CN106892564B - Preparation method of high silica scintillation glass - Google Patents
Preparation method of high silica scintillation glass Download PDFInfo
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- CN106892564B CN106892564B CN201710017505.2A CN201710017505A CN106892564B CN 106892564 B CN106892564 B CN 106892564B CN 201710017505 A CN201710017505 A CN 201710017505A CN 106892564 B CN106892564 B CN 106892564B
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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
The invention relates to a preparation method of high silica scintillation glass, belonging to the technical field of glass preparation, aiming at solving the problem of small rare earth ion doping amount caused by the luminescence quenching phenomenon generated by rare earth ion clusters doped in the scintillation glass, and the preparation method of the high silica scintillation glass enables rare earth ions to be adsorbed to the inner surfaces of uniformly distributed holes.
Description
Technical Field
The invention belongs to the technical field of glass preparation.
Background
With the rapid development of high-energy physics, nuclear physics, industrial detection and other technologies, the research on high-performance nuclear detectors becomes a trend, and in recent years, more and more research institutions for researching novel high-density scintillation materials applied to the field of high-energy physics are provided, and scintillators have a very important role in the research of high-energy particles. The scintillator is a photoconductive type luminescent material that converts ionization energy of high-energy photons (X-rays, gamma rays) or particles (hadrons, electrons, protons, alpha-particles, etc.) into ultraviolet/visible photons, and is an energy converter. Identification of particles, determination of particle properties, and discovery of new particles are all without departing from high performance scintillators.
The crystal material is the main scintillator material in the present application, however, the crystal has great disadvantages, such as: the production cost is very high, the requirement on production equipment is very high, the growth cycle is long, and the method is very easily influenced by the external environment. Due to the development of optical detection technology and the urgent need of the following small medical imaging detection devices, the research of solid scintillator materials which are easy to apply is urgently needed, and glass scintillator materials are produced, and the scintillation glass becomes an important component of the scintillator materials.
Disclosure of Invention
The invention aims to solve the problem of small doping amount of rare earth ions caused by luminescence quenching phenomenon generated by rare earth ion clusters doped in scintillation glass, and the preparation method of the high silica scintillation glass enables the rare earth ions to be adsorbed to the inner surfaces of uniformly distributed holes.
The method comprises the following steps:
① preparing the matrix glass by composing SiO according to weight fraction2:B2O3:Na2O:Al2O3=50 ~ 70:20 ~ 40:5 ~ 15:1 ~ 5 as matrix, and clarifier Sb with the weight part of the matrix being 1 percent is added2O3Weighing and uniformly mixing the raw materials according to the proportion to obtain a batch, putting the batch into a platinum or corundum crucible, putting the crucible into a high-temperature furnace at 1400-1500 ℃ for melting for 30-200 min, and then casting and cooling the batch on an iron plate at 400-600 ℃ to form borosilicate glass serving as matrix glass;
② phase separation, namely putting the matrix glass in the step ① into a muffle furnace, carrying out phase separation heat treatment for 12-72h at the temperature of 500-650 ℃, and separating a sodium-boron phase and a silicon phase to obtain a turbid devitrified phase separation glass sample;
③ porous glass preparation:
a. pretreating the phase-separated borosilicate glass, using a strong acid solution with a corrosion effect to perform surface treatment on the glass to destroy the silicon phase on the surface of the glass, soaking the glass in the strong acid solution for 1-10min, then taking out the glass, and washing the glass;
b. then using one of hydrochloric acid or nitric acid and water to prepare H+Acid solution with concentration of 0.03-L mol/L, preparing buffer solution with concentration of 0.1-1 mol/L, soaking borosilicate glass in step a in the acid solution mixed according to a certain proportionPutting the mixed solution of the glass and the buffer solution into a constant-temperature water bath kettle at the temperature of 60-100 ℃ for 12-48 h, taking out the mixed solution, naturally cooling the mixed solution, washing the glass with deionized water, and drying the glass;
