CN113754288B - Fluorescent lithium silicate glass ceramic enhanced by ion exchange and preparation method thereof - Google Patents
Fluorescent lithium silicate glass ceramic enhanced by ion exchange and preparation method thereof Download PDFInfo
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- CN113754288B CN113754288B CN202111049905.4A CN202111049905A CN113754288B CN 113754288 B CN113754288 B CN 113754288B CN 202111049905 A CN202111049905 A CN 202111049905A CN 113754288 B CN113754288 B CN 113754288B
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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
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- 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
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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
- 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
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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
- 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
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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
- 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
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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
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
Abstract
The application provides a fluorescent lithium silicate glass ceramic enhanced by ion exchange and a preparation method thereof, which comprises the steps of mixing a basic glass material and a coloring agent, melting and water quenching to obtain a glass frit, wherein the basic glass material comprises the following components in parts by weight: siO 2 2 :40‑70wt％，Li 2 O:8‑24wt％，K 2 O:2‑14wt％，Al 2 O 3 :4‑12wt％，Na 2 O:5‑13wt％，P 2 O 5 :3‑13wt％，CaO:0‑4wt％，ZrO 2 :0‑22wt％，Tb 4 O 7 :0‑10wt％，B 2 O 3 0-8wt%; and performing secondary melting on the obtained glass frit, pouring the glass frit into a CAD (computer aided design) or pressing mold to obtain formed lithium silicate glass, further performing heat treatment, processing the formed lithium silicate glass by a CAD/CAM (computer aided manufacturing) or hot die casting process to obtain a restoration, immersing the restoration in a molten salt containing sodium salt, potassium salt, cesium salt and/or rubidium salt and a fluorescent agent, and performing secondary crystallization to obtain the ion exchange enhanced fluorescent glass ceramic restoration. The preparation method provided by the application can improve and stabilize the ion exchange efficiencyThe fluorescent lithium silicate glass ceramic is produced in batch.
Description
Technical Field
The application relates to the technical field of lithium silicate glass ceramics, in particular to fluorescent lithium silicate glass ceramics enhanced by ion exchange and a preparation method thereof.
Background
The lithium silicate glass ceramic has wide application range in the field of dental restoration, has the transparency of glass and the strength of ceramic, and has great advantages in the field of aesthetic restoration compared with the traditional zirconia dental restoration material.
Dental restorative materials are required to be closer to natural teeth, which can fluoresce under light irradiation in a specific wavelength range, such as artificial light sources in special occasions, in which case dental restorative materials without fluorescence effect cannot achieve simulation effect. Most dental repair materials on the market at present have no fluorescent effect and are usually realized through fluorescent glaze, but the fluorescent effect is influenced by a substrate and is easy to wear, so that the final effect is influenced.
At present, most of the methods are to mix fluorescent powder with basic glass frit before melting to realize the fluorescent effect of the lithium disilicate glass ceramic, but the method can affect the crystallization process, so that the crystallization is not uniform. And part of fluorescent agent is added in a sintering process under a reducing atmosphere, so that the process requirement is high, and batch production is difficult to realize.
At present, most of ion exchange methods for glass ceramics adopt an additive method, the method has simple and practical process and is easy for mass production, but the ion exchange rate of the additive method is slower mainly because of Na in ion exchange + And K + Thermal diffusion in molten salt, high ion migration speedSlow. The invention further accelerates the ion diffusion rate and greatly shortens the production time by improving the internal network structure of the glass ceramic.
Disclosure of Invention
The application aims to provide a fluorescent lithium silicate glass ceramic enhanced by ion exchange and a preparation method thereof, which can emit fluorescence close to natural teeth under the irradiation of lamplight with a wavelength of 365nm, enhance the hardness of the fluorescent lithium silicate glass ceramic and endow the fluorescent lithium silicate glass ceramic with a fluorescent effect under the condition of not influencing the light transmission of the fluorescent lithium silicate glass ceramic, and are used for solving the problems of low ion exchange efficiency, complex process and long production time in the preparation process of the fluorescent lithium silicate glass ceramic. The specific technical scheme is as follows:
the application provides a preparation method of fluorescent lithium silicate glass ceramic, which comprises the following steps:
(1) Mixing a base glass material and a coloring agent, melting and water quenching to obtain a glass frit, wherein the base glass material comprises the following components in parts by weight:
(2) Carrying out secondary melting and molding on the glass frit to obtain molded lithium silicate glass;
(3) Heat treating the formed lithium silicate glass;
(4) Processing the formed lithium silicate glass to obtain a restoration;
(5) Immersing the restoration in molten salt for 0.3-6h, and obtaining the fluorescent glass ceramic restoration with enhanced ion exchange through secondary crystallization, wherein the molten salt comprises sodium salt, potassium salt, cesium salt and/or rubidium salt and fluorescent agent, and the immersion time is preferably 1-3h.
In some embodiments of the present application, the colorant comprises 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 based on the total weight of the base glass frit and the colorantThe content of the colorant is 0 to 10wt%.
In some embodiments of the present application, the colorant comprises Fe, based on the total weight of the base glass frit and the colorant 2 O 3 The content of (B) is not more than 0.01wt%.
