WO2023035692A1 - 通过离子交换增强的荧光硅酸锂玻璃陶瓷及其制备方法 - Google Patents

通过离子交换增强的荧光硅酸锂玻璃陶瓷及其制备方法 Download PDF

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WO2023035692A1
WO2023035692A1 PCT/CN2022/096200 CN2022096200W WO2023035692A1 WO 2023035692 A1 WO2023035692 A1 WO 2023035692A1 CN 2022096200 W CN2022096200 W CN 2022096200W WO 2023035692 A1 WO2023035692 A1 WO 2023035692A1
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melting
glass
heat treatment
time
temperature
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PCT/CN2022/096200
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English (en)
French (fr)
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韩成玮
郑海峰
王彦宇
侯成
张君锋
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深圳爱尔创口腔技术有限公司
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Publication of WO2023035692A1 publication Critical patent/WO2023035692A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents
    • C03C10/0027—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 containing SiO2, Al2O3 and monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents
    • 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

Definitions

  • the present application relates to the technical field of lithium silicate glass ceramics, in particular to a fluorescent lithium silicate glass ceramic enhanced by ion exchange and a preparation method thereof.
  • Lithium silicate glass-ceramic has a wide range of applications in the field of dental restoration. Lithium silicate glass-ceramic not only has the transparency of glass, but also has the strength of ceramics. Compared with traditional zirconia tooth restoration materials, it has great potential in the field of aesthetic restoration. The advantages.
  • Dental restoration materials are required to be closer to natural teeth. Human natural teeth will fluoresce under light in a specific wavelength range, such as artificial light sources in some special occasions. In these cases, dental restoration materials without fluorescence effects cannot achieve simulation effects . At present, most dental restoration materials on the market have no fluorescent effect, and are often realized by fluorescent glaze, but the fluorescent effect is affected by the matrix and is easy to wear, which affects the final effect.
  • the purpose of this application is to provide a fluorescent lithium silicate glass ceramic enhanced by ion exchange and its preparation method, which can emit fluorescence close to that of natural teeth under the irradiation of light with a wavelength near 365nm, without affecting the light transmittance of the material
  • enhance its hardness and give it a fluorescent effect so as to solve the problems of low ion exchange efficiency, complicated process and long production time in the preparation process of fluorescent lithium silicate ceramics.
  • the application provides a preparation method of fluorescent lithium silicate glass-ceramic, which comprises:
  • the basic glass frit is mixed with the coloring agent, it is melted and water-quenched to obtain a glass frit, wherein the basic glass frit includes the following components by weight:
  • the immersion time is preferably 1-3h.
  • the colorant includes CeO 2 , Pr 2 O 3 , Cr 2 O 3 , Co 2 O 3 , Nd 2 O 3 , Er 2 O 3 , V 2 O 5 , NiO, MnO At least one, based on the total weight of the base glass frit and the colorant, the content of the colorant is 0-10 wt%.
  • the content of Fe2O3 in the colorant is no more than 0.01 wt %, based on the total weight of the base glass frit and the colorant.
  • the following mass components are included in the basic glass frit:
  • the melting temperature of the base glass is 1350-1750°C, preferably 1550-1650°C, and the melting time is 10-120min, preferably 30-90min.
  • the secondary melting temperature is 1350-1750° C., preferably 1550-1650° C., and the time is 10-120 minutes, preferably 30-90 minutes.
  • computer-aided design is used for forming, and heat treatment is performed on the shaped lithium silicate glass after forming.
  • the heat treatment temperature is 600-900°C, preferably 680-800°C, and the time is 20-180min, preferably 30 -120min, and then processed into a restoration by CAD/CAM.
  • the molding adopts a pressing process, and heat treatment is performed on the shaped lithium silicate glass after molding.
  • the heat treatment temperature is 700-900°C, preferably 820-880°C, and the time is 20-180min, preferably 30- 120min, and then processed into a restoration by hot die casting.
  • the molten salt contains potassium salt
  • the potassium salt is selected from at least one of KNO 3 , K 2 CO 3 and K 2 SiCO 3 , based on the total weight of the molten salt, the content of KNO 3 is 97 -99 wt%, K 2 CO 3 content is 0-2 wt%, preferably 0.5-1 wt%, K 2 SiCO 3 content is 0-3 wt%, preferably 0.5-2 wt%.
  • the fluorescent agent contained in the molten salt is selected from Eu (europium), Dy (dysprosium), Tm (thulium), Er (erbium), Ho (holmium), Yb (ytterbium), Nd ( At least one of nitric acid hydrates of neodymium), Sm (samarium), and Gd (gadolinium), based on the total weight of the molten salt, the amount of fluorescent agent added is 1-2wt%.
  • the added amount of the fluorescent agent is based on the total weight of the potassium molten salt, and the added amount of the fluorescent agent is the added amount.
  • the temperature of the molten salt is 300-620°C, preferably 400-450°C.
  • the hot die casting temperature is 850-1050° C., preferably 910-950° C., and the time is 5-60 min, preferably 10-20 min.
  • the present application provides a fluorescent lithium silicate glass ceramic enhanced by ion exchange and its preparation method, which is based on the preparation of four oxides with high content of K 2 O, Na 2 O, Al 2 O 3 and B 2 O 3 Glass, improve the network structure of the basic glass to make it easy for ion exchange, and then immerse the prepared restoration in molten salt containing potassium salt and fluorescent agent, and the strength of the glass ceramic restoration can be enhanced by ion exchange for a short time and endow it with fluorescence.
  • the process of the present application is simple, easy to produce in batches, and the fluorescent color is easy to control.
  • the composition of the base glass frit of glass ceramics is shown on the basis of oxides.
  • the "base glass composition based on oxides” refers to the basic glass composition obtained by converting the basic glass material that is completely decomposed during melting and exists in the form of oxides in the glass ceramics.
  • the composition of each basic glass material The sub-expression is recorded as SiO 2 , Al 2 O 3 and so on according to the custom.
  • the content of each component in the basic glass frit can be carried out by known methods, such as inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and other methods. Quantitative.
  • ICP-AES inductively coupled plasma atomic emission spectrometry
  • ICP-MS inductively coupled plasma mass spectrometry
  • Quantitative Quantitative.