④ doping rare earth ions, namely cerium ions and terbium ions, wherein the concentration of the cerium ions in the mixed solution is 0.05 ~ 0.5.5 mol%, and the concentration of the terbium ions in the mixed solution is 0.1 ~ 0.5.5 mol%, preparing rare earth ion solutions with different concentrations, soaking porous glass in the prepared rare earth ion solution for 12h to realize doping, taking out the porous glass after doping is finished, washing and drying the porous glass, and storing the porous glass in a dryer;
⑤ high-temperature sintering, sintering the doped glass according to the following temperature rise gradient, wherein the temperature rise step in the sintering process is that a, the temperature is raised from room temperature to 300 ~ 500 ℃ range, the temperature rise rate is less than 2 ℃/min, and the temperature is maintained for at least 60 minutes in the 300 ~ 500 ℃ range;
b. heating from 300 ~ 500 deg.C to 700 ~ 900 deg.C at a heating rate of less than 2 deg.C/min, and maintaining at 700 ~ 900 deg.C for at least 60 min;
c. heating from 700 ~ 900 deg.C to 900 ~ 1200 deg.C at a heating rate of less than 2 deg.C/min, and maintaining at 900 ~ 1200 deg.C for at least 60 min;
d. sintering for 3-13 h at 800-1200 ℃ in a reducing atmosphere to obtain the transparent high silica glass.
The pre-treated strong acid solution described in step a of step ③ of the present invention is hydrofluoric acid.
According to the invention, rare earth ions are doped into the nano porous glass by adopting an impregnation method, so that the rare earth ions in the glass prepared by the method are uniformly distributed by being adsorbed on the inner surfaces of the pores, the luminescence quenching caused by clusters of the rare earth ions is reduced, the doping amount of the rare earth ions is increased, and the luminescence intensity of the rare earth ions is increased. The invention also researches the energy transfer among particles by doping various rare earth ions.
Drawings
Fig. 1 is a spectrum and lifetime test chart.
Detailed Description
The method comprises the following steps:
① preparing the matrix glass by composing SiO according to weight fraction2:B2O3:Na2O:Al2O3=50 ~ 70:20 ~ 40:5 ~ 15:1 ~ 5 as matrix, and clarifier Sb with the weight part of the matrix being 1 percent is added2O3Weighing and uniformly mixing the raw materials according to the proportion to obtain a batch, putting the batch into a platinum or corundum crucible, putting the crucible into a high-temperature furnace at 1400-1500 ℃ for melting for 30-200 min, and then casting and cooling the batch on an iron plate at 400-600 ℃ to form borosilicate glass serving as matrix glass;
② phase separation, namely putting the matrix glass in the step ① into a muffle furnace, carrying out phase separation heat treatment for 12-72h at the temperature of 500-650 ℃, and separating a sodium-boron phase and a silicon phase to obtain a turbid devitrified phase separation glass sample;
③ porous glass preparation:
a. pretreating the phase-separated borosilicate glass, using a strong acid solution with a corrosion effect to perform surface treatment on the glass to destroy the silicon phase on the surface of the glass, soaking the glass in the strong acid solution for 1-10min, then taking out the glass, and washing the glass;
b. then using one of hydrochloric acid or nitric acid and water to prepare H+C, preparing 0.03-L mol/L acid solution, preparing 0.1-1 mol/L buffer solution, soaking the borosilicate glass in the step a in the mixed solution of the acid solution and the buffer solution which are mixed in proportion, placing the mixture in a constant-temperature water bath kettle at the temperature of 60-100 ℃ for 12-48 h, taking out the mixture, naturally cooling the mixture, washing the glass with deionized water, and drying the glass;
④ doping rare earth ions, namely cerium ions and terbium ions, wherein the concentration of the cerium ions in the mixed solution is 0.05 ~ 0.5.5 mol%, and the concentration of the terbium ions in the mixed solution is 0.1 ~ 0.5.5 mol%, preparing rare earth ion solutions with different concentrations, soaking porous glass in the prepared rare earth ion solution for 12h to realize doping, taking out the porous glass after doping is finished, washing and drying the porous glass, and storing the porous glass in a dryer;
⑤ high-temperature sintering, sintering the doped glass according to the following temperature rise gradient, wherein the temperature rise step in the sintering process is that a, the temperature is raised from room temperature to 300 ~ 500 ℃ range, the temperature rise rate is less than 2 ℃/min, and the temperature is maintained for at least 60 minutes in the 300 ~ 500 ℃ range;
b. heating from 300 ~ 500 deg.C to 700 ~ 900 deg.C at a heating rate of less than 2 deg.C/min, and maintaining at 700 ~ 900 deg.C for at least 60 min;
c. heating from 700 ~ 900 deg.C to 900 ~ 1200 deg.C at a heating rate of less than 2 deg.C/min, and maintaining at 900 ~ 1200 deg.C for at least 60 min;
d. sintering for 3-13 h at 800-1200 ℃ in a reducing atmosphere to obtain the transparent high silica glass.