In some embodiments of the present application, the base frit comprises the following components by mass:
in some embodiments of the present application, the base glass has a melting temperature of 1350-1750 deg.C, preferably 1550-1650 deg.C, and a time of 10-120min, preferably 30-90min.
In some embodiments of the present application, the temperature of the secondary melting is 1350-1750 ℃, preferably 1550-1650 ℃, for 10-120min, preferably 30-90min.
In some embodiments of the present application, the forming is computer aided design, the formed lithium silicate glass is heat treated after forming at a temperature of 600-900 ℃, preferably 680-800 ℃ for 20-180min, preferably 30-120min, and then processed into the prosthesis by CAD/CAM.
In some embodiments of the present application, the forming is performed by a pressing process, the formed lithium silicate glass is subjected to a heat treatment after the forming, the heat treatment temperature is 700-900 ℃, preferably 820-880 ℃, the time is 20-180min, preferably 30-120min, and then the restoration is processed by hot press casting.
In some embodiments of the present application, the molten salt comprises a potassium salt selected from KNO 3 、K 2 CO 3 And K 2 SiCO 3 Based on the total weight of the molten salt, KNO 3 97-99 wt.%, K 2 CO 3 In an amount of 0 to 2 wt.%, preferably 0.5 to 1 wt.%, K 2 SiCO 3 The content is 0 to 3wt%, preferably 1 to 2wt%.
In some embodiments of the present application, the fluorescer comprised in the molten salt is selected from at least one of nitrate hydrates of Eu (europium), dy (dysprosium), tm (thulium), er (erbium), ho (holmium), yb (ytterbium), nd (neodymium), sm (samarium), gd (gadolinium), the fluorescer being added in an amount of 1-2wt% based on the total weight of the molten salt. Here, the amount of the fluorescer is based on the total weight of the molten potassium salt, and the amount of the fluorescer is added as an additional amount.
In some embodiments herein, the temperature of the molten salt is from 300 to 620 ℃, preferably from 400 to 450 ℃.
In some embodiments of the present application, the hot-die casting temperature is 850-1050 deg.C, preferably 910-950 deg.C, and the time is 5-60min, preferably 10-20min, in the hot-die casting process.
The beneficial effect of this application:
the application provides a fluorescent lithium silicate glass ceramic enhanced by ion exchange and a preparation method thereof, and K is prepared 2 O、NaO、Al 2 O 3 、B 2 O 3 The four kinds of basic glass with higher oxide content improve the network structure of the basic glass, so that the basic glass is easy to carry out ion exchange, and then the prepared restoration is immersed in the fused salt containing sylvite and fluorescent agent, so that the strength of the glass ceramic restoration can be enhanced and the glass ceramic restoration can be endowed with fluorescence through short-time ion exchange. The method has the advantages of simple process, easy batch production and easy control of the fluorescence color.
Of course, it is not necessary for any product or method of the present application to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the present application will be described clearly and completely below, and it should be apparent that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application are within the scope of protection of the present application.
In the present application, unless otherwise specified, the composition of the base glass frit of the glass ceramic is expressed on an oxide basis. Wherein "oxide-based base glass composition" means that the base glass frit is completely decomposed at the time of melting and oxides are formed in the glass ceramicThe base glass composition obtained by conversion of the substances present in the form, the compositional expression of each base glass frit being conventionally denoted as SiO 2 、Al 2 O 3 And the like.
In the present application, the content of each component in the base glass frit can be quantified by a known method, for example, inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), or the like.
In the present application, both the thermal stability and devitrification resistance of a glass ceramic mean the degree of difficulty in crystal precipitation in a glass. In particular, the thermal stability refers to the ease with which crystals precipitate when the glass in a molten state is solidified, and the devitrification resistance refers to the ease with which crystals precipitate when the solidified glass is reheated, such as in reheat pressing.
The application provides a preparation method of fluorescent lithium silicate glass ceramic, which comprises the following steps:
(1) Mixing a base glass material and a coloring agent, melting and water quenching to obtain a glass frit, wherein the base glass material comprises the following components in parts by weight:
(2) Carrying out secondary melting and molding on the glass frit to obtain molded lithium silicate glass;
(3) Carrying out heat treatment on the formed lithium silicate glass;
(4) Processing the formed lithium silicate glass to obtain a restoration;
(5) Immersing the restoration in molten salt for 0.3-6h, and obtaining the fluorescent glass ceramic restoration with enhanced ion exchange through secondary crystallization, wherein the molten salt comprises sodium salt, potassium salt, cesium salt and/or rubidium salt and fluorescent agent, and the immersion time is preferably 1-3h.
In some embodiments of the present application, the colorant comprises 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 At least one of NiO and MnO in an amount of 0 to 10wt% based on the total weight of the base glass frit and the colorant.
In some embodiments of the present application, the colorant comprises Fe, based on the total weight of the base glass frit and the colorant 2 O 3 The content of (B) is not more than 0.01wt%.