  • thermal stability and devitrification resistance of glass ceramics refer to the easiness of crystallization in glass.
  • thermal stability refers to the easiness of crystallization when molten glass is solidified
  • devitrification resistance refers to the easiness of crystallization when the solidified glass is reheated during reheat pressing.
  • the application provides a preparation method of fluorescent lithium silicate glass-ceramic, which comprises:
  • the basic glass frit is mixed with the coloring agent, it is melted and water-quenched to obtain a glass frit, wherein the basic glass frit includes the following components by weight:
  • the immersion time is preferably 1-3h.
  • the colorant includes CeO 2 , Pr 2 O 3 , Cr 2 O 3 , Co 2 O 3 , Nd 2 O 3 , Er 2 O 3 , V 2 O 5 , NiO, MnO At least one, based on the total weight of the base glass frit and the colorant, the content of the colorant is 0-10 wt%.
  • the content of Fe2O3 in the colorant is no more than 0.01 wt %, based on the total weight of the base glass frit and the colorant.
  • the following mass components are included in the basic glass frit:
  • SiO 2 is a network forming component of glass, which has the functions of improving the thermal stability, chemical durability, weather resistance of glass, increasing the viscosity of molten glass, and easily forming molten glass; but when the content of SiO 2 is too high, there will be The devitrification resistance of the glass tends to decrease; SiO 2 is the main component of the main crystal phase of lithium disilicate, therefore, the content of SiO 2 is preferably within the above range.
  • Li 2 O is a component that contributes to the reduction of the specific gravity of the glass, and has the effect of improving the melting property of the glass and increasing the average linear thermal expansion coefficient, but when the Li 2 O content is too high, the devitrification resistance of the glass decreases; Li 2 O is the main component of the main crystal phase of lithium disilicate, so the content of Li 2 O is preferably within the above range.
  • K 2 O has the effect of improving the thermal stability of glass, but when the content of K 2 O is too high, the chemical durability and weather resistance of glass ceramics tend to decrease, so the content of K 2 O is preferably within the above range.
  • Na 2 O has the effect of improving the thermal stability of glass, but when the content of Na 2 O is too high, the chemical durability and weather resistance of glass ceramics tend to decrease, so the content of Na 2 O is preferably within the above range.
  • Al 2 O 3 is a glass component that can improve the durability and weather resistance of glass. It can be regarded as the network composition of glass. However, when the content of Al 2 O 3 is too high, the devitrification resistance of glass ceramics will decrease. , so the content of Al 2 O 3 is preferably within the above range.
  • P 2 O 5 is a network-forming component of the glass, and is an essential component for containing a large amount of highly dispersed components in the glass.
  • glass ceramics with high thermal stability can be obtained.
  • CaO is a glass component that has the effect of improving the thermal stability and devitrification resistance of glass, but when the CaO content is too high, the high dispersibility is impaired, and the thermal stability and devitrification resistance of glass ceramics are reduced.
  • the content is preferably within the above range.
  • ZrO 2 is a glass component that has the effect of improving the thermal stability and devitrification resistance of glass, but when the ZrO 2 content is too high, it shows a tendency to reduce thermal stability; ZrO 2 can be used as a nucleation agent in glass ceramics. agent, so the content of ZrO 2 is preferably within the above range.
  • the content of Tb 4 O 7 is preferably within the above range. .
  • B 2 O 3 is a network-forming component of glass and has the effect of improving the thermal stability of glass ceramics.
  • the content of B 2 O 3 is preferably within the above-mentioned range. .
  • the raw materials of the above-mentioned oxides can be selected from their oxides, carbonate compounds, and phosphate compounds.
  • the invention further accelerates the ion diffusion rate by improving the internal network structure of the glass ceramics, and greatly shortens the production time.
  • the inventors of the present application found that K 2 O, Na 2 O, Al 2 O 3 and B 2 O 3 can improve the ion exchange capacity of glass ceramics.
  • the melting temperature of the base glass is 1350-1750°C, preferably 1550-1650°C, and the melting time is 10-120min, preferably 30-90min.
  • the secondary melting temperature is 1350-1750° C., preferably 1550-1650° C., and the time is 10-120 minutes, preferably 30-90 minutes.
  • computer-aided design is used for forming, and heat treatment is performed on the shaped lithium silicate glass after forming.
  • the heat treatment temperature is 600-900°C, preferably 680-800°C, and the time is 20-180min, preferably 30 -120min, and then processed into a restoration by computer-aided design/computer-aided manufacturing (CAD/CAM).
  • CAD/CAM computer-aided design/computer-aided manufacturing
  • the molding adopts a pressing process, and heat treatment is performed on the shaped lithium silicate glass after molding.
  • the heat treatment temperature is 700-900°C, preferably 820-880°C, and the time is 20-180min, preferably 30- 120min, and then processed into a restoration by hot die casting.
  • the molten salt contains potassium salt
  • the potassium salt is selected from at least one of KNO 3 , K 2 CO 3 and K 2 SiCO 3 , based on the total weight of the molten salt, the content of KNO 3 is 97 -99 wt%, K 2 CO 3 content is 0-2 wt%, preferably 0.5-1 wt%, K 2 SiCO 3 content is 0-3 wt%, preferably 0.5-2 wt%.
  • the fluorescent agent contained in the molten salt is selected from at least one of the nitric acid hydrates of Eu, Dy, Tm, Er, Ho, Yb, Nd, Sm, and Gd, based on the total amount of the molten salt.
  • Weight, the amount of fluorescent agent added is 1-2wt%. In this application, based on the total weight of the molten salt, the added amount of the fluorescent agent is the added amount.
  • the temperature of the molten salt is 300-620°C, preferably 400-450°C.
  • the hot die casting temperature is 850-1050° C., preferably 910-950° C., and the time is 5-60 min, preferably 10-20 min.
  • the fluorescent lithium silicate glass ceramics of the embodiment and the comparative example were tested to obtain the flexural strength of the glass ceramics.
  • ingredients of formula 1 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1550°C, and the melting time is 90min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1550°C and the melting time is 90 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 680°C, and the heat treatment time is 120 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology, and the restorations are immersed in the molten salt shown in Table 2.
