CN110451810B - CuO doped Bi2SiO5Method for producing polycrystalline glass - Google Patents

CuO doped Bi2SiO5Method for producing polycrystalline glass Download PDF

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CN110451810B
CN110451810B CN201910889620.8A CN201910889620A CN110451810B CN 110451810 B CN110451810 B CN 110451810B CN 201910889620 A CN201910889620 A CN 201910889620A CN 110451810 B CN110451810 B CN 110451810B
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郭宏伟
刘磊
党梦阳
汪枫帆
王翠翠
陈平
谢驰
李荣悦
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Xianyang Yinghe Electronic Material Co ltd
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition

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Abstract

The invention discloses a CuO doped Bi2SiO5The preparation method of the polycrystalline glass comprises the steps of taking boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide according to the mole fraction, and mixing to obtain a mixture; placing the mixture into a crucible with the preheating temperature of 800-900 ℃, heating to 950-1100 ℃, and preserving heat to obtain glass liquid; and (3) placing the molten glass into a mold, forming, then placing the molten glass into an annealing furnace, preserving the heat at 400-600 ℃, and cooling the molten glass to room temperature along with the furnace to obtain the CuO doped Bi2SiO5 polycrystalline glass. The method has the advantages of high conversion rate, low cost, no pollution and no damage to human body.