In some embodiments of the present application, the base frit comprises the following components by mass:
wherein, siO 2 Is a network forming component of glass, and has the functions of improving the thermal stability, chemical durability and weather resistance of the glass, improving the viscosity of the molten glass and easily forming the molten glass; but SiO 2 When the content of (b) is too high, devitrification resistance of the glass tends to decrease; siO 2 2 Is a main component of a main crystal phase of lithium disilicate, and thus, siO 2 The content of (b) is preferably in the above range.
Wherein, li 2 O is a component contributing to the low specific gravity of the glass and has the effect of improving the meltability of the glass and increasing the average linear thermal expansion coefficient, but Li 2 When the content of O is too high, devitrification resistance of the glass is lowered; li 2 O is a main component of the main crystal phase of lithium disilicate, so Li 2 The content of O is preferably in the above range.
Wherein, K 2 O has the effect of improving the thermal stability of the glass, but K 2 When the O content is too high, the chemical durability and weather resistance of the glass-ceramic tend to be lowered, so that K 2 The content of O is preferably in the above range.
Wherein, na 2 O has the effect of improving the thermal stability of the glass, but Na 2 When the O content is too high, the chemical durability and weather resistance of the glass ceramic tend to be lowered, so that Na 2 The content of O is preferably in the above range.
Wherein, al 2 O 3 Is a glass component having an effect of improving the durability and weather resistance of the glass, and can be regarded as a network component of the glass, but Al 2 O 3 When the content is too high, the devitrification resistance of the glass ceramic is lowered, so that Al 2 O 3 The content of (b) is preferably in the above range.
Wherein, P 2 O 5 Is a network-forming component of the glass, and is an essential component for containing a large amount of a highly dispersed component in the glass, and a glass ceramic having high thermal stability can be obtained in a preferable range of the above content.
Among them, caO is a glass component having an effect of improving thermal stability and devitrification resistance of the glass, but if the content of CaO is too high, high dispersibility is impaired, and thermal stability and devitrification resistance of the glass ceramic are lowered, so the content of CaO is preferably in the above range.
Wherein, zrO 2 Is a glass component having an effect of improving the thermal stability and resistance to devitrification of the glass, but ZrO 2 When the content is too high, the thermal stability tends to be lowered; zrO (ZrO) 2 Can act as a nucleating agent in the glass ceramic, thus ZrO 2 The content of (b) is preferably in the above range.
Wherein, tb 4 O 7 When the content of (b) is too high, the thermal stability and devitrification resistance of the glass are lowered, and therefore Tb is considered to suppress the lowering of the thermal stability and devitrification resistance 4 O 7 The content of (b) is preferably in the above range.
Wherein, B 2 O 3 Is a network-forming component of glass and has an effect of improving the thermal stability of glass ceramics, but if the content is too high, the devitrification resistance tends to decrease, so that B 2 O 3 The content of (b) is preferably in the above range.
Furthermore, the inventors of the present application found that K 2 O、Na 2 O、Al 2 O 3 And B 2 O 3 The ion exchange capacity of the glass-ceramic can be improved.
In some embodiments of the present application, the base glass is melted at a temperature of 1350-1750 deg.C, preferably 1550-1650 deg.C, for a time of 10-120min, preferably 30-90min.
In some embodiments of the present application, the temperature of the secondary melting is 1350-1750 ℃, preferably 1550-1650 ℃, for 10-120min, preferably 30-90min.
In some embodiments of the present application, the forming is computer aided design, the formed lithium silicate glass is heat treated after forming at a temperature of 600-900 deg.C, preferably 680-800 deg.C for 20-180min, preferably 30-120min, and then processed into a restoration by CAD/CAM.
In some embodiments of the present application, the forming is performed by a pressing process, the formed lithium silicate glass is subjected to a heat treatment after the forming, the heat treatment temperature is 700-900 ℃, preferably 820-880 ℃, the time is 20-180min, preferably 30-120min, and then the restoration is processed by hot press casting.
In some embodiments of the present application, the molten salt comprises a potassium salt selected from KNO 3 、K 2 CO 3 And K 2 SiCO 3 Based on the total weight of the molten salt, KNO 3 97-99 wt.%, K 2 CO 3 In an amount of 0 to 2 wt.%, preferably 0.5 to 1 wt.%, K 2 SiCO 3 The content is 0 to 3wt%, preferably 1 to 2wt%.
In some embodiments of the present application, the fluorescer comprised in the molten salt is selected from at least one of nitrate hydrates of Eu, dy, tm, er, ho, yb, nd, sm, gd, the fluorescer being added in an amount of 1-2wt% based on the total weight of the molten salt. In the present application, the amount of the fluorescent agent added is an additional amount based on the total weight of the molten salt.
In some embodiments herein, the temperature of the molten salt is in the range of 300 to 620 ℃, preferably 400 to 450 ℃.
In some embodiments herein, the hot-die-casting process is carried out at a temperature of 850-1050 deg.C, preferably 910-950 deg.C, for a period of 5-60min, preferably 10-20min.
The specific test process is as follows:
glass ceramic flexural strength test:
the fluorescent lithium silicate glass ceramics of the examples and comparative examples were tested according to ISO6872-2015 dental ceramic standard by a TH-8201 Universal Material testing machine stress analyzer to obtain flexural strength of the glass ceramics.