The pre-treated strong acid solution described in step a of step ③ of the present invention is hydrofluoric acid.
The present invention is described in further detail below:
unlike other scintillating materials, scintillating glass has great advantages: the glass has the advantages of convenient and easy manufacture, uniform forming texture and strong shape variability, can meet different size requirements, more importantly, the cost of the glass is far lower than that of a scintillation crystal, different glass formulas can be applied in a large range to correspond to different purposes, and the formula of the glass can be adjusted in a large range to meet different spectrum requirements. The glass is easy to draw the scintillating fiber, so that the scintillating fiber panel is prepared, and if the glass contains the B component, neutrons can be detected simultaneously. The problem to be solved by the current research on the scintillation glass is that the density and the light yield are low. The latest detection components can compensate the defect of low optical output of glass to a certain extent through the development of detection technology, namely the problem of low optical yield is solved.
Generally, in order to improve the yield and simplify the production process, a high-temperature melting method is generally used at present, and the method can actually improve the productivity and shorten the production period. The method of the invention adopts the nanometer porous glass to prepare the high silica scintillation glass, and the high silica porous glass is an excellent silicate glass substrate material because of SiO2The content is more than 96%, and the optical and mechanical properties of the productThe performance of the quartz glass is very close to that of quartz glass, and in fact, the early quartz glass products are prepared by sintering high silica porous glass. The high silica porous glass has high specific surface area and high porosity, so that the active ions are more easily and uniformly distributed on the surface of a pore structure, and a physical method is adopted to uniformly disperse the distribution of the active ions in the porous glass, thereby avoiding cluster of the active ions and concentration quenching of an excited state of the active ions, and enhancing the luminous intensity of the porous glass.
The method adopts a soda borosilicate glass system, firstly, matrix glass is melted according to a certain weight percentage, then the prepared matrix glass is kept at a certain temperature for a period of time to separate a soda borosilicate phase and a silicon phase, then the phase-separated glass is subjected to acid dissolution treatment in a constant-temperature water bath to form porous glass (the pore size is intensively distributed in 1-100 nm) with uniformly distributed pore diameters, then the porous glass is soaked in a mixed solution of a solution of cerium terbium rare earth ions, the rare earth ions are adsorbed to the inner surfaces of pores in a free diffusion mode to uniformly distribute the rare earth ions in the matrix glass, and finally, the physically adsorbed water is removed through sintering, and the glass is densified to obtain a transparent glass sample. In contrast, although this method is somewhat more complicated than the high-temperature melting method, it can uniformly distribute the rare earth dopant without forming the rare earth polymer, and suppress the concentration quenching phenomenon, thereby increasing the doping amount of rare earth ions in the scintillating glass and also increasing the scintillating efficiency of the rare earth ions.