Description

CuO doped Bi2SiO5Method for producing polycrystalline glass
Technical Field
The invention belongs to the technical field of glass preparation, and relates to CuO doped Bi2SiO5A method for preparing polycrystalline glass.
Background
Bi2O3-SiO2Bi can be generated in the system12SiO20、Bi2SiO5And Bi4Si3O12And three compounds. Wherein Bi12SiO20And Bi4Si3O12Is a stable phase, Bi2SiO5Is a metastable phase. In recent years, Bi is synthesized in China12SiO20And Bi4Si3O12The research, preparation process and application field of powder material are mature, but Bi is in Bi2SiO5The research on the aspects is not uncommon,such as Bi2SiO5The crystal growth, performance and preparation method of the crystal are still under deep investigation. The main reason for this is to prepare Bi of high purity2SiO5Metastable phasing has greater difficulty. In 2007, Wang Yan and Wang Xiupeng are in Bi2O3-SiO2In the research of the system solid phase reaction, Bi is found to be generated at about 750 DEG C2SiO5However, when the reaction temperature is raised from 750 ℃ to 900 ℃, the metastable Bi state2SiO5Bi gradually transformed into a stable state12SiO20And Bi4Si3O12. From this, it can be seen that Bi is synthesized by the solid phase method2SiO5In the case of powders, the reaction temperature plays a decisive role. Zhereb v.p. et al studied Bi by a large number of XRD and DTA2SiO5Formation of metastable phase, according to stoichiometric ratio of oxide, Bi is prepared by solid phase method2SiO5、Bi12SiO20And Bi4Si3O12A mixture of compositions which, using kinetic measurements, derive the optimum temperature for the transition to the metastable phase in the solid phase method at 700 ℃ and a conversion of not more than 10%.
Ruigen Chen et al hydrothermally react with Bi (NO)3)3Different silicon sources are used as raw materials, and orthorhombic Bi with the thickness of 10-20 nm is synthesized for the first time by a template-free hydrothermal synthesis method2SiO5A nano-sheet. The results show that different precursors lead to samples with different morphologies, particle sizes, BET surface areas. However, the hydrothermal method has a long reaction time, and the reaction process cannot be directly observed due to the reaction in a closed pressure vessel; secondly, the powder prepared by the currently known hydrothermal method only has oxides, and reports about preparing other powder of non-oxide type by the hydrothermal method are very few; finally, hydrothermal reaction can only be carried out under high pressure, and the hydrothermal kettle has to have excellent performance, so that the method has strong dependence on instruments and equipment, and requires standard operation, which hinders the development of the hydrothermal method.
Synthesis of Bi by gel-sol method, L.Armelao et al, Italy2SiO5And Bi4Si3O12Crystal, and research shows that: the reason for the crystallization is that the formation of Bi-O-Bi bonds is not fine Bi2O3(ii) a In the temperature range of 400-600 ℃, Bi begins to be generated in the powder along with the increase of the temperature2SiO5And Bi4Si3O12(ii) a Although Bi2SiO5Is a metastable phase compound, but is still easy to crystallize and exist stably at high temperature. However, most of the raw materials used in this method are all water-soluble reagents and metal alkoxides, which leads to high cost; the intermediate products produced in the reaction process pollute the environment if not treated; in addition, the obtained xerogel needs to be heated and calcined, which wastes time and energy.
Patent CN106948006A discloses a preparation method of high light output bismuth silicate scintillation crystal, in which Ta is doped5+，Ta5+With Ta2O5The doping amount is 0.2-4 mol%/mol. Synthesizing the bismuth silicate doped polycrystalline powder by a solid-phase sintering method, and pressing the synthesized bismuth silicate doped polycrystalline powder into a compact cylindrical material block; fixing seed crystals at the middle part of the bottom of the crucible, then filling the polycrystalline material blocks into the crucible, sealing, placing the crucible in a crystal growth furnace, controlling the temperature at 1050-1200 ℃, and controlling the crystal growth speed at 0.2-0.6 mm/h. Due to Ta5+The light output of the obtained BSO crystal is greatly improved by the doping of the silicon nitride. Although the method improves the growth efficiency and application of the bismuth silicate scintillation crystal, the tantalum element is expensive, difficult to melt and not suitable for popularization and application; patent CN103643293B discloses a bismuth silicate scintillation crystal and a preparation method thereof, which is obtained by adopting BSO seed crystal and performing crystal growth by a Bridgman-Stockbarge method under air atmosphere. Due to Y3+The ion doping reduces the formation of heterogeneous silicon bismuth compound and corresponding macroscopic defects to a certain extent, so that the transmission performance of the BSO crystal in a visible light wave band is improved, and the improvement of the scintillation performance of the BSO crystal with large size is particularly remarkable, but because the doping agent is Y2O3It has damage to eyes, skin, and even liver and lung, so it is not recommended to be put into mass production.
Disclosure of Invention
The invention aims to provide the CuO doped Bi which has high conversion rate, low cost, no pollution and no damage to human body2SiO5A method for preparing polycrystalline glass.
The invention is realized by the following technical scheme:
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: taking 4-6% of boron trioxide, 13-15% of silicon dioxide, 55-59% of bismuth trioxide, 0.5-2% of manganese dioxide, 16-19% of copper oxide, 0.8-1.5% of tungsten trioxide, 1-2% of antimony trioxide and 0.8-2% of germanium dioxide according to molar fraction, and mixing to obtain a mixture;
step 2: placing the mixture into a crucible with the preheating temperature of 800-900 ℃, heating to 950-1100 ℃, and preserving heat to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 400-600 ℃, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
Further, the uniformity of the mixture in the step 1 is more than 98%.