  • the molten salt temperature is 400°C
  • the immersion time is 3h.
  • the ingredients of formula 2 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 30 minutes, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 880°C, and the heat treatment time is 30 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 910°C, and the time is 20 minutes.
  • the ingredients of formula 3 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 30 minutes, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 800°C, and the heat treatment time is 30 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology, and the restorations are immersed in the molten salt shown in Table 2.
  • the molten salt temperature is 450°C
  • the immersion time is 1h.
  • ingredients of formula 4 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1550°C, and the melting time is 90min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1550°C and the melting time is 90 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 820°C, and the heat treatment time is 120 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 950°C, and the time is 10 minutes.
  • Immerse the restoration in molten salt 8 in Table 2 the temperature of the molten salt is 400°C, and the immersion time is 3h.
  • ingredients of formula 5 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1630°C, and the melting time is 40min, pour the melted glass liquid Put it into cold water to obtain glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1610°C and the melting time is 40min.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 780°C, and the heat treatment time is 100 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology, and the restorations are immersed in the molten salt shown in Table 2. In 10, the molten salt temperature was 410°C, and the immersion time was 2.5h.
  • the ingredients of formula 6 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1600°C, and the melting time is 60 minutes, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1600°C and the melting time is 60 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 860°C, and the heat treatment time is 60 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 930°C, and the time is 15 minutes.
  • the ingredients of formula 7 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1580 ° C, and the melting time is 60 minutes, pour the melted glass liquid into cold water to obtain a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1580°C and the melting time is 60 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 720°C, and the heat treatment time is 60 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology, and the restorations are immersed in the molten salt shown in Table 2.
  • the molten salt temperature is 410°C, and the immersion time is 1.5h.
  • ingredients of formula 8 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1620°C, and the melting time is 70min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1620°C and the melting time is 70min.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 860°C, and the heat treatment time is 40 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 920°C, and the time is 20 minutes.
  • ingredients of formula 9 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1640°C, and the melting time is 30min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1640°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 700°C, and the heat treatment time is 100 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology, and the restorations are immersed in the molten salt shown in Table 2. In 18, the molten salt temperature was 420°C, and the immersion time was 2h.
  • ingredients of formula 10 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 60min, pour the melted glass liquid Put it into cold water to obtain glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 60min.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 870°C, and the heat treatment time is 30 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 940°C, and the time is 15 minutes.
  • ingredients of formula 1 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1550°C, and the melting time is 90min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1550°C and the melting time is 90 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 680°C, and the heat treatment time is 120 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology.
  • ingredients of formula 1 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1550°C, and the melting time is 90min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1550°C and the melting time is 90 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 680°C, and the heat treatment time is 120 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology, and the restorations are immersed in the molten salt shown in Table 2.
  • the molten salt temperature is 400°C
  • the immersion time is 3h.
  • ingredients of formula 2 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 30 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 880°C, and the heat treatment time is 30 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 910°C, and the time is 20 minutes.
  • ingredients of formula 2 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 30 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 880°C, and the heat treatment time is 30 minutes.
  • the heat-treated glass ceramics are processed into a prosthetic body through a hot die-casting process.
  • the hot die-casting temperature is 910°C, and the time is 20 minutes.
  • the restoration was immersed in the molten salt 3 in Table 2, the temperature of the molten salt was 450°C, and the immersion time was 1h.
  • ingredients of formula 3 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 30 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 800°C, and the heat treatment time is 30 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology.
  • ingredients of formula 3 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 30 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 800°C, and the heat treatment time is 30 minutes.
  • the heat-treated glass ceramics are processed into restorations by CAD/CAM technology, and the restorations are immersed in molten salt 5 in Table 2. , the molten salt temperature is 450°C, and the immersion time is 1h.
  • ingredients of formula 4 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1550°C, and the melting time is 90 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1550°C and the melting time is 90 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 820°C, and the heat treatment time is 120 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 950°C, and the time is 10 minutes.
  • ingredients of formula 4 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1550°C, and the melting time is 90 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1550°C and the melting time is 90 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 820°C, and the heat treatment time is 120 minutes.
  • the heat-treated glass ceramics are processed into a prosthetic body through a hot die-casting process.
  • the hot die-casting temperature is 950°C, and the time is 10 minutes.
  • the restoration was immersed in the molten salt 7 in Table 2, the temperature of the molten salt was 400°C, and the immersion time was 3h.
  • ingredients of formula 5 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1630°C, and the melting time is 40 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1610°C and the melting time is 40 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 780°C, and the heat treatment time is 100 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology.
  • ingredients of formula 5 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1630°C, and the melting time is 40 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1610°C and the melting time is 40 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 780°C, and the heat treatment time is 100 minutes.
  • the heat-treated glass ceramics are processed into restorations by CAD/CAM technology, and the restorations are immersed in molten salt 9 in Table 2. , the molten salt temperature is 410°C, and the immersion time is 2.5h.
  • ingredients of formula 6 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1600°C, and the melting time is 60 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1600°C and the melting time is 60 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 860°C, and the heat treatment time is 60 minutes.
  • the heat-treated glass ceramics are processed into restorations by a hot die-casting process.
  • the hot die-casting temperature is 930°C, and the time is 15 minutes.
  • the ingredients of formula 6 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1600°C, and the melting time is 60 minutes, pour the melted glass into Get glass frit in cold water, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1600°C and the melting time is 60 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 860°C, and the heat treatment time is 60 minutes.
  • the glass ceramics after heat treatment are processed into restorations by hot die casting process.
  • the hot die casting temperature is 930°C, and the time is 15 minutes.
  • the prosthesis was immersed in the molten salt 11 in Table 2, the temperature of the molten salt was 430°C, and the immersion time was 2.5h.
  • ingredients of formula 7 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1580 ° C, and the melting time is 60 minutes, pour the melted glass liquid into cold water to obtain a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1580°C and the melting time is 60 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 720°C, and the heat treatment time is 60 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology.