And (3) testing the brightness:
the method comprises the steps of observing fluorescent lithium silicate glass ceramic placed in a standard light source color matching lamp box by randomly extracting 20 experience personnel, and performing 1-10 point scoring, and finally taking the average value, wherein 1-4 points to the grade II, 5-7 points to the grade III, and 8-10 points to the grade II, wherein the grade I is fluorescent light, the grade III is relatively bright in fluorescence, and the grade III is relatively weak in fluorescence.
Examples
Example 1
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds according to the formula 1 ingredient in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting, wherein the melting temperature is 1550 ℃, the melting time is 90min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting, wherein the melting temperature is 1550 ℃, the melting time is 90min, pouring the molten glass into a prepared CAD (computer aided design) mold, cooling, carrying out heat treatment, wherein the heat treatment temperature is 680 ℃, the heat treatment time is 120min, processing the glass ceramic subjected to heat treatment into a restoration by a CAD/CAM (computer aided design/computer aided manufacturing) process, immersing the restoration into the molten salt 2 in the table 2, the molten salt temperature is 400 ℃, and the immersion time is 3h.
Example 2
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds according to the formula 2 in the table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace to be melted, the melting temperature is 1650 ℃, the melting time is 30min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again to be melted, the melting temperature is 1650 ℃, the melting time is 30min, the melted glass liquid is poured into a prepared Press die to be cooled and then subjected to heat treatment, the heat treatment temperature is 880 ℃, the heat treatment time is 30min, the glass ceramic after the heat treatment is processed into the prosthesis through a hot compression casting process, the hot compression casting temperature is 910 ℃, the heat treatment time is 20min, the prosthesis is immersed into the molten salt 4 in the table 2, the molten salt temperature is 450 ℃, and the immersion time is 1h.
Example 3
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds according to formula 3 in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace for melting, the melting temperature is 1650 ℃, the melting time is 30min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again for melting, the melting temperature is 1650 ℃, the melting time is 30min, the melted glass liquid is poured into a prepared CAD mold, heat treatment is carried out after cooling, the heat treatment temperature is 800 ℃, the heat treatment time is 30min, the glass ceramic after heat treatment is processed into a restoration by a CAD/CAM process, the restoration is immersed into the fused salt 6 in the table 2, the fused salt temperature is 450 ℃, and the immersion time is 1h.
Example 4
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds thereof according to the formula 4 in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace for melting, the melting temperature is 1550 ℃, the melting time is 90min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again for melting, the melting temperature is 1550 ℃, the melting time is 90min, the melted glass liquid is poured into a prepared Press die, the heat treatment is carried out after cooling, the heat treatment temperature is 820 ℃, the heat treatment time is 120min, the glass ceramic after the heat treatment is processed into a restoration by a hot-Press casting process, the hot-Press casting temperature is 950 ℃, the hot-Press casting time is 10min, the restoration is immersed into the fused salt 8 in the table 2, the fused salt temperature is 400 ℃, and the immersion time is 3h.
Example 5
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds thereof according to formula 5 in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting, wherein the melting temperature is 1630 ℃, the melting time is 40min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting, wherein the melting temperature is 1610 ℃, the melting time is 40min, pouring the molten glass into a prepared CAD (computer aided design) mold, cooling, and then carrying out heat treatment, wherein the heat treatment temperature is 780 ℃, the heat treatment time is 100min, processing the glass ceramic after heat treatment into a restoration by a CAD/CAM (computer aided design/computer aided manufacturing) process, immersing the restoration into the molten salt 10 in the table 2, wherein the temperature of the molten salt is 410 ℃, and the immersion time is 2.5h.
Example 6
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds thereof according to the formula 6 in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace to be melted, the melting temperature is 1600 ℃, the melting time is 60min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again to be melted, the melting temperature is 1600 ℃, the melting time is 60min, the melted glass liquid is poured into a prepared Press die, the heat treatment is carried out after the cooling, the heat treatment temperature is 860 ℃, the heat treatment time is 60min, the glass ceramic after the heat treatment is processed into a restoration body through a hot compression casting process, the hot compression casting temperature is 930 ℃, the heat treatment time is 15min, the restoration body is immersed into the molten salt 12 in the table 2, the molten salt temperature is 430 ℃, and the immersion time is 2.5h.
Example 7
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof, formulated according to formulation 7 in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1580 ℃ for 60min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible for melting at 1580 ℃ for 60min, pouring the molten glass into a prepared CAD (computer aided design) mold, cooling, carrying out heat treatment at 720 ℃ for 60min, processing the heat-treated glass ceramic into a restoration by a CAD/CAM (computer aided design/computer aided manufacturing) process, immersing the restoration into the molten salt 14 in the table 2, wherein the temperature of the molten salt is 410 ℃, and the immersion time is 1.5h.