Ce3+The 5d-4f transition is an allowable electric dipole transition, the electron lifetime of the 5d configuration is very short (generally 30 ~ 100 ns), and the probability of energy transfer is high3+The doped silicate glass has the characteristics of high X-ray excitation light yield, good transparency, strong green light generated at 542nm, matching with the sensitive wavelength of a photoelectric device and the like, and becomes a research hotspot of the scintillating glass. Tb3+Has a weak linear absorption band between 350nm and 370nm, and the line is just the same as Ce3+The emission bands of (1) and (3) coincide, so Tb3+Can be covered with Ce3+Is sensitized and excited to5D3At energy level, Tb3+5D3Two energy level generationThe transition is made by5D3 is transferred directly to the substrate, and the other is5D3Is relaxed to5D4Then is further prepared by5D4The transition to the ground state generates fluorescence. So that the nano-porous glass is adopted as a carrier, Tb3+Being a luminescent ion, Ce3+In order to sensitize ions and reduce the decay time of the material, the characteristics of sufficient physical dispersion and adsorption of rare earth ions in the glass are obtained by utilizing the uniformly distributed micropores and large specific surface area of the nano porous glass, so that the terbium-cerium double-doped high silica glass scintillation glass material is prepared. Thereby achieving the purposes of increasing the doping amount of rare earth ions and improving the optical yield of the glass.
Example 1:
1) SiO by weight fraction of the base glass2: B2O3: Na2O：Al2O3=58:30:10:2，SiO2Introduction of silicon dioxide powder, B2O3Introduced with boric acid, Na2O is introduced with anhydrous sodium carbonate, Al2O3Introduced with alumina powder, Sb2O3Introducing antimony trioxide powder, weighing the raw materials according to molar ratio conversion, and adding 1% Sb2O3Weighing SiO2Grinding and uniformly mixing boric acid, anhydrous sodium carbonate, aluminum oxide and antimony trioxide to obtain a batch;
2) placing the batch in a high-temperature furnace by using a corundum crucible, melting at the high temperature of 1450 ℃ for 3h, and then pouring the batch in a stainless steel mold for molding to obtain a glass sample A;
3) immediately putting the glass sample A into a muffle furnace, and carrying out phase-splitting heat treatment for 30h at 580 ℃ to obtain milk white
A devitrified phase separated glass sample;
4) putting the milky white devitrified and phase-separated glass sample into a beaker filled with a dilute hydrochloric acid solution with the mass concentration of 1mol/L and an ammonium chloride buffer solution with the mass concentration of 1mol/L, putting the beaker into a constant-temperature water bath, leaching and leaching the soluble sodium-rich boron phase at the constant temperature of 90 ℃ until the glass sample is clear and transparent in the solution to obtain a glass sample B,
5) taking out the leached glass sample B, soaking the glass sample B in deionized water, washing and drying; obtaining opaque porous high silica glass;
6) soaking the porous high silica glass into 0.2mol/L terbium nitrate solution for 12h, and washing and drying after soaking to obtain the high silica glass;
7) and (3) putting the high silica glass into a high-temperature electric heating furnace, and sintering in a reducing atmosphere. The temperature rising procedure is as follows: and (3) keeping the temperature of the room temperature to 400 ℃ for 4h, keeping the temperature for 1h, heating the temperature to 800 ℃ for 4h, keeping the temperature for 1h, then heating the temperature to 1000 ℃ for 2h, keeping the temperature for 1h, and finally naturally cooling to obtain the transparent high silica glass.
The spectrum and lifetime tests were performed on example 1, and the results are shown in fig. 1.