  • the ingredients of formula 7 in Table 1 mix well and pour it into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1580 ° C, and the melting time is 60 minutes, pour the melted glass liquid into cold water to obtain a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1580°C and the melting time is 60 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 720°C, and the heat treatment time is 60 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology, and the restorations are immersed in the molten salt shown in Table 2. In 13, the molten salt temperature is 410°C, and the immersion time is 1.5h.
  • ingredients of formula 8 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1620°C, and the melting time is 70min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1620°C and the melting time is 70min.
  • heat treatment was carried out after cooling.
  • the heat treatment temperature was 860°C and the heat treatment time was 40 minutes.
  • the heat-treated glass ceramics were processed into prostheses through a hot die-casting process.
  • the hot die-casting temperature was 920°C and the time was 20 minutes.
  • ingredients of formula 8 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1620°C, and the melting time is 70min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1620°C and the melting time is 70min.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 860°C, and the heat treatment time is 40 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 920°C, and the time is 20 minutes.
  • ingredients of formula 9 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1640°C, and the melting time is 30min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1640°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 700°C, and the heat treatment time is 100 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology.
  • ingredients of formula 9 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1640°C, and the melting time is 30min, pour the melted glass liquid Put it into cold water to get a glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1640°C and the melting time is 30 minutes.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 700°C, and the heat treatment time is 100 minutes.
  • the glass ceramics after heat treatment are processed into restorations by CAD/CAM technology, and the restorations are immersed in the molten salt shown in Table 2. In 17, the molten salt temperature is 420°C, and the immersion time is 2h.
  • ingredients of formula 10 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 60min, pour the melted glass liquid Put it into cold water to obtain glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 60min.
  • heat treatment was carried out after cooling.
  • the heat treatment temperature was 870°C and the heat treatment time was 30 minutes.
  • the glass ceramics after heat treatment were processed into restorations by hot die casting process.
  • the hot die casting temperature was 940°C and the time was 15 minutes.
  • ingredients of formula 10 in Table 1 mix well and pour into a platinum crucible, put the platinum crucible into the furnace for melting, the melting temperature is 1650°C, and the melting time is 60min, pour the melted glass liquid Put it into cold water to obtain glass frit, dry the obtained glass frit and pour it into a platinum crucible for melting again.
  • the melting temperature is 1650°C and the melting time is 60min.
  • heat treatment is carried out after cooling.
  • the heat treatment temperature is 870°C, and the heat treatment time is 30 minutes.
  • the heat-treated glass ceramics are processed into restorations through a hot die-casting process.
  • the hot die-casting temperature is 940°C, and the time is 15 minutes.