Example 8
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds thereof according to the formula 8 ingredients in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace to be melted, the melting temperature is 1620 ℃, the melting time is 70min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again to be melted, the melting temperature is 1620 ℃, the melting time is 70min, the melted glass liquid is poured into a prepared Press die, the heat treatment is carried out after the cooling, the heat treatment temperature is 860 ℃, the heat treatment time is 40min, the heat-treated glass ceramic is processed into a restoration body through a hot compression casting process, the hot compression casting temperature is 920 ℃, the heat treatment time is 20min, the restoration body is immersed into the fused salt 16 in the table 2, the fused salt temperature is 420 ℃, and the immersion time is 1h.
Example 9
The raw materials can be selected from oxides, carbonate compounds, phosphate compounds thereof according to formulation 9 in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at the melting temperature of 1640 ℃ for 30min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible for melting at the melting temperature of 1640 ℃ for 30min, pouring the molten glass into a prepared CAD (computer aided design) mold, cooling, performing heat treatment at the heat treatment temperature of 700 ℃ for 100min, processing the heat-treated glass ceramic into a restoration by a CAD/CAM (computer aided design/computer aided manufacturing) process, immersing the restoration into the molten salt 18 in the table 2, wherein the molten salt temperature is 420 ℃, and the immersion time is 2h.
Example 10
The raw materials can be selected from oxides, carbonate compounds, phosphate compounds thereof according to the formulation 10 in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace to be melted, the melting temperature is 1650 ℃, the melting time is 60min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again to be melted, the melting temperature is 1650 ℃, the melting time is 60min, the melted glass liquid is poured into a prepared Press die to be cooled and then subjected to heat treatment, the heat treatment temperature is 870 ℃, the heat treatment time is 30min, the heat-treated glass ceramic is processed into the restoration by a hot-Press casting process, the hot-Press casting temperature is 940 ℃, the hot-Press casting time is 15min, the restoration is immersed into the molten salt 20 in the table 2, the molten salt temperature is 430 ℃, and the immersion time is 2h.
Comparative examples 1 to 1
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds according to the formula 1 ingredient in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace for melting, the melting temperature is 1550 ℃, the melting time is 90min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again for melting, the melting temperature is 1550 ℃, the melting time is 90min, the melted glass liquid is poured into a prepared CAD mould, heat treatment is carried out after cooling, the heat treatment temperature is 680 ℃, the heat treatment time is 120min, and the glass ceramic after heat treatment is processed into a restoration body through a CAD/CAM process.
Comparative examples 1 to 2
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds according to formula 1 in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace to be melted, the melting temperature is 1550 ℃, the melting time is 90min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again to be melted, the melting temperature is 1550 ℃, the melting time is 90min, the melted glass liquid is poured into a prepared CAD mold, heat treatment is carried out after cooling, the heat treatment temperature is 680 ℃, the heat treatment time is 120min, the heat-treated glass ceramic is processed into a restoration by a CAD/CAM process, the restoration is immersed into the fused salt 1 in the table 2, the fused salt temperature is 400 ℃, and the immersion time is 3h.
Comparative example 2 to 1
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds according to formula 2 ingredients in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1650 ℃ for 30min, pouring molten glass liquid into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting at 1650 ℃ for 30min, pouring the molten glass liquid into a prepared Press die, cooling, and then carrying out heat treatment at 880 ℃ for 30min, processing the heat-treated glass ceramic into a prosthesis by a hot compression casting process, wherein the hot compression casting temperature is 910 ℃ and the hot compression casting time is 20min.
Comparative examples 2 to 2
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds according to formula 2 ingredients in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1650 ℃ for 30min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting at 1650 ℃ for 30min, pouring the molten glass into a prepared Press mold, cooling, carrying out heat treatment at 880 ℃ for 30min, processing the heat-treated glass ceramic into a prosthesis by a hot-Press casting process, carrying out hot-Press casting at 910 ℃ for 20min, immersing the prosthesis into molten salt 3 in table 2, wherein the molten salt temperature is 450 ℃, and the immersion time is 1h.
Comparative example 3-1
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds thereof according to formula 3 ingredients of table 1. Fully and uniformly mixing the raw materials, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1650 ℃ for 30min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible for melting at 1650 ℃ for 30min, pouring the molten glass into a prepared CAD (computer aided design) mould, cooling, and then carrying out heat treatment at 800 ℃ for 30min, and processing the glass ceramic subjected to heat treatment into a prosthesis by a CAD/CAM (computer aided design/computer aided manufacturing) process.
Comparative examples 3 and 2
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds thereof according to formula 3 ingredients of table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1650 ℃ for 30min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible for melting at 1650 ℃ for 30min, pouring the molten glass into a prepared CAD (computer aided design) mold, cooling, and then carrying out heat treatment at 800 ℃ for 30min, processing the heat-treated glass ceramic into a restoration by a CAD/CAM (computer aided design/computer aided manufacturing) process, immersing the restoration into the molten salt 5 in the table 2, wherein the temperature of the molten salt is 450 ℃, and the immersion time is 1h.