Example 2:
1) SiO by weight fraction of the base glass2: B2O3: Na2O：Al2O3=58:30:10:2，SiO2Introduction of silicon dioxide powder, B2O3Introduced with boric acid, Na2O is introduced with anhydrous sodium carbonate, Al2O3Introduced with alumina powder, Sb2O3Introducing antimony trioxide powder, weighing the raw materials according to molar ratio conversion, and adding 1% Sb2O3Weighing SiO2Boric acid, anhydrous sodium carbonate, aluminum oxide and antimony trioxide are ground and mixed uniformly to obtain a batch
2) Placing the batch in a high-temperature furnace by using a corundum crucible, melting at the high temperature of 1450 ℃ for 3h, and then pouring the batch in a stainless steel mold for molding to obtain a glass sample A;
3) immediately putting the glass sample A into a muffle furnace, and carrying out phase-splitting heat treatment for 30h at 580 ℃ to obtain milk white
A devitrified phase separated glass sample;
4) putting the milky white devitrified and phase-separated glass sample into a beaker filled with a dilute hydrochloric acid solution with the mass concentration of 1mol/L and an ammonium chloride buffer solution with the mass concentration of 1mol/L, putting the beaker into a constant-temperature water bath, leaching and leaching the soluble sodium-rich boron phase at the constant temperature of 90 ℃ until the glass sample is clear and transparent in the solution to obtain a glass sample B,
5) taking out the leached glass sample B, soaking the glass sample B in deionized water, washing and drying; obtaining devitrified porous high silica glass;
6) soaking the porous high silica glass into 0.2mol/L terbium nitrate solution and 0.05mol/L cerium nitrate solution for 12 hours, and washing and drying after soaking to obtain the high silica glass;
7) and (3) putting the high silica glass into a high-temperature electric heating furnace, and sintering in a reducing atmosphere. The temperature rising procedure is as follows: and (3) keeping the temperature of the room temperature to 400 ℃ for 4h, keeping the temperature for 1h, heating the temperature to 800 ℃ for 4h, keeping the temperature for 1h, then heating the temperature to 1000 ℃ for 2h, keeping the temperature for 1h, and finally naturally cooling to obtain the transparent high silica glass.
Example 3:
1) SiO by weight fraction of the base glass2: B2O3: Na2O：Al2O3=58:30:10:2，SiO2Introduction of silicon dioxide powder, B2O3Introduced with boric acid, Na2O is introduced with anhydrous sodium carbonate, Al2O3Introduced with alumina powder, Sb2O3Introducing antimony trioxide powder, weighing the raw materials according to molar ratio conversion, and adding 1% Sb2O3Weighing SiO2Grinding and uniformly mixing boric acid, anhydrous sodium carbonate, aluminum oxide and antimony trioxide to obtain a batch;
2) placing the batch in a high-temperature furnace by using a corundum crucible, melting at the high temperature of 1450 ℃ for 3h, and then pouring the batch in a stainless steel mold for molding to obtain a glass sample A;
3) immediately putting the glass sample A into a muffle furnace, and carrying out phase-splitting heat treatment for 30h at 580 ℃ to obtain milk white
A devitrified phase separated glass sample;
4) putting the milky white devitrified and phase-separated glass sample into a beaker filled with a dilute hydrochloric acid solution with the mass concentration of 1mol/L and an ammonium chloride buffer solution with the mass concentration of 1mol/L, putting the beaker into a constant-temperature water bath, leaching and leaching the soluble sodium-rich boron phase at the constant temperature of 90 ℃ until the glass sample is clear and transparent in the solution to obtain a glass sample B,
5) taking out the leached glass sample B, soaking the glass sample B in deionized water, washing and drying; obtaining opaque porous high silica glass;
6) soaking the porous high silica glass into 0.2mol/L terbium nitrate solution and 0.1mol/L cerium nitrate solution for 12h, and washing and drying after soaking to obtain the high silica glass;
7) and (3) putting the high silica glass into a high-temperature electric heating furnace, and sintering in a reducing atmosphere. The temperature rising procedure is as follows: and (3) keeping the temperature of the room temperature to 400 ℃ for 4h, keeping the temperature for 1h, heating the temperature to 800 ℃ for 4h, keeping the temperature for 1h, then heating the temperature to 1000 ℃ for 2h, keeping the temperature for 1h, and finally naturally cooling to obtain the transparent high silica glass.