  • Example 1 Compared to Comparative Examples 1-1 to 10-2, which were not immersed in molten salt for ion exchange and did not add fluorescent agent in molten salt, the glass prepared by the preparation method provided by the application Ceramics exhibit better fluorescence properties. From Example 1 to Example 10, Comparative Example 1-1 to Comparative Example 10-1, it can also be seen that the fluorescent performance of glass ceramics immersed in molten salt is better, and its flexural strength is also significantly improved. Taking Example 1 and Comparative Example 1-1 as examples, it can be seen that the flexural strength of the glass-ceramic in Example 1 of the present application is increased by 41% compared with Comparative Example 1-1 by performing ion exchange in molten salt.

Abstract

本申请提供了一种通过离子交换增强的荧光硅酸锂玻璃陶瓷及其制备方法，其包括:将基础玻璃料与着色剂混合后，熔制、水淬得到玻璃熔块，其中，基础玻璃料包括以下重量的组分：SiO2:40-70wt％，Li2O:8-24wt％，K2O:2-14wt％，Al2O3:4-12wt％，Na2O:5-13wt％，P2O5:3-13wt％，CaO:0-4wt％，ZrO2:0-22wt％，Tb4O7:0-10wt％，B2O3:0-8wt％；将得到的玻璃熔块进行二次熔制，倒入CAD或压制模具中得到成型硅酸锂玻璃，进一步热处理后，将成型硅酸锂玻璃通过CAD/CAM或热压铸工艺加工得到修复体，将修复体浸没在包含钠盐、钾盐、铯盐和/或铷盐以及荧光剂的熔盐中，通过二次晶化得到离子交换增强的荧光玻璃陶瓷修复体。通过本申请提供的制备方法，可以提高离子交换效率，稳定批量生产荧光硅酸锂玻璃陶瓷。

Description

通过离子交换增强的荧光硅酸锂玻璃陶瓷及其制备方法
本申请要求于2021年9月8日提交中国专利局、申请号为202111049905.4发明名称为“通过离子交换增强的荧光硅酸锂玻璃陶瓷及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及硅酸锂玻璃陶瓷技术领域，特别是涉及一种通过离子交换增强的荧光硅酸锂玻璃陶瓷及其制备方法。
背景技术
硅酸锂玻璃陶瓷在齿科修复领域应用范围广泛，硅酸锂玻璃陶瓷不仅具有玻璃的透度，还具有陶瓷的强度，与传统的氧化锆牙齿修复材料相比，在美学修复领域具有非常大的优势。
齿科修复材料要求更接近天然牙，人的天然牙在特定波长范围的光照射下会发出荧光，例如一些特殊场合的人造光源，在这些情况下，无荧光效果的牙科修复材料无法达到仿真效果。目前市场上大多数齿科修复材料无荧光效果，往往通过荧光釉来实现，但是荧光效果受基体影响、并且容易磨损，影响最终效果。
目前，多数是通过熔制前将荧光粉与基础玻璃料混合的方法，实现二硅酸锂玻璃陶瓷的荧光效果，但是这种方式对析晶过程会造成影响，导致析晶不均匀。部分荧光剂的加入还需要在还原气氛下进行烧结过程，工艺要求较高，难以实现批量化生产。
目前，对于玻璃陶瓷的离子交换方法多数采用添加剂法，该方法工艺简单实用，易于大批量生产，但是添加剂法的离子交换速率较慢，主要是因为离子交换中Na +和K +在熔盐中属于热扩散，离子迁移速度很慢。
发明内容
本申请的目的在于提供一种通过离子交换增强的荧光硅酸锂玻璃陶瓷及其制备方法，可以在365nm附近波长的灯光照射下发出与自然牙接近的荧光，在不影响材料透光性的情况下，增强其硬度和赋予其荧光效果，用以解决在荧光硅酸锂陶瓷制备过程中离子交换效率低，工艺复杂且生产时间长的问题。具体技术方案如下：
本申请提供一种荧光硅酸锂玻璃陶瓷的制备方法，其包括：
(1)将基础玻璃料与着色剂混合后，熔制、水淬得到玻璃熔块，其中，所述基础玻 璃料包括以下重量的组分：
Figure PCTCN2022096200-appb-000001
(2)将所述玻璃熔块进行二次熔制、成型，得到成型硅酸锂玻璃；
(3)对所述成型硅酸锂玻璃进行热处理；
(4)将成型硅酸锂玻璃加工得到修复体；
(5)将所述修复体浸没在熔盐中，浸没时间为0.3-6h，通过二次晶化得到离子交换增强的荧光玻璃陶瓷修复体，其中，所述熔盐包括钠盐、钾盐、铯盐和/或铷盐以及荧光剂，浸没时间优选为1-3h。
在本申请的一些实施方案中，着色剂包括CeO 2、Pr 2O 3、Cr 2O 3、Co 2O 3、Nd 2O 3、Er 2O 3、V 2O 5、NiO、MnO中的至少一种，基于基础玻璃料和着色剂的总重量，着色剂含量为0-10wt％。
在本申请的一些实施方案中，基于基础玻璃料和着色剂的总重量，着色剂中Fe 2O 3的含量不超过0.01wt％。
在本申请的一些实施方案中，基础玻璃料中包含以下质量的组分：
Figure PCTCN2022096200-appb-000002
Figure PCTCN2022096200-appb-000003
在本申请的一些实施方案中，基础玻璃的熔制温度为1350-1750℃，优选为1550-1650℃，时间为10-120min，优选为30-90min。
在本申请的一些实施方案中，二次熔制的温度为1350-1750℃，优选为1550-1650℃，时间为10-120min，优选为30-90min。
在本申请的一些实施方案中，成型采用计算机辅助设计，成型后对成型硅酸锂玻璃进行热处理，热处理温度为600-900℃，优选为680-800℃，时间为20-180min，优选为30-120min，然后通过CAD/CAM加工成修复体。
在本申请的一些实施方案中，成型采用压制工艺，成型后对成型硅酸锂玻璃进行热处理，热处理温度为700-900℃，优选为820-880℃，时间为20-180min，优选为30-120min，然后通过热压铸加工成修复体。
在本申请的一些实施方案中，熔盐中包含钾盐，钾盐选自KNO 3、K 2CO 3和K 2SiCO 3中的至少一种，基于熔盐的总重量，KNO 3含量为97-99wt％，K 2CO 3含量为0-2wt％，优选为0.5-1wt％，K 2SiCO 3含量为0-3wt％，优选为0.5-2wt％。
在本申请的一些实施方案中，熔盐中包含的荧光剂选自Eu(铕)、Dy(镝)、Tm(铥)、Er(铒)、Ho(钬)、Yb(镱)、Nd(钕)、Sm(钐)、Gd(钆)的硝酸水合物中的至少一种，基于熔盐的总重量，荧光剂加入量为1-2wt％。这里，荧光剂的加入量是以钾熔盐的总重量为基准，荧光剂的加入量为外加量。
在本申请的一些实施方案中，熔盐的温度为300-620℃，优选为400-450℃。
在本申请的一些实施方案中，在热压铸工艺中，热压铸温度为850-1050℃，优选为910-950℃，时间为5-60min，优选为10-20min。
本申请的有益效果：
本申请提供的一种通过离子交换增强的荧光硅酸锂玻璃陶瓷及其制备方法，通过制备K 2O、Na 2O、Al 2O 3、B 2O 3四种氧化物含量较高的基础玻璃，改善基础玻璃的网络结构，使其易于进行离子交换，再将制备好的修复体浸没在含有钾盐和荧光剂的熔盐中，通过短时间的离子交换可以增强玻璃陶瓷修复体的强度并赋予其荧光性。本申请工艺简单，易于批量生产，荧光颜色容易控制。
当然，实施本申请的任一产品或方法并不一定需要同时达到以上所述的所有优点。
具体实施方式
为使本发明的目的、技术方案、及优点更加清楚明白，以下参照附图并举实施例，对本发明进一步详细说明。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在本申请中，只要没有特别记载，玻璃陶瓷的基础玻璃料的组成以氧化物为基准表示。其中“氧化物为基准的基础玻璃组成”是指按照基础玻璃料在熔融时全部分解而在玻璃陶瓷中以氧化物的形式存在的物质进行换算而得到的基础玻璃组成，各基础玻璃料的组分表达按照习惯记为SiO 2、Al 2O 3等。
在本申请中，基础玻璃料中各组分的含量可以通过公知的方法，例如电感耦合等离子体原子发射光谱法(ICP-AES)、电感耦合等离子体质谱分析法(ICP-MS)等方法进行定量。
在本申请中，玻璃陶瓷的热稳定性及耐失透性都是指在玻璃中的结晶析出的难易度。特别地，热稳定性是指熔融状态的玻璃固化时结晶析出的难易度，耐失透性是指在再热压制时这样的将固化后的玻璃再加热时结晶析出的难易度。
本申请提供一种荧光硅酸锂玻璃陶瓷的制备方法，其包括：
(1)将基础玻璃料与着色剂混合后，熔制、水淬得到玻璃熔块，其中，所述基础玻璃料包括以下重量的组分：
Figure PCTCN2022096200-appb-000004
(2)将所述玻璃熔块进行二次熔制、成型，得到成型硅酸锂玻璃；
(3)对所述成型硅酸锂玻璃进行热处理；
(4)将成型硅酸锂玻璃加工得到修复体；
(5)将所述修复体浸没在熔盐中，浸没时间为0.3-6h，通过二次晶化得到离子交换增强的荧光玻璃陶瓷修复体，其中，所述熔盐包括钠盐、钾盐、铯盐和/或铷盐以及荧光剂，浸没时间优选为1-3h。
在本申请的一些实施方案中，着色剂包括CeO 2、Pr 2O 3、Cr 2O 3、Co 2O 3、Nd 2O 3、Er 2O 3、V 2O 5、NiO、MnO中的至少一种，基于基础玻璃料和着色剂的总重量，着色剂含量为0-10wt％。
在本申请的一些实施方案中，基于基础玻璃料和着色剂的总重量，着色剂中Fe 2O 3的含量不超过0.01wt％。
在本申请的一些实施方案中，基础玻璃料中包含以下质量的组分：
Figure PCTCN2022096200-appb-000005