Comparative example 4-1
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof according to the formulation 4 of table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1550 ℃ for 90min, pouring molten glass liquid into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting at 1550 ℃ for 90min, pouring the molten glass liquid into a prepared Press die, cooling, and then carrying out heat treatment at 820 ℃ for 120min, processing the heat-treated glass ceramic into a restoration by a hot compression casting process, wherein the hot compression casting temperature is 950 ℃ and the hot compression casting time is 10min.
Comparative examples 4 to 2
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof according to the formulation 4 of table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace for melting, the melting temperature is 1550 ℃, the melting time is 90min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again for melting, the melting temperature is 1550 ℃, the melting time is 90min, the melted glass liquid is poured into a prepared Press die, the heat treatment is carried out after cooling, the heat treatment temperature is 820 ℃, the heat treatment time is 120min, the glass ceramic after the heat treatment is processed into a restoration by a hot-Press casting process, the hot-Press casting temperature is 950 ℃, the hot-Press casting time is 10min, the restoration is immersed into the fused salt 7 in the table 2, the fused salt temperature is 400 ℃, and the immersion time is 3h.
Comparative example 5-1
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof according to the formulation 5 ingredients of table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1630 ℃ for 40min, pouring the melted glass liquid into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible for melting at 1610 ℃ for 40min, pouring the melted glass liquid into a prepared CAD (computer aided design) mold, cooling, and then carrying out heat treatment at 780 ℃ for 100min, wherein the glass ceramic after heat treatment is processed into a prosthesis by a CAD/CAM (computer aided design/computer aided manufacturing) process.
Comparative examples 5 to 2
The raw materials can be selected from oxides, carbonate compounds, phosphate compounds thereof according to formulation 5 of table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace for melting, the melting temperature is 1630 ℃, the melting time is 40min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again for melting, the melting temperature is 1610 ℃, the melting time is 40min, the melted glass liquid is poured into a prepared CAD mold, heat treatment is carried out after cooling, the heat treatment temperature is 780 ℃, the heat treatment time is 100min, the glass ceramic after heat treatment is processed into a restoration by a CAD/CAM process, the restoration is immersed into the fused salt 9 in the table 2, the fused salt temperature is 410 ℃, and the immersion time is 2.5h.
Comparative example 6-1
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof, formulated according to formulation 6 of table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1600 ℃ for 60min, pouring molten glass liquid into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting at 1600 ℃ for 60min, pouring the molten glass liquid into a prepared Press die, cooling, and then carrying out heat treatment at 860 ℃ for 60min, processing the heat-treated glass ceramic into a restoration by a hot compression casting process, wherein the hot compression casting temperature is 930 ℃ and the hot compression casting time is 15min.
Comparative examples 6 to 2
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof, formulated according to formulation 6 of table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1600 ℃ for 60min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting at 1600 ℃ for 60min, pouring the molten glass into a prepared Press mold, cooling, carrying out heat treatment at 860 ℃ for 60min, processing the heat-treated glass ceramic into a restoration by a hot-Press casting process, carrying out hot-Press casting at 930 ℃ for 15min, immersing the restoration into the molten salt 11 in the table 2, wherein the molten salt temperature is 430 ℃ and the immersion time is 2.5h.
Comparative example 7-1
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof, formulated according to formulation 7 in table 1. Fully and uniformly mixing the raw materials, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1580 ℃ for 60min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible for melting at 1580 ℃ for 60min, pouring the molten glass into a prepared CAD (computer aided design) mould, cooling, and then carrying out heat treatment at 720 ℃ for 60min, and processing the glass ceramic subjected to heat treatment into a prosthesis by a CAD/CAM (computer aided design/computer aided manufacturing) process.
Comparative examples 7 to 2
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof, formulated according to formulation 7 in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace to be melted, the melting temperature is 1580 ℃, the melting time is 60min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again to be melted, the melting temperature is 1580 ℃, the melting time is 60min, the melted glass liquid is poured into a prepared CAD mold, after cooling, heat treatment is carried out, the heat treatment temperature is 720 ℃, the heat treatment time is 60min, the heat-treated glass ceramic is processed into a restoration by a CAD/CAM process, the restoration is immersed into the fused salt 13 in the table 2, the fused salt temperature is 410 ℃, and the immersion time is 1.5h.
Comparative example 8-1
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds thereof according to the formulation 8 in table 1. Fully and uniformly mixing the raw materials, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1620 ℃ for 70min, pouring the molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting at 1620 ℃ for 70min, pouring the molten glass into a prepared Press mould, cooling, and then carrying out heat treatment at 860 ℃ for 40min, processing the heat-treated glass ceramic into a restoration by a hot-Press casting process, wherein the hot-Press casting temperature is 920 ℃ and the hot-Press casting time is 20min.
Comparative examples 8 to 2
The raw materials can be selected from oxides, carbonate compounds and phosphate compounds thereof according to the formula 8 ingredients in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting, wherein the melting temperature is 1620 ℃, the melting time is 70min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting, wherein the melting temperature is 1620 ℃, the melting time is 70min, pouring the molten glass into a prepared Press mold, cooling, carrying out heat treatment, wherein the heat treatment temperature is 860 ℃, the heat treatment time is 40min, processing the glass ceramic after heat treatment into a restoration by a hot-Press casting process, wherein the hot-Press casting temperature is 920 ℃, the hot-Press casting time is 20min, immersing the restoration into the molten salt 15 in the table 2, the molten salt temperature is 420 ℃, and the immersion time is 1h.