Example 4:
1) SiO by weight fraction of the base glass2: B2O3: Na2O：Al2O3=58:30:10:2，SiO2Introduction of silicon dioxide powder, B2O3Introduced with boric acid, Na2O is introduced with anhydrous sodium carbonate, Al2O3Introduced with alumina powder, Sb2O3Introducing antimony trioxide powder, weighing the raw materials according to molar ratio conversion, and adding 1% Sb2O3Weighing SiO2Grinding and uniformly mixing boric acid, anhydrous sodium carbonate, aluminum oxide and antimony trioxide to obtain a batch;
2) placing the batch in a high-temperature furnace by using a corundum crucible, melting at the high temperature of 1450 ℃ for 3h, and then pouring the batch in a stainless steel mold for molding to obtain a glass sample A;
3) immediately putting the glass sample A into a muffle furnace, and carrying out phase-splitting heat treatment for 30h at 580 ℃ to obtain milk white
A devitrified phase separated glass sample;
4) putting the milky white devitrified and phase-separated glass sample into a beaker filled with a dilute hydrochloric acid solution with the mass concentration of 1mol/L and an ammonium chloride buffer solution with the mass concentration of 1mol/L, putting the beaker into a constant-temperature water bath, leaching and leaching the soluble sodium-rich boron phase at the constant temperature of 90 ℃ until the glass sample is clear and transparent in the solution to obtain a glass sample B,
5) taking out the leached glass sample B, soaking the glass sample B in deionized water, washing and drying; obtaining opaque porous high silica glass;
6) soaking the porous high silica glass into 0.2mol/L terbium nitrate solution and 0.15mol/L cerium nitrate solution for 12 hours, and washing and drying after soaking to obtain the high silica glass;
7) and (3) putting the high silica glass into a high-temperature electric heating furnace, and sintering in a reducing atmosphere. The temperature rising procedure is as follows: and (3) keeping the temperature of the room temperature to 400 ℃ for 4h, keeping the temperature for 1h, heating the temperature to 800 ℃ for 4h, keeping the temperature for 1h, then heating the temperature to 1000 ℃ for 2h, keeping the temperature for 1h, and finally naturally cooling to obtain the transparent high silica glass.
Example 5:
1) SiO by weight fraction of the base glass2: B2O3: Na2O：Al2O3=58:30:10:2，SiO2Introduction of silicon dioxide powder, B2O3Introduced with boric acid, Na2O is introduced with anhydrous sodium carbonate, Al2O3Introduced with alumina powder, Sb2O3Introducing antimony trioxide powder, weighing the raw materials according to molar ratio conversion, and adding 1% Sb2O3Weighing SiO2Grinding and uniformly mixing boric acid, anhydrous sodium carbonate, aluminum oxide and antimony trioxide to obtain a batch;
2) placing the batch in a high-temperature furnace by using a corundum crucible, melting at the high temperature of 1450 ℃ for 3h, and then pouring the batch in a stainless steel mold for molding to obtain a glass sample A;
3) immediately putting the glass sample A into a muffle furnace, and carrying out phase-splitting heat treatment for 30h at 580 ℃ to obtain milk white
A devitrified phase separated glass sample;
4) putting the milky white devitrified and phase-separated glass sample into a beaker filled with a dilute hydrochloric acid solution with the mass concentration of 1mol/L and an ammonium chloride buffer solution with the mass concentration of 1mol/L, putting the beaker into a constant-temperature water bath, leaching and leaching the soluble sodium-rich boron phase at the constant temperature of 90 ℃ until the glass sample is clear and transparent in the solution to obtain a glass sample B,
5) taking out the leached glass sample B, soaking the glass sample B in deionized water, washing and drying; obtaining opaque porous high silica glass;
6) soaking the porous high silica glass into 0.2mol/L terbium nitrate solution and 0.2mol/L cerium nitrate solution for 12 hours, and washing and drying after soaking to obtain the high silica glass;
7) and (3) putting the high silica glass into a high-temperature electric heating furnace, and sintering in a reducing atmosphere. The temperature rising procedure is as follows: and (3) keeping the temperature of the room temperature to 400 ℃ for 4h, keeping the temperature for 1h, heating the temperature to 800 ℃ for 4h, keeping the temperature for 1h, then heating the temperature to 1000 ℃ for 2h, keeping the temperature for 1h, and finally naturally cooling to obtain the transparent high silica glass.