其中，SiO 2是玻璃的网络形成成分，具有改善玻璃的热稳定性、化学耐久性、耐候性、提高熔融玻璃的粘度、容易将熔融玻璃成型的作用；但是SiO 2的含量过高时，存在玻璃的耐失透性降低的倾向；SiO 2是二硅酸锂主晶相的主要成分，因此，SiO 2的含量优选为上述范围。
其中，Li 2O是有助于玻璃的低比重化的成分，具有改善玻璃的熔融性同时增大平均线性热膨胀系数的作用，但是Li 2O含量过高时，玻璃的耐失透性降低；Li 2O是二硅酸锂主晶相的主要成分，因此Li 2O的含量优选为上述范围。
其中，K 2O具有改善玻璃的热稳定性的作用，但是K 2O含量过高时，玻璃陶瓷的化学 耐久性和耐候性有降低的趋势，因此K 2O的含量优选为上述范围。
其中，Na 2O具有改善玻璃的热稳定性的作用，但是Na 2O含量过高时，玻璃陶瓷的化学耐久性和耐候性有降低的趋势，因此Na 2O的含量优选为上述范围。
其中，Al 2O 3是具有改善玻璃的耐久性和耐候性作用的玻璃成分，可以将其视为玻璃的网络组成成分，但是Al 2O 3含量过高时，玻璃陶瓷的耐失透性降低，因此Al 2O 3的含量优选为上述范围。
其中，P 2O 5是玻璃的网络形成成分，是为了在玻璃中大量含有高分散成分的必要成分，在上述含量的优选范围中，可以得到热稳定性高的玻璃陶瓷。
其中，CaO是具有改善玻璃的热稳定性及耐失透性的作用的玻璃成分，但是CaO含量过高时，损害高分散性，玻璃陶瓷的热稳定性及耐失透性降低，因此CaO的含量优选为上述范围。
其中，ZrO 2是具有改善玻璃的热稳定性及耐失透性的作用的玻璃成分，但是ZrO 2含量过高时，显示出热稳定性降低的倾向；ZrO 2在玻璃陶瓷中可以作为形核剂，因此ZrO 2的含量优选为上述范围。
其中，Tb 4O 7的含量过高时，玻璃的热稳定性和耐失透性降低，因此从抑制热稳定性及耐失透性降低的观点考虑，Tb 4O 7的含量优选为上述范围。
其中，B 2O 3是玻璃的网络形成成分，具有改善玻璃陶瓷热稳定性的作用，但是其含量过高时，存在耐失透性降低的倾向，因此B 2O 3的含量优选为上述范围。
在配料时，上述各氧化物的原料可以选自其氧化物、碳酸盐化合物、磷酸盐化合物。
本发明通过改进玻璃陶瓷的内部网络结构，进一步加快离子扩散速率，大幅缩短生产时间。此外，本申请发明人发现，K 2O、Na 2O、Al 2O 3和B 2O 3可以提高玻璃陶瓷的离子交换能力。
在本申请的一些实施方案中，基础玻璃的熔制温度为1350-1750℃，优选为1550-1650℃，时间为10-120min，优选为30-90min。
在本申请的一些实施方案中，二次熔制的温度为1350-1750℃，优选为1550-1650℃，时间为10-120min，优选为30-90min。
在本申请的一些实施方案中，成型采用计算机辅助设计，成型后对成型硅酸锂玻璃进行热处理，热处理温度为600-900℃，优选为680-800℃，时间为20-180min，优选为30-120min，然后通过计算机辅助设计/计算机辅助制造(CAD/CAM)加工成修复体。
在本申请的一些实施方案中，成型采用压制工艺，成型后对成型硅酸锂玻璃进行热处理，热处理温度为700-900℃，优选为820-880℃，时间为20-180min，优选为30-120min，然后通过热压铸加工成修复体。
在本申请的一些实施方案中，熔盐中包含钾盐，钾盐选自KNO 3、K 2CO 3和K 2SiCO 3中的至少一种，基于熔盐的总重量，KNO 3含量为97-99wt％，K 2CO 3含量为0-2wt％，优选为0.5-1wt％，K 2SiCO 3含量为0-3wt％，优选为0.5-2wt％。
在本申请的一些实施方案中，熔盐中包含的荧光剂选自Eu、Dy、Tm、Er、Ho、Yb、Nd、Sm、Gd的硝酸水合物中的至少一种，基于熔盐的总重量，荧光剂加入量为1-2wt％。在本申请中，以熔盐的总重量为基准，荧光剂的加入量为外加量。
在本申请的一些实施方案中，熔盐的温度为300-620℃，优选为400-450℃。
在本申请的一些实施方案中，在热压铸工艺中，热压铸温度为850-1050℃，优选为910-950℃，时间为5-60min，优选为10-20min。
具体测试过程：
玻璃陶瓷挠曲强度测试：
通过TH-8201万能材料试验机应力分析仪，根据ISO6872-2015牙科陶瓷标准对实施例及对比例的荧光硅酸锂玻璃陶瓷进行测试，得到玻璃陶瓷的挠曲强度。
辉度测试：
通过随机抽取20名实验人员对放置在标准光源对色灯箱内的荧光硅酸锂玻璃陶瓷进行观察，并进行1-10分打分，最终取其平均值，1-4分为ΙΙΙ级，5-7分为ΙΙ级，8-10为Ι级，其中，Ι级为荧光亮，ΙΙ级为荧光较亮，ΙΙΙ级为荧光较弱。
实施例
实施例1
根据表1中的配方1配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1550℃，熔制时间为90min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1550℃，熔制时间为90min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为680℃，热处理时间为120min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐2中，熔盐温度为400℃，浸没时间为3h。
实施例2
根据表1中的配方2配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为880℃，热处理时间为30min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为910℃，时间为20min，将修复体浸没到表2的熔盐4中，熔盐温度为450℃，浸没时间为1h。
实施例3
根据表1中的配方3配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为800℃，热处理时间为30min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐6中，熔盐温度为450℃，浸没时间为1h。
实施例4
根据表1中的配方4配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1550℃，熔制时间为90min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1550℃，熔制时间为90min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为820℃，热处理时间为120min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为950℃，时间为10min，将修复体浸没到表2的熔盐8中，熔盐温度为400℃，浸没时间为3h。
实施例5
根据表1中的配方5配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1630℃，熔制时间为40min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1610℃，熔制时间为40min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为780℃，热处理时间为100min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐10中，熔盐温度为410℃，浸没时间为2.5h。
实施例6
根据表1中的配方6配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1600℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1600℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为860℃，热处理时间为60min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为930℃，时间为15min，将修复体浸没到表2的熔盐12中，熔盐温度为430℃，浸没时间为2.5h。
实施例7
根据表1中的配方7配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1580℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1580℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为720℃，热处理时间为60min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐14中，熔盐温度为410℃，浸没时间为1.5h。
实施例8
根据表1中的配方8配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1620℃，熔制时间为70min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1620℃，熔制时间为70min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为860℃，热处理时间为40min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为920℃，时间为20min，将修复体浸没到表2的熔盐16中，熔盐温度为420℃，浸没时间为1h。