Comparative example 9-1
The raw materials can be selected from oxides, carbonate compounds, phosphate compounds thereof according to formulation 9 in table 1. Fully and uniformly mixing the raw materials, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at the melting temperature of 1640 ℃ for 30min, pouring the molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible for melting at the melting temperature of 1640 ℃ for 30min, pouring the molten glass into a prepared CAD (computer aided design) die, cooling, and then carrying out heat treatment at the heat treatment temperature of 700 ℃ for 100min, and processing the glass ceramic subjected to heat treatment into a prosthesis by a CAD/CAM (computer aided design/computer aided manufacturing) process.
Comparative examples 9 to 2
The raw materials can be selected from oxides, carbonate compounds, phosphate compounds thereof according to formulation 9 in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at the melting temperature of 1640 ℃ for 30min, pouring molten glass into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible for melting at the melting temperature of 1640 ℃ for 30min, pouring the molten glass into a prepared CAD (computer-aided design) mold, cooling, performing heat treatment at the heat treatment temperature of 700 ℃ for 100min, processing the heat-treated glass ceramic into a restoration by a CAD/CAM (computer-aided design-computer-aided manufacturing) process, immersing the restoration into the molten salt 17 in the table 2, wherein the molten salt temperature is 420 ℃, and the immersion time is 2h.
Comparative example 10-1
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof, formulated according to formulation 10 in table 1. The preparation method comprises the steps of fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1650 ℃ for 60min, pouring molten glass liquid into cold water to obtain glass frit, drying the obtained glass frit, pouring the dried glass frit into the platinum crucible again for melting at 1650 ℃ for 60min, pouring the molten glass liquid into a prepared Press die, cooling, and then carrying out heat treatment at 870 ℃ for 30min, processing the heat-treated glass ceramic into a restoration by a hot compression casting process, wherein the hot compression casting temperature is 940 ℃ and the hot compression casting time is 15min.
Comparative example 10-2
The raw materials can be selected from the oxides, carbonate compounds, phosphate compounds thereof, formulated according to formulation 10 in table 1. The mixture is fully and uniformly mixed and poured into a platinum crucible, the platinum crucible is placed into a furnace for melting, the melting temperature is 1650 ℃, the melting time is 60min, the melted glass liquid is poured into cold water to obtain glass frit, the obtained glass frit is dried and poured into the platinum crucible again for melting, the melting temperature is 1650 ℃, the melting time is 60min, the melted glass liquid is poured into a prepared Press die, the heat treatment is carried out after cooling, the heat treatment temperature is 870 ℃, the heat treatment time is 30min, the heat treated glass ceramic is processed into a restoration by a hot-Press casting process, the hot-Press casting temperature is 940 ℃, the heat treatment time is 15min, the restoration is immersed into the molten salt 19 in the table 2, the molten salt temperature is 430 ℃, and the immersion time is 2h.
The base frit and colorant formulations for each example and comparative example are shown in table 1;
the formulations of the molten salts used in the examples and comparative examples are shown in Table 2;
the flexural strength and luminance results of the glass ceramics of each example and comparative example are shown in Table 3.
TABLE 1 base glass frit and colorant formulations
In Table 1, "-" indicates no inclusion.
TABLE 3 flexural Strength and Brightness results of the glass-ceramics
| Numbering | Flexural strength MPa | Luminance of a light | Numbering | Flexural strength MPa | Luminance of a light | Number of | Flexural strength MPa | Luminance of a light |
| Example 1 | 583.27 | I stage | Comparative examples 1 to 1 | 414.35 | I stage | Comparative examples 1 to 2 | 586.48 | I stage |
| Example 2 | 611.28 | I stage | Comparative example 2-1 | 442.73 | I level | Comparative examples 2 to 2 | 591.69 | I stage |
| Example 3 | 620.94 | I stage | Comparative example 3-1 | 443.61 | I stage | Comparative examples 3 to 2 | 634.36 | I stage |
| Example 4 | 631.39 | I stage | Comparative example 4-1 | 438.92 | I stage | Comparative examples 4 and 2 | 627.75 | I stage |
| Example 5 | 569.95 | I stage | Comparative example 5-1 | 433.52 | I level | Comparative examples 5 to 2 | 580.92 | I level |
| Example 6 | 579.45 | I stage | Comparative example 6-1 | 438.72 | I level | Comparative examples 6 to 2 | 582.67 | I level |
| Example 7 | 568.36 | I stage | Comparative example 7-1 | 428.65 | I level | Comparative examples 7 to 2 | 583.32 | I level |
| Example 8 | 572.74 | I stage | Comparative example 8-1 | 433.21 | I level | Comparative examples 8 to 2 | 569.58 | I level |
| Example 9 | 565.23 | I stage | Comparative example 9-1 | 411.96 | I stage | Comparative examples 9 to 2 | 568.76 | I level |
| Example 10 | 552.49 | I stage | Comparative example 10-1 | 424.56 | I level | Comparative examples 10 to 2 | 559.23 | I level |
As can be seen from Table 3, the glass-ceramics of the present application exhibited better fluorescence properties than comparative examples 1-1 to 10-2, in which ion exchange was not performed by immersion in molten salt and no fluorescent agent was added to the molten salt; as can be seen from example 1 and comparative examples 1 to 1, the strength of the glass-ceramic of example 1 of the present application is greatly improved by ion exchange in a molten salt.