Further, in the step 1, silicon dioxide is introduced through quartz sand, the purity is 99.9%, and the granularity is 400 meshes; boron trioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide are introduced through analytically pure raw materials.
Further, the crucible in the step 2 is a porcelain crucible, and the porcelain crucible is placed in a silicon carbide rod resistance furnace for preheating, temperature rising and heat preservation.
Further, the temperature rise rate in the step 2 is 5-15 ℃/min.
Further, the heat preservation time in the step 2 is 15-25 min.
Further, the heat preservation time in the step 3 is 2-3 h.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention providesCuO doped Bi2SiO5The preparation method of polycrystalline glass, the raw materials are added into crucible preheated at high temperature and heated to the melting temperature for melting after mixing in the method, it adds raw materials and melts rapidly under the high-temperature state, the raw materials can form the products to be prepared after annealing treatment in the annealing furnace after melting at high temperature, avoid the influence of the material composition unevenness brought by volatilization of bismuth oxide in the gradual heating process, its technological process only includes melting and annealing treatment, its technological process is short, the operation process is relatively easy and simple too; in addition, gaseous substances or other pollutants cannot be discharged in the high-temperature smelting process, so that the preparation method is pollution-free and cannot cause harm to operators; the raw materials adopted in the method are all cheap raw materials, and meanwhile, the method has simple process, reduces the temperature required by melting the raw materials by doping substances such as CuO and the like, and reduces the raw material cost and energy consumption, so the method has low cost and good social benefit and economic benefit; the CuO doping is adopted, so that the activation energy of a system can be reduced, the formation energy for inducing the formation of bismuth silicate crystals is low, the formation speed is high, the crystallization speed is high, the nucleation and growth of the crystals are promoted, the growth efficiency of the prepared crystals is high, the integrity is good, the quality is high, the permeability of a visible light waveband is good, and the scintillation performance is high; in addition, the preparation method does not generate Bi12SiO20And Bi4Si3O12Equal miscellaneous items, greatly improves the preparation of metastable phase Bi2SiO5The conversion of polycrystals.
Drawings
FIG. 1 is a schematic representation of Bi doped CuO prepared in example 12SiO5X-ray diffraction patterns of the polycrystalline glasses.
Detailed Description
Specific examples are given below.
Example 1
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 5.6% of boron trioxide, 14.5% of silicon dioxide, 57% of bismuth trioxide, 1% of manganese dioxide, 17.9% of copper oxide, 1.2% of tungsten trioxide, 1.5% of antimony trioxide and 1.3% of germanium dioxide according to the mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a biscuit porcelain crucible preheated to 800 ℃ in a silicon-carbon rod resistance furnace, heating to 950 ℃ at a heating rate of 10 ℃/min, and preserving heat for 20min to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 500 ℃ for 2.5h, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5The expansion coefficient of the polycrystalline glass is 7.22 x 10-6/deg.C, transition temperature 586.8 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
Doping prepared CuO with Bi2SiO5For the polycrystalline glass sample, as shown in FIG. 1, the angle corresponding to the characteristic peak of the sample includes Bi of PDF No. 36-02872SiO5The angle corresponding to the characteristic peak shows that the prepared bismuth silicate polycrystal is Bi with higher purity2SiO5A nanocrystalline phase.
Example 2
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 5% of boron trioxide, 14% of silicon dioxide, 58.2% of bismuth trioxide, 2% of manganese dioxide, 17% of copper oxide, 1.5% of tungsten trioxide, 1% of antimony trioxide and 1.3% of germanium dioxide according to the mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a celadon crucible preheated to 830 ℃ in a silicon-carbon rod resistance furnace, heating to 950 ℃ at the heating rate of 15 ℃/min, and preserving heat for 20min to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 450 ℃ for 2h, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5The expansion coefficient of the polycrystalline glass is 7.26 multiplied by 10-6/deg.C, transition temperature 590.2 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
Example 3
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 4% of boron trioxide, 15% of silicon dioxide, 55% of bismuth trioxide, 2% of manganese dioxide, 19% of copper oxide, 1.5% of tungsten trioxide, 1.5% of antimony trioxide and 2% of germanium dioxide according to the mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a celadon crucible preheated to 850 ℃ in a silicon-carbon rod resistance furnace, heating to 1000 ℃ at the heating rate of 12 ℃/min, and preserving heat for 15min to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 480 ℃ for 3h, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5The expansion coefficient of the polycrystalline glass is 7.68 x 10-6/deg.C, transition temperature 573.6 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
Example 4
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 4.8% of boron trioxide, 13.9% of silicon dioxide, 58% of bismuth trioxide, 1.1% of manganese dioxide, 18.7% of copper oxide, 1% of tungsten trioxide, 1.3% of antimony trioxide and 1.2% of germanium dioxide according to the mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a celadon crucible preheated to 870 ℃ in a silicon-carbon rod resistance furnace, heating to 1050 ℃ at the heating rate of 12 ℃/min, and preserving heat for 20min to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 550 ℃ for 2h, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5The expansion coefficient of the polycrystalline glass is 7.34 x 10-6/deg.C, transition temperature 590.5 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
Example 5