实施例9
根据表1中的配方9配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1640℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1640℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为700℃，热处理时间为100min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成 修复体，将修复体浸没到表2的熔盐18中，熔盐温度为420℃，浸没时间为2h。
实施例10
根据表1中的配方10配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为870℃，热处理时间为30min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为940℃，时间为15min，将修复体浸没到表2的熔盐20中，熔盐温度为430℃，浸没时间为2h。
对比例1-1
根据表1中的配方1配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1550℃，熔制时间为90min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1550℃，熔制时间为90min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为680℃，热处理时间为120min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体。
对比例1-2
根据表1中的配方1配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1550℃，熔制时间为90min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1550℃，熔制时间为90min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为680℃，热处理时间为120min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐1中，熔盐温度为400℃，浸没时间为3h。
对比例2-1
根据表1的配方2配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为880℃，热处理时间为30min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压 铸温度为910℃，时间为20min。
对比例2-2
根据表1的配方2配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为880℃，热处理时间为30min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为910℃，时间为20min，将修复体浸没到表2的熔盐3中，熔盐温度为450℃，浸没时间为1h。
对比例3-1
根据表1的配方3配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为800℃，热处理时间为30min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体。
对比例3-2
根据表1的配方3配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为800℃，热处理时间为30min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐5中，熔盐温度为450℃，浸没时间为1h。
对比例4-1
根据表1的配方4配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1550℃，熔制时间为90min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1550℃，熔制时间为90min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为820℃，热处理时间为120min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为950℃，时间为10min。
对比例4-2
根据表1的配方4配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1550℃，熔制时间为90min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1550℃，熔制时间为90min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为820℃，热处理时间为120min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为950℃，时间为10min，将修复体浸没到表2的熔盐7中，熔盐温度为400℃，浸没时间为3h。
对比例5-1
根据表1的配方5配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1630℃，熔制时间为40min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1610℃，熔制时间为40min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为780℃，热处理时间为100min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体。
对比例5-2
根据表1的配方5配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1630℃，熔制时间为40min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1610℃，熔制时间为40min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为780℃，热处理时间为100min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐9中，熔盐温度为410℃，浸没时间为2.5h。
对比例6-1
根据表1的配方6配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1600℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1600℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为860℃，热处理时间为60min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为930℃，时间为15min。
对比例6-2
根据表1的配方6配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1600℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1600℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为860℃，热处理时间为60min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为930℃，时间为15min，将修复体浸没到表2的熔盐11中，熔盐温度为430℃，浸没时间为2.5h。
对比例7-1
根据表1中的配方7配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1580℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1580℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为720℃，热处理时间为60min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体。
对比例7-2
根据表1中的配方7配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1580℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1580℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为720℃，热处理时间为60min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐13中，熔盐温度为410℃，浸没时间为1.5h。
对比例8-1