The above description is only for the preferred embodiment of the present application and is not intended to limit the scope of the present application. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application are included in the protection scope of the present application.
Claims (20)
1. A method of making a fluorescent lithium silicate glass-ceramic, comprising:
(1) Mixing a base glass frit and a colorant, melting and water quenching to obtain a glass frit, wherein the base glass frit comprises the following components in parts by weight:
(2) Carrying out secondary melting and molding on the glass frit to obtain molded lithium silicate glass;
(3) Heat treating the formed lithium silicate glass;
(4) Processing the formed lithium silicate glass to obtain a restoration;
(5) Immersing the restoration in molten salt for 0.3-6h, and obtaining the fluorescent glass ceramic restoration with enhanced ion exchange through secondary crystallization, wherein the molten salt comprises sodium salt, potassium salt, cesium salt and/or rubidium salt and a fluorescent agent.
2. The method of claim 1, wherein the immersion time is 1-3 hours.
3. The production method according to claim 1, wherein the colorant comprises 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 At least one of NiO, mnO and 0 to 10wt% of the colorant based on the total weight of the base frit and the colorant.
4. The method of claim 1, wherein the colorant comprises Fe based on the total weight of the base frit and the colorant 2 O 3 The content of (A) is not more than 0.01wt%.
5. The production method according to claim 1, wherein the base glass frit comprises the following components by mass:
6. the manufacturing method according to claim 1, wherein the melting temperature of the base glass is 1350 to 1750 ℃ and the time is 10 to 120min.
7. The method according to claim 6, wherein the base glass has a melting temperature of 1550 to 1650 ℃ and a melting time of 30 to 90min.
8. The preparation method according to claim 1, wherein the temperature of the secondary melting is 1350-1750 ℃ and the time is 10-120min.
9. The method according to claim 8, wherein the temperature of the secondary melting is 1550 to 1650 ℃ and the time is 30 to 90min.
10. The preparation method according to claim 1, wherein the forming is computer aided design, the formed lithium silicate glass is subjected to heat treatment after forming, the heat treatment temperature is 600-900 ℃, the time is 20-180min, and then the formed lithium silicate glass is processed into the restoration by CAD/CAM.
11. The method of claim 10, wherein the heat treatment temperature is 680-800 ℃ and the time is 30-120min.
12. The method for preparing a lithium silicate material as claimed in claim 1, wherein the forming is performed by a pressing process, the formed lithium silicate glass is heat-treated at 700-900 ℃ for 20-180min after forming, and then processed into a restoration by hot press molding.
13. The method of claim 12, wherein the heat treatment temperature is 820-880 ℃ for 30-120min.
14. The method of claim 1, wherein the molten salt comprises a potassium salt comprising KNO 3 、K 2 CO 3 And K 2 SiCO 3 Said KNO based on the total weight of said molten salt 3 The content is 97-99wt%, the K is 2 CO 3 The content is 0-2wt%, the K is 2 SiCO 3 The content is 0-3wt%.
15. The method of claim 14, wherein K is 2 CO 3 The content is 0.5-1wt%, and the K is 2 SiCO 3 The content is 1-2wt%.
16. The production method according to claim 1, wherein a fluorescent agent contained in the molten salt is selected from at least one of nitrate hydrates of Eu, dy, tm, er, ho, yb, nd, sm, gd, the fluorescent agent being added in an amount of 1-2wt% based on the total weight of the molten salt.
17. The production method according to claim 1, wherein the temperature of the molten salt is 300-620 ℃.
18. The method of claim 17 in which the molten salt has a temperature of 400-450 ℃.
19. The method according to claim 12, wherein in the hot-press molding process, the hot-press molding temperature is 850-1050 ℃ and the time is 5-60min.
20. The method according to claim 19, wherein the hot press molding temperature is 910-950 ℃ and the time is 10-20min.
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|---|
| Glasses-ceramics of LAS(Li2O-Al2O3-SiO2) system enhanced by ion-exchange in KNO3 salt bath;Karolina Laczka等;《Journal of Non-crystalline Solids》;20150828;全文 * |
| Ion-exchanged glass microrods as hybrid SERS/fluorescence substrates for molecular beacon-based DNA detection;Simone Berneschi等;《Analytical and Bioanalytical Chemistry》;20210719;全文 * |
| 热离子交换型铝锗酸盐波导玻璃中钬离子的1.2μm近红外荧光发射;杨佳心等;《发光学报》;20181130;第39卷(第11期);全文 * |
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| CN113754288A (en) | 2021-12-07 |
| WO2023035692A1 (en) | 2023-03-16 |
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