CN112694253B - Starting glass, lithium silicate glass with core, preparation method and application thereof - Google Patents

Starting glass, lithium silicate glass with core, preparation method and application thereof Download PDF

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Publication number
CN112694253B
CN112694253B CN202011564799.9A CN202011564799A CN112694253B CN 112694253 B CN112694253 B CN 112694253B CN 202011564799 A CN202011564799 A CN 202011564799A CN 112694253 B CN112694253 B CN 112694253B
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glass
lithium silicate
fluorescent
silicate glass
core
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CN112694253A (en
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张兵
张曦
宋锡滨
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Shandong Sinocera Functional Material Co Ltd
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Shandong Sinocera Functional Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/836—Glass
    • 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
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
    • C03C4/0021—Compositions for glass with special properties for biologically-compatible glass for dental use
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
    • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Abstract

The invention provides starting glass, lithium silicate glass with a core, and a preparation method and application thereof, and belongs to the technical field of fluorescent materials. The lithium silicate glass with the core is prepared by uniformly mixing basic glass components and fluorescent components, melting and water quenching, and remelting the water quenched glass frit in an air atmosphere but no reducing atmosphere to obtain glass liquid; pouring the obtained glass liquid into a specific mould for molding, cooling the molded ceramic block, and performing heat treatment to obtain the ceramic block. According to the preparation method provided by the invention, the compound of the fluorescent element is introduced into the raw material, so that no fluorescent powder is required to be added, the required fluorescent effect can be achieved without reducing atmosphere in the melting process, the process is simple, and the fluorescent color is easy to control. The obtained lithium silicate glass with the core can be effectively used in the preparation of dental restoration materials, and can simulate the effect of gradual change of the color of natural teeth from neck to cutting off, thereby achieving the fluorescent effect similar to that of the natural teeth and effectively improving the aesthetic effect.

Description

Starting glass, lithium silicate glass with core, preparation method and application thereof
Technical Field
The invention belongs to the technical field of fluorescent materials, and particularly relates to starting glass, lithium silicate glass with cores, and a preparation method and application thereof.
Background
Lithium disilicate (Li) 2 Si 2 O 5 ) Glass ceramic is widely applied in the field of dental restoration, has the permeability of glass and the strength of ceramic, has unique advantages in aesthetic restoration, and especially has the advantages of minimally invasive restoration or ultrathin veneering, and compared with the traditional zirconia material, the texture and opalescence of the lithium disilicate glass ceramic material are more obvious.
Dental restorative materials generally mimic natural teeth in all respects, thereby achieving a simulated effect. The natural teeth of people have fluorescent effect, and can emit fluorescent light under the irradiation of ultraviolet light with a certain wavelength range, so that the sunlight contains ultraviolet light components, and artificial light sources in special occasions can also generate similar ultraviolet light components. In these cases, if a dental restoration material having no fluorescence or weak fluorescence effect is used, the effect is significantly different from that of a natural tooth, and thus, the dental restoration material cannot be coordinated with other natural teeth, and thus, the simulated effect cannot be obtained. Thus, only dental restorative materials having a fluorescent effect can achieve an effect approaching that of natural teeth. However, the dental restoration materials on the market have little autofluorescence effect, most of the known restoration materials are realized by matching fluorescent glaze, but the glaze layer is easy to wear, and can wear off in a period of several months, so that the restoration and coordination effects of teeth are more affected, the glaze layer is thinner, and the color of the restoration body can interfere with the fluorescence effect of the glaze layer.
At present, a method for realizing a fluorescent effect of lithium disilicate glass ceramic mainly comprises the steps of introducing a fluorescent agent, for example, introducing the fluorescent agent through a fusion method, and introducing the fluorescent agent through a sintering method, wherein the fluorescent agent is added in the fusion stage, but a matrix material in the fluorescent agent often influences the crystallization process of a glass ceramic material, so that crystallization is uneven, and the light transmittance and the strength of the material are reduced; the latter may have particle size mismatch or refractive index mismatch, resulting in reduced light transmittance, and even some fluorescent agents are added and sintered in a reducing atmosphere, which has high sintering requirements, and is difficult to realize industrial production or has high cost.
Disclosure of Invention
The invention provides starting glass, lithium silicate glass with a core, a preparation method and application thereof, wherein fluorescent element compounds are introduced into raw materials in the preparation method, no fluorescent powder is needed to be added, and the melting process can achieve the required fluorescent effect without reducing atmosphere, and the preparation method is simple in process and easy to control fluorescent color.
In order to achieve the above object, the present invention provides a starting glass comprising or consisting of the following components in weight percent: 97% -99.9% of base glass component and 0.1% -3% of fluorescent component.