Claims (2)
1. A preparation method of high silica scintillation glass is characterized by comprising the following steps:
① preparing the matrix glass by composing SiO according to weight fraction2: B2O3: Na2O：Al2O3Taking the mixture as a matrix, and adding 1 weight percent of a clarifying agent Sb into the matrix2O3Weighing and uniformly mixing the raw materials according to the proportion to obtain a batch, putting the batch into a platinum or corundum crucible, putting the crucible into a high-temperature furnace at 1400-1500 ℃ for melting for 30-200 min, and then casting and cooling the batch on an iron plate at 400-600 ℃ to form borosilicate glass serving as matrix glass;
② phase separation, namely putting the matrix glass in the step ① into a muffle furnace, carrying out phase separation heat treatment for 12-72h at the temperature of 500-650 ℃, and separating a sodium-boron phase and a silicon phase to obtain a turbid devitrified phase separation glass sample;
③ porous glass preparation:
a. pretreating the phase-separated borosilicate glass, using a strong acid solution with a corrosion effect to perform surface treatment on the glass to destroy the silicon phase on the surface of the glass, soaking the glass in the strong acid solution for 1-10min, then taking out the glass, and washing the glass;
b. then hydrochloric acid is usedOr one of the nitric acids is prepared into H with water+Acid solution with the concentration of 0.03-L mol/L, then 0.1-1 mol/L buffer solution is prepared, the borosilicate glass in the step a is soaked in the mixed solution of the acid solution and the buffer solution in the step b which are mixed according to the proportion, the mixture is placed in a constant temperature water bath kettle at the temperature of 60-100 ℃ for 12-48 h, the mixture is taken out and naturally cooled, and then the glass is washed by deionized water and dried;
④ doping rare earth ions, namely cerium ions and terbium ions, wherein the concentration of the cerium ions in the mixed solution is 0.05 ~ 0.5.5 mol%, and the concentration of the terbium ions in the mixed solution is 0.1 ~ 0.5.5 mol%, preparing rare earth ion solutions with different concentrations, soaking porous glass in the prepared rare earth ion solution for 12h to realize doping, taking out the porous glass after doping is finished, washing and drying the porous glass, and storing the porous glass in a dryer;
⑤ high-temperature sintering, sintering the doped glass according to the following temperature rise gradient, wherein the temperature rise step in the sintering process is that a, the temperature is raised from room temperature to 300 ~ 500 ℃ range, the temperature rise rate is less than 2 ℃/min, and the temperature is maintained for at least 60 minutes in the 300 ~ 500 ℃ range;
b. heating from 300 ~ 500 deg.C to 700 ~ 900 deg.C at a heating rate of less than 2 deg.C/min, and maintaining at 700 ~ 900 deg.C for at least 60 min;
c. heating from 700 ~ 900 deg.C to 900 ~ 1200 deg.C at a heating rate of less than 2 deg.C/min, and maintaining at 900 ~ 1200 deg.C for at least 60 min;
d. sintering for 3-13 h at 800-1200 ℃ in a reducing atmosphere to obtain the transparent high silica glass.
2. The method of claim 1, wherein the pre-treated strong acid solution of step a of step ③ is hydrofluoric acid.
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| CN101691279A (en) * | 2009-09-30 | 2010-04-07 | 华中科技大学 | Method for manufacturing vycor glass emitting green light |
| CN102320746A (en) * | 2011-06-09 | 2012-01-18 | 华中科技大学 | Method for manufacturing high-silica glass emitting white light |
| CN102701590A (en) * | 2012-06-29 | 2012-10-03 | 中国科学院上海光学精密机械研究所 | Preparation method of near ultraviolet-excited high silica blue-light-emitting glass |
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