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 4.8% of boron trioxide, 14.2% of silicon dioxide, 57.9% of bismuth trioxide, 1.5% of manganese dioxide, 17.9% of copper oxide, 1% of tungsten trioxide, 1.5% of antimony trioxide and 1.2% of germanium dioxide according to the mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a biscuit porcelain crucible preheated to 890 ℃ in a silicon-carbon rod resistance furnace, heating to 1100 ℃ at a heating rate of 13 ℃/min, and preserving heat for 15min to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 580 ℃ for 2.5h, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5The expansion coefficient of the polycrystalline glass is 7.42 multiplied by 10-6/deg.C, transition temperature 592.2 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
Example 6
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 5.5% of boron trioxide, 14.1% of silicon dioxide, 57% of bismuth trioxide, 1.3% of manganese dioxide, 17.6% of copper oxide, 1.5% of tungsten trioxide, 2% of antimony trioxide and 1% of germanium dioxide by mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a biscuit porcelain crucible preheated to 900 ℃ in a silicon-carbon rod resistance furnace, heating to 1030 ℃ at the heating rate of 8 ℃/min, and preserving heat for 18min to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 570 ℃ for 2h, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5The expansion coefficient of the polycrystalline glass is 7.55 x 10-6/deg.C, transition temperature 581.2 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
Example 7
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 6% of boron trioxide, 13.5% of silicon dioxide, 59% of bismuth trioxide, 0.5% of manganese dioxide, 16% of copper oxide, 2% of tungsten trioxide, 1% of antimony trioxide and 2% of germanium dioxide according to mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a celadon crucible preheated to 880 ℃ in a silicon-carbon rod resistance furnace, heating to 1030 ℃ at a heating rate of 10 ℃/min, and preserving heat for 21min to obtain glass liquid;
and step 3: putting the molten glass into a mould, shaping and putting into an annealing furnaceKeeping the temperature at 570 ℃ for 2h, cooling to room temperature along with the furnace to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5The expansion coefficient of the polycrystalline glass is 7.64 x 10-6/deg.C, transition temperature 586.2 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
Example 8
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 4.5% of boron trioxide, 15% of silicon dioxide, 56.8% of bismuth trioxide, 1.8% of manganese dioxide, 18.8% of copper oxide, 0.8% of tungsten trioxide, 1.5% of antimony trioxide and 0.8% of germanium dioxide according to the mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a biscuit porcelain crucible preheated to 900 ℃ in a silicon-carbon rod resistance furnace, heating to 1070 ℃ at the heating rate of 5 ℃/min, and preserving heat for 16min to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 400 ℃ for 3h, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5Polycrystalline glassThe expansion coefficient of glass is 7.47 x 10-6/deg.C, transition temperature 585.5 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
Example 9
CuO doped Bi2SiO5A method of making polycrystalline glass comprising the steps of:
step 1: mixing 5.5% of boron trioxide, 13% of silicon dioxide, 55.8% of bismuth trioxide, 1.6% of manganese dioxide, 19% of copper oxide, 1.7% of tungsten trioxide, 1.8% of antimony trioxide and 1.6% of germanium dioxide according to the mole fraction to obtain a mixture, wherein the uniformity of the mixture is more than 98%;
wherein, the silicon dioxide is introduced through quartz sand, the purity is 99.9 percent, and the granularity is 400 meshes; introducing boron trioxide, silicon dioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide by analytically pure raw materials; the method for measuring the uniformity of the mixture comprises the steps of randomly sampling 10g of the mixture at three points, putting the mixture into a 500mL plastic beaker, adding 250mL of deionized water, stirring for 5min by using a magnetic stirrer, and testing the conductivity of the mixture to obtain the value with the uniformity ratio of the maximum value to the minimum value of the conductivity, wherein the uniformity of the mixture is more than 98% and the mixture can be used.
Step 2: placing the mixture into a celadon crucible preheated to 900 ℃ in a silicon-carbon rod resistance furnace, heating to 1020 ℃ at the heating rate of 15 ℃/min, and preserving heat for 25min to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature for 2 hours at 600 ℃, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
The prepared CuO doped Bi is measured by a linear expansion coefficient determinator2SiO5The expansion coefficient of the polycrystalline glass is 7.38 multiplied by 10-6temperature/deg.C, 591.3 deg.C; the prepared CuO doped Bi is measured by a WFC Faraday effect tester2SiO5The Verdet constant of the polycrystalline glass was-0.19 min/Oe.cm.
According to the invention, through the processes of adding raw materials at high temperature and rapidly melting and stirring at high temperature, the influence of uneven components caused by volatilization of bismuth trioxide at high temperature is avoided; simultaneously, the temperature required by melting the raw materials is reduced by doping CuO and the like, and the prepared Bi2SiO5The polycrystal has good permeability in a visible light wave band, high scintillation performance, high crystal growth efficiency, good integrity and high quality; bi is not generated in the process of preparing the material by adopting the method12SiO20And Bi4Si3O12Equal miscellaneous items, greatly improves the preparation of metastable phase Bi2SiO5The conversion of polycrystals. The problems that the solid-phase reaction sintering method has low conversion rate, the hydrothermal method limits instruments, the sol-gel method wastes time and energy, and the raw materials used in the patent pollute the environment are solved. Prepared Bi2SiO5The polycrystal can be widely applied to the fields of photoelectron, photocatalysis and the like, has good economic benefit and social benefit and has very wide application prospect.

