at least
Kept for 60 minutes；
B, 700 ~ 900 DEG C of intervals are warmed up to from 300 ~ 500 DEG C of temperature ranges, heating rate is less than 2 DEG C/min, at 700 ~ 900 DEG C
Temperature range at least keeps 60min；
C, 900 ~ 1200 DEG C of intervals are warmed up to from 700 ~ 900 DEG C of intervals, heating rate is less than 2 DEG C/min, in 900 ~ 1200 DEG C of temperature
Degree interval at least keeps 60min；
D, under reducing atmosphere in 800-1200 DEG C sinter 3-13h, obtain transparent vagcor.
2. the preparation method of the silica scintillation glass high described in claims 1, it is characterised in that：Described in step a steps 3.
Pretreatment strong acid solution be hydrofluoric acid.
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| CN108467196A (en) * | 2018-03-27 | 2018-08-31 | 华南理工大学 | A kind of RGB light full-inorganic perovskite quantum dot and cellular glass composite luminescent material and preparation method thereof |
| CN112913839A (en) * | 2021-01-21 | 2021-06-08 | 科立视材料科技有限公司 | Glass carrier rare earth composite inorganic antibacterial agent and preparation method thereof |
| CN113293435A (en) * | 2021-05-25 | 2021-08-24 | 南京邮电大学 | Halide perovskite nanocrystalline material based on cerium-doped glass matrix and preparation method thereof |
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| CN112913839B (en) * | 2021-01-21 | 2022-04-22 | 科立视材料科技有限公司 | Glass carrier rare earth composite inorganic antibacterial agent and preparation method thereof |
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