Preferably, the base glass component comprises or consists of the following components in percentage by weight:
SiO 2 48-78％
Li 2 O 12-20.5％
P 2 O 5 0.5-12.5％
K 2 O 0.5-8％
Al 2 O 3 0.5-6％
ZrO 2 0-16％
ZnO 0.5-8.5％
Tb 4 O 7 0.2-3.2％。
in the above embodiments, the base glass component may preferably further comprise an alkali metal oxide for adjusting the thermal expansion coefficient, generally referred to as Li-removal 2 Alkali metal oxide other than O, which may be selected from Na 2 O、K 2 O、Cs 2 O、Rb 2 At least one of O, preferably K 2 O. In addition to this, the base glass component comprises Al which can adjust the optical properties, in particular the light transmission 2 O 3 ZnO capable of adjusting softening point of glass ceramic and yellow colorant Tb 4 O 7 。
It will be appreciated that the content of each component in the above base glass component may be adjusted accordingly within the above range as desired, for example SiO 2 The content of (c) may also be 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77% or any point value within the above ranges; li (Li) 2 The O content may also be 13, 14, 15, 16, 17, 18, 19, 20% or any point value within the above ranges; p (P) 2 O 5 The content of (2) may also be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12% or any point value within the above range; k (K) 2 The O content may also be 1, 2, 3, 4, 5, 6, 7% or any point value within the above ranges; al (Al) 2 O 3 The content of (2) may also be 1, 2, 3, 4, 5% or any point value within the above range; zrO (ZrO) 2 The content of (2) may also be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15% or any point value within the above range; content of ZnOBut also 1, 2, 3, 4, 5, 6, 7, 8% or any point value within the above range; tb (Tb) 4 O 7 The content of (c) may also be 0.5, 1, 1.5, 2, 2.5, 3% or any point value within the above range.
Preferably, the base glass component comprises or consists of the following components in percentage by weight:
SiO 2 60-72％
Li 2 O 13-18％
P 2 O 5 2-7％
K 2 O 2-6％
Al 2 O 3 1-4％
ZrO 2 0.5-10％
ZnO 2-6％
Tb 4 O 7 0.3-1.8％。
it will be appreciated that further limiting the amount of each component to the ranges set forth above provides a base glass component having better light transmission.
Preferably, the fluorescent component is selected from the group consisting of oxides, carbonates, nitrates, and phosphates of at least two elements of Sm, dy, er, yb, nd, tm, eu. It will be appreciated that the fluorescent component added in this embodiment is introduced as a compound of fluorescent elements, without the need for external fluorescent agents. In this way, in the high-temperature melting process, fluorescent ions can enter the reticular structure of the matrix glass and generate transition under the excitation of light with a certain wavelength, and a fluorescent effect is emitted.
Preferably, the composition comprises or consists of the following components in percentage by weight: 98.5 to 99.8 percent of basic glass component and 0.2 to 1.5 percent of fluorescent component. It will be appreciated that the above base glass components 98.6%, 98.7%, 98.8%, 98.9%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7% or any point in the above range, and the content of the fluorescent component may be adjusted accordingly within the above range, for example, the addition amount may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4% or any point in the above range.
The invention also provides lithium silicate glass with a core, which is obtained by adding a nucleating agent into a basic glass component of the starting glass according to the technical scheme and then performing heat treatment on the basic glass component.
Preferably, the nucleating agent is selected from the group consisting of P 2 O 5 、TiO 2 、Nb 2 O 5 、ZrO 2 At least one of the above and any mixture thereof, and the addition amount of the nucleating agent is 2-10wt%. It will be appreciated that the amount of nucleating agent added may be adjusted accordingly within the above ranges depending on the actual situation, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9% or any point value within the above ranges.
Preferably, the temperature of the heat treatment is 500-950 ℃ and the treatment time is 3-360min. It will be appreciated that the temperature of the heat treatment may be adjusted accordingly within the above range depending on the actual situation, and may be, for example, 550, 600, 650, 700, 750, 800, 850, 900 ℃ or any point value within the above range.
The invention also provides a preparation method of the lithium silicate glass with the core according to any one of the technical schemes, which comprises the following steps:
uniformly mixing a basic glass component and a fluorescent component, melting and water quenching, and remelting the water quenched glass frit in an air atmosphere but no reducing atmosphere to obtain molten glass;
pouring the obtained glass liquid into a specific mold for molding, cooling the molded ceramic block, and performing heat treatment to obtain the lithium silicate glass with the core.
It will be appreciated that the tiles produced by the above method may be press tiles, in which case the phosphor-effect restoration may be produced by a hot-die casting process, or CAD tiles, in which case the phosphor-effect restoration may be produced by a CAD/CAM process (with or without crystallization). For both hot die casting processes and CAD/CAM processes, which are well known to those skilled in the art, for example, the hot die casting process may be specifically: preparing a wax pattern of the prosthesis, inserting a casting channel on the wax pattern, embedding, solidifying the embedding material, burning the ring, then placing the press porcelain block and the embedding ring into a die casting furnace, and pressing the melted press porcelain block into a cavity left after the wax pattern is burned off at high temperature; the CAD/CAM process may be: and (3) putting the CAD porcelain blocks into a processing machine, and processing corresponding repairing bodies by using a turning needle according to a program. Of course, the implementation of the above process is not limited to the above list, and may be implemented in other reasonable manners.
Preferably, the melting stage of the base glass component and the fluorescent component further comprises the step of adding additives and/or colorants.
Preferably, the additive is added in an amount of 0 to 17.5% by weight, and the colorant is added in an amount of 0 to 5.5% by weight. It will be appreciated that the content of the above additives and colorants may be adjusted accordingly within the above ranges as desired, for example, the additives may be added in amounts of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16% or any point value within the above ranges; the colorant may also be added in an amount of 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5% or any point value within the above ranges.
Preferably, the additive is selected from alkaline earth metal oxides, oxides of trivalent elements, oxides of tetravalent elements, oxides of pentavalent elements and/or oxides of hexavalent elements.
Preferably, the alkaline earth metal oxide is selected from at least one of CaO, baO, mgO, srO and any mixtures thereof; the oxide of trivalent element is other than Al 2 O 3 Oxides of other trivalent elements, selected from B 2 O 3 、Y 2 O 3 、La 2 O 3 、Bi 2 O 3 At least one of (a) and any mixtures thereof; the oxide of tetravalent element is SiO-removed 2 、ZrO 2 Oxides of tetravalent elements other than SnO 2 、TiO 2 、GeO 2 At least one of (a) and (b); the oxides of the pentavalent elements are other than P 2 O 5 Oxides of pentavalent elements other than Nb 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The oxides of hexavalent elements are selected from WO 3 And/or MoO 3 。
Preferably, the colorant is selected from at least one of yellow colorant, red colorant and gray colorant.
Preferably, the yellow colorant is selected from CeO 2 、Pr 2 O 3 、V 2 O 5 At least one of zirconium vanadium yellow and zirconium praseodymium yellow; the red colorant is selected from Er 2 O 3 At least one of chrome-tin red and spinel red; the grey colorant is selected from MnO, niO, nd 2 O 3 At least one of them.
Preferably, the temperature for uniformly mixing the basic glass components and the fluorescent components to melt is 1350-1650 ℃ and the heat preservation time is 30-120min. It can be understood that the melting temperature and the holding time can be adjusted correspondingly in the above range according to practical situations, for example, the temperature can also be 1400, 1450, 1500, 1550, 1600 ℃ or any point value in the above range; the incubation time may also be 40, 50, 60, 70, 80, 90, 100, 110 minutes or any point value within the above ranges.
Preferably, the glass frit is remelted at 1350-1650 ℃ for 30-120min. It will be appreciated that the remelting temperature and holding time may be adjusted accordingly in the above ranges according to practical situations, for example, the temperature may also be 1400, 1450, 1500, 1550, 1600 ℃ or any point value in the above ranges; the incubation time may also be 40, 50, 60, 70, 80, 90, 100, 110 minutes or any point value within the above ranges.
Preferably, the temperature of the heat treatment is 500-950 ℃, preferably 600-900 ℃, and the heat treatment time is 3-360min. It will be appreciated that the temperature of the heat treatment may be adjusted accordingly within the above range depending on the actual situation, and may be, for example, 550, 600, 650, 700, 750, 800, 850, 900 ℃ or any point value within the above range.
Preferably, the resulting lithium silicate glass having a core comprises lithium silicate glass and/or lithium silicate glass ceramic.
The invention also provides application of the lithium silicate glass with the core prepared by the method according to any one of the technical schemes in preparation of dental restoration materials.
The invention also provides a dental prosthesis, which is prepared from the lithium silicate glass with the core according to any one of the technical schemes or the lithium silicate glass with the core prepared by the preparation method according to any one of the technical schemes. It is understood that dental restorations including, but not limited to, inlays, onlays, veneers, partial crowns, facets, or abutments may be prepared from the lithium silicate glass with core provided by the present invention.
Compared with the prior art, the invention has the advantages and positive effects that:
the lithium silicate glass with the core is prepared by adopting a melting method, and is prepared by simultaneously melting a basic glass material and fluorescent components in the melting stage, quenching the basic glass material and the fluorescent components into glass frit by water, then melting the glass frit into glass liquid, pouring the glass liquid into a mold for molding, and then performing heat treatment. The method introduces the fluorescent element compound into the raw materials, does not need to synthesize fluorescent powder, can achieve the required fluorescent effect without reducing atmosphere in the melting process, has simple process, is easy for batch production, and has easily controlled fluorescent color. The prepared lithium silicate glass material can simulate the gradual change effect of the color of natural teeth from neck to cutting off, thereby achieving the fluorescent effect similar to that of the natural teeth and effectively improving the aesthetic effect.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1 (fusion method press)
Taking all raw material components of the base glass according to the component content shown in the following table 1, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1350 ℃, and melting for 30min to homogenize glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit at 1550 ℃ for 60min, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 900 ℃ to obtain the press ceramic block. The press ceramic block can be used for preparing a lithium disilicate glass material restoration with a fluorescent effect through a hot die casting process.
TABLE 1
Composition of the components Content wt%
SiO 2 65
Li 2 O 15
P 2 O 5 5
K 2 O 3
Al 2 O 3 3
ZrO 2 1.3
ZnO 5
Tb 4 O 7 1.2
V 2 O 5 0.4
Er 2 O 3 0.7
Tm 2 O 3 0.2
Eu 2 O 3 0.2
Example 2 (melting method CAD primary crystallization)
Taking all raw material components of the base glass according to the component content shown in the following table 2, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1500 ℃, and melting for 120min to homogenize glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit for 30min at 1650 ℃, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 850 ℃ to obtain the CAD ceramic block. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration with fluorescent effect through a CAD/CAM process, and crystallization treatment is not needed.
TABLE 2
Composition of the components Content wt%
SiO 2 60
Li 2 O 14
P 2 O 5 4
K 2 O 5
Al 2 O 3 1
ZrO 2 0.5
ZnO 2
Tb 4 O 7 0.3
BaO 2
MgO 2
La 2 O 3 0.2
TiO 2 2
WO 3 2
CeO 2 1.5
MnO 2
Tm 2 O 3 1
Eu 2 O 3 0.5
Example 3 (melting method CAD secondary crystallization)
Taking all raw material components of the base glass according to the component content shown in the following table 3, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1650 ℃ and the melting time to 80 minutes, homogenizing glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit for 120min at 1350 ℃, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 500 ℃ to obtain the CAD ceramic block. The CAD porcelain block is subjected to CAD/CAM technology, and crystallization treatment at 900 ℃ is required, so that the lithium disilicate glass material prosthesis with fluorescent effect can be prepared.
TABLE 3 Table 3
Composition of the components Content wt%
SiO 2 70
Li 2 O 13
P 2 O 5 2
K 2 O 4
Al 2 O 3 2
ZrO 2 0.5
ZnO 2
Tb 4 O 7 0.3
CaO 2
La 2 O 3 0.5
TiO 2 0.5
Nb 2 O 5 0.3
MoO 3 1
Pr 2 O 3 1
NiO 0.5
Tm 2 O 3 0.4
Example 4 (fusion method press)
Taking all raw material components of the base glass according to the component content shown in the following table 4, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1650 ℃ and the melting time to 120min, homogenizing glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit for 80min at 1550 ℃, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 840 ℃ to obtain a press ceramic block. The press ceramic block can be used for preparing a lithium disilicate glass material restoration with a fluorescent effect through a hot die casting process.
TABLE 4 Table 4
Figure BDA0002860297810000091
Figure BDA0002860297810000101
Example 5 (fusion process CAD primary crystallization)
Taking all raw material components of the base glass according to the component content shown in the following table 5, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; placing the mixed raw materials into a platinum crucible, placing the platinum crucible into a furnace for melting, controlling the melting temperature to 1550 ℃ and the melting time to 120min, homogenizing glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit at 1450 ℃ for 60min, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 880 ℃ to obtain the CAD ceramic block. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration with fluorescent effect through a CAD/CAM process, and crystallization treatment is not needed.
TABLE 5
Composition of the components Content wt%
SiO 2 62
Li 2 O 14
P 2 O 5 7
K 2 O 3
Al 2 O 3 2
ZrO 2 2
ZnO 3
Tb 4 O 7 0.6
BaO 2
MgO 0.5
SrO 0.5
La 2 O 3 1
Nb 2 O 5 0.1
MoO 3 0.5
CeO 2 0.4
NiO 0.6
Nd 2 O 3 0.4
Eu 2 O 3 0.4
Example 6 (fusion process CAD secondary crystallization)
Taking all raw material components of the base glass according to the component content shown in the following table 6, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; placing the mixed raw materials into a platinum crucible, placing the platinum crucible into a furnace for melting, controlling the melting temperature to 1450 ℃, and melting for 30min to homogenize glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit at 1600 ℃ for 60min, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 680 ℃ to obtain the CAD ceramic block. The CAD porcelain block is subjected to CAD/CAM technology, and crystallization treatment at 860 ℃ is required, so that the lithium disilicate glass material prosthesis with fluorescent effect can be prepared.
TABLE 6
Composition of the components Content wt%
SiO 2 61
Li 2 O 13
P 2 O 5 5
K 2 O 6
Al 2 O 3 2
ZrO 2 1
ZnO 2
Tb 4 O 7 1.4
CaO 2
BaO 1.3
SrO 2
TiO 2 0.5
WO 3 0.5
V 2 O 5 0.5
Er 2 O 3 0.5
MnO 0.5
Dy 2 O 3 0.4
Yb 2 O 3 0.4
Example 7 (fusion method press)
Taking all raw material components of the base glass according to the component content shown in the following table 7, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1500 ℃, and melting for 60 minutes to homogenize glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit for 120min at 1400 ℃, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 850 ℃ to obtain a press ceramic block. The press ceramic block can be used for preparing a lithium disilicate glass material prosthesis with a fluorescent effect through a hot die casting process.
TABLE 7
Figure BDA0002860297810000111
Figure BDA0002860297810000121
Example 8 (fusion process CAD primary crystallization)
Taking all raw material components of the base glass according to the component content shown in the following table 8, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1350 ℃, and melting for 120min to homogenize glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit for 30min at 1350 ℃, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 900 ℃ to obtain the CAD ceramic block. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration with fluorescent effect through a CAD/CAM process, and crystallization treatment is not needed.
TABLE 8
Composition of the components Content wt%
SiO 2 63
Li 2 O 13
P 2 O 5 2
K 2 O 2
Al 2 O 3 1
ZrO 2 10
ZnO 4
Tb 4 O 7 1.1
CaO 1
MgO 1
TiO 2 0.7
V 2 O 5 0.5
NiO 0.5
Tm 2 O 3 0.2
Example 9 (melting method CAD secondary crystallization)
Taking all raw material components of the base glass according to the component content shown in the following table 9, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1350 ℃, and melting for 120min to homogenize glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit at 1450 ℃ for 60min, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 660 ℃ to obtain the CAD ceramic block. The CAD porcelain block is subjected to CAD/CAM technology, and crystallization treatment at 840 ℃ is required, so that the lithium disilicate glass material prosthesis with fluorescent effect can be prepared.
TABLE 9
Composition of the components Content wt%
SiO 2 62
Li 2 O 13
P 2 O 5 3
K 2 O 4
Al 2 O 3 1.5
ZrO 2 0.5
ZnO 6
Tb 4 O 7 1
CaO 2
BaO 2
MgO 2
SrO 1
Er 2 O 3 0.5
Sm 2 O 3 0.5
Eu 2 O 3 1
Comparative example 1 (fusion method press)
Taking all raw material components of the base glass according to the component content shown in the following table 10, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1500 ℃, and melting for 60 minutes to homogenize glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit for 120min at 1400 ℃, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 850 ℃ to obtain a press ceramic block. The press ceramic block can be used for preparing a lithium disilicate glass material restoration without a fluorescence effect through a hot die casting process. The content of the fluorescent component deleted in the comparative example was supplemented in the content of ZnO mainly because ZnO did not affect the intensity and transmittance while not producing a fluorescent effect, as in the following examples.
Table 10
Figure BDA0002860297810000131
/>
Figure BDA0002860297810000141
Comparative example 2 (melting method CAD primary crystallization)
Taking all raw material components of the base glass according to the component content shown in the following table 11, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1350 ℃, and melting for 120min to homogenize glass liquid, and then pouring into cold water to obtain glass frit; and melting the glass frit for 30min at 1350 ℃, casting into a die for molding, and crystallizing the ceramic block in a box furnace at 900 ℃ to obtain the CAD ceramic block. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration without fluorescence effect through CAD/CAM technology, and crystallization treatment is not needed.
TABLE 11
Composition of the components Content wt%
SiO 2 63
Li 2 O 13
P 2 O 5 2
K 2 O 2
Al 2 O 3 1
ZrO 2 10
ZnO 4.2
Tb 4 O 7 1.1
CaO 1
MgO 1
TiO 2 0.7
V 2 O 5 0.5
NiO 0.5
Comparative example 3