Claims (7)

1. CuO doped Bi2SiO5A method for producing polycrystalline glass, characterized by comprising the steps of:
step 1: taking 4-6% of boron trioxide, 13-15% of silicon dioxide, 55-59% of bismuth trioxide, 0.5-2% of manganese dioxide, 16-19% of copper oxide, 0.8-1.5% of tungsten trioxide, 1-2% of antimony trioxide and 0.8-2% of germanium dioxide according to molar fraction, and mixing to obtain a mixture;
step 2: placing the mixture into a crucible with the preheating temperature of 800-900 ℃, heating to 950-1100 ℃, and then preserving heat to obtain glass liquid;
and step 3: placing the molten glass into a mold, forming, placing the mold into an annealing furnace, keeping the temperature at 400-600 ℃, and cooling the furnace to room temperature to obtain CuO doped Bi2SiO5Polycrystalline glass.
2. The CuO doped Bi of claim 12SiO5A method for producing a polycrystalline glass, characterized in that,the uniformity of the mixture in the step 1 is more than 98%.
3. The CuO doped Bi of claim 12SiO5The preparation method of the polycrystalline glass is characterized in that in the step 1, silicon dioxide is introduced through quartz sand, the purity is 99.9%, and the granularity is 400 meshes; boron trioxide, bismuth trioxide, manganese dioxide, copper oxide, tungsten trioxide, antimony trioxide and germanium dioxide are introduced through analytically pure raw materials.
4. The CuO doped Bi of claim 12SiO5The preparation method of the polycrystalline glass is characterized in that the crucible in the step 2 is a porcelain crucible, and the porcelain crucible is placed in a silicon carbide rod resistance furnace for preheating, temperature rising and heat preservation.
5. The CuO doped Bi of claim 12SiO5The preparation method of the polycrystalline glass is characterized in that the temperature rise rate in the step 2 is 5-15 ℃/min.
6. The CuO doped Bi of claim 12SiO5The preparation method of the polycrystalline glass is characterized in that the heat preservation time in the step 2 is 15-25 min.
7. The CuO doped Bi of claim 12SiO5The preparation method of the polycrystalline glass is characterized in that the heat preservation time in the step 3 is 2-3 h.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101708863A (en) * 2009-11-10 2010-05-19 陕西科技大学 Preparation method of bismuth silicate micro crystal
CN101792181A (en) * 2010-02-09 2010-08-04 陕西科技大学 Preparation method of bismuth silicate nanocrystalline
CN102140688A (en) * 2011-03-12 2011-08-03 陕西科技大学 Preparation method of Bi2O3 polycrystal
CN102275944A (en) * 2011-07-06 2011-12-14 陕西科技大学 Preparation method of new scintillating bismuth silicate powder
CN102856261A (en) * 2012-09-07 2013-01-02 北京航空航天大学 Method for preparing metal, ferroelectric substance, insulator and semiconductor structure
CN103643293A (en) * 2013-12-25 2014-03-19 中国科学院上海硅酸盐研究所 Bismuth silicate scintillation crystal as well as preparation method and application thereof
WO2016203431A1 (en) * 2015-06-18 2016-12-22 Universita' Ca' Foscari Luminescent bismuth silicates, use and method for producing thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101708863A (en) * 2009-11-10 2010-05-19 陕西科技大学 Preparation method of bismuth silicate micro crystal
CN101792181A (en) * 2010-02-09 2010-08-04 陕西科技大学 Preparation method of bismuth silicate nanocrystalline
CN102140688A (en) * 2011-03-12 2011-08-03 陕西科技大学 Preparation method of Bi2O3 polycrystal
CN102275944A (en) * 2011-07-06 2011-12-14 陕西科技大学 Preparation method of new scintillating bismuth silicate powder
CN102856261A (en) * 2012-09-07 2013-01-02 北京航空航天大学 Method for preparing metal, ferroelectric substance, insulator and semiconductor structure
CN103643293A (en) * 2013-12-25 2014-03-19 中国科学院上海硅酸盐研究所 Bismuth silicate scintillation crystal as well as preparation method and application thereof
WO2016203431A1 (en) * 2015-06-18 2016-12-22 Universita' Ca' Foscari Luminescent bismuth silicates, use and method for producing thereof

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