根据表1中的配方8配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1620℃，熔制时间为70min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1620℃，熔制时间为70min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为860℃，热处理时间为40min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为920℃，时间为20min。
对比例8-2
根据表1中的配方8配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1620℃，熔制时间为70min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1620℃，熔制时间为70min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为860℃，热处理时间为40min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为920℃，时间为20min，将修复体浸没到表2的熔盐15中，熔盐温度为420℃，浸没时间为1h。
对比例9-1
根据表1中的配方9配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1640℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1640℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为700℃，热处理时间为100min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体。
对比例9-2
根据表1中的配方9配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1640℃，熔制时间为30min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1640℃，熔制时间为30min，将再次熔制好的玻璃液倒入准备好的CAD模具中，待冷却后进行热处理，热处理温度为700℃，热处理时间为100min，将热处理后的玻璃陶瓷通过CAD/CAM工艺加工成修复体，将修复体浸没到表2的熔盐17中，熔盐温度为420℃，浸没时间为2h。
对比例10-1
根据表1中的配方10配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为870℃，热处理时间为30min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为940℃，时间为15min。
对比例10-2
根据表1中的配方10配料，充分混合均匀后倒入铂金坩埚中，将铂金坩埚放入炉内熔制，熔制温度为1650℃，熔制时间为60min，将熔制好的玻璃液倒入冷水中，得到玻璃熔块，将得到的玻璃熔块烘干后再次倒入铂金坩埚中熔制，熔制温度为1650℃，熔制时间为60min，将再次熔制好的玻璃液倒入准备好的Press模具中，待冷却后进行热处理，热处理温度为870℃，热处理时间为30min，将热处理后的玻璃陶瓷通过热压铸工艺加工成修复体，热压铸温度为940℃，时间为15min，将修复体浸没到表2的熔盐19中，熔盐温度为430℃，浸没时间为2h。
各实施例和对比例的基础玻璃料与着色剂配方见表1；
各实施例和对比例所用熔盐的配方见表2；
各实施例和对比例的玻璃陶瓷挠曲强度及辉度结果见表3。
表1基础玻璃料与着色剂配方
Figure PCTCN2022096200-appb-000006
Figure PCTCN2022096200-appb-000007
表1中，“-”表示不含有。
表2熔盐配方表
Figure PCTCN2022096200-appb-000008
表2中，“-”表示不含有。
表3玻璃陶瓷挠曲强度和辉度结果
编号 挠曲强度MPa 辉度 编号 挠曲强度MPa 辉度 编号 挠曲强度MPa 辉度
实施例1 583.27 Ι级 对比例1-1 414.35 ΙΙΙ级 对比例1-2 586.48 ΙΙΙ级
实施例2 611.28 Ι级 对比例2-1 442.73 ΙΙΙ级 对比例2-2 591.69 ΙΙΙ级
实施例3 620.94 Ι级 对比例3-1 443.61 ΙΙΙ级 对比例3-2 634.36 ΙΙΙ级
实施例4 631.39 ΙΙ级 对比例4-1 438.92 ΙΙΙ级 对比例4-2 627.75 ΙΙΙ级
实施例5 569.95 Ι级 对比例5-1 433.52 ΙΙΙ级 对比例5-2 580.92 ΙΙΙ级
实施例6 579.45 Ι级 对比例6-1 438.72 ΙΙΙ级 对比例6-2 582.67 ΙΙΙ级
实施例7 568.36 Ι级 对比例7-1 428.65 ΙΙΙ级 对比例7-2 583.32 ΙΙΙ级
实施例8 572.74 Ι级 对比例8-1 433.21 ΙΙΙ级 对比例8-2 569.58 ΙΙΙ级
实施例9 565.23 Ι级 对比例9-1 411.96 ΙΙΙ级 对比例9-2 568.76 ΙΙΙ级
实施例10 552.49 Ι级 对比例10-1 424.56 ΙΙΙ级 对比例10-2 559.23 ΙΙΙ级
从表3中可以看出，相比于未在熔盐中浸没进行离子交换和熔盐中未添加荧光剂的对比例1-1到10-2，采用本申请提供的制备方法制得的玻璃陶瓷表现出了更好的荧光性能。从实施例1至实施例10、对比例1-1至对比例10-1还可以看出，经过熔盐浸没的玻璃陶瓷的荧光性能更好，同时其挠曲强度也明显提升，例如以实施例1和对比例1-1为例可以看出，通过在熔盐中进行离子交换，本申请实施例1的玻璃陶瓷的挠曲强度相比于对比例1-1提升了41％。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明保护的范围之内。

Claims (12)

  1. 一种荧光硅酸锂玻璃陶瓷的制备方法，其包括：
    (1)将基础玻璃料与着色剂混合后，熔制、水淬得到玻璃熔块，其中，所述基础玻璃料包括以下重量的组分：
    Figure PCTCN2022096200-appb-100001
    (2)将所述玻璃熔块进行二次熔制、成型，得到成型硅酸锂玻璃；
    (3)对所述成型硅酸锂玻璃进行热处理；
    (4)将成型硅酸锂玻璃加工得到修复体；
    (5)将所述修复体浸没在熔盐中，浸没时间为0.3-6h，通过二次晶化得到离子交换增强的荧光玻璃陶瓷修复体，其中，所述熔盐包括钠盐、钾盐、铯盐和/或铷盐以及荧光剂，所述浸没时间优选为1-3h。
  2. 根据权利要求1所述的制备方法，其中，所述着色剂包括CeO 2、Pr 2O 3、Cr 2O 3、Co 2O 3、Nd 2O 3、Er 2O 3、V 2O 5、NiO、MnO中的至少一种，基于所述基础玻璃料和所述着色剂的总重量，所述着色剂含量为0-10wt％。
  3. 根据权利要求1所述的制备方法，其中，基于所述基础玻璃料和所述着色剂的总重量，所述着色剂中Fe 2O 3的含量不超过0.01wt％。
  4. 根据权利要求1所述的制备方法，其中，所述基础玻璃料中包含以下质量的组分：
    Figure PCTCN2022096200-appb-100002
    Figure PCTCN2022096200-appb-100003
  5. 根据权利要求1所述的制备方法，其中，所述基础玻璃的熔制温度为1350-1750℃，优选为1550-1650℃，时间为10-120min，优选为30-90min。
  6. 根据权利要求1所述的制备方法，其中，所述二次熔制的温度为1350-1750℃，优选为1550-1650℃，时间为10-120min，优选为30-90min。
  7. 根据权利要求1所述的制备方法，其中，所述成型采用计算机辅助设计，成型后对所述成型硅酸锂玻璃进行热处理，所述热处理温度为600-900℃，优选为680-800℃，时间为20-180min，优选为30-120min，然后通过CAD/CAM加工成修复体。
  8. 根据权利要求1所述的制备方法，其中，所述成型采用压制工艺，成型后对所述成型硅酸锂玻璃进行热处理，所述热处理温度为700-900℃，优选为820-880℃，时间为20-180min，优选为30-120min，然后通过热压铸加工成修复体。
  9. 根据权利要求1所述的制备方法，其中，所述熔盐中包含钾盐，所述钾盐包含KNO 3、K 2CO 3和K 2SiCO 3，基于所述熔盐的总重量，所述KNO 3含量为97-99wt％，所述K 2CO 3含量为0-2wt％，优选为0.5-1wt％，所述K 2SiCO 3含量为0-3wt％，优选为0.5-2wt％。
  10. 根据权利要求1所述的制备方法，其中，所述熔盐中包含的荧光剂选自Eu、Dy、Tm、Er、Ho、Yb、Nd、Sm、Gd的硝酸水合物中的至少一种，基于所述熔盐的总重量，所述荧光剂加入量为1-2wt％。
  11. 根据权利要求1所述的制备方法，其中，所述熔盐的温度为300-620℃，优选为400-450℃。
  12. 根据权利要求8所述的制备方法，其中，在所述热压铸工艺中，热压铸温度为850-1050℃，优选为910-950℃，时间为5-60min，优选为10-20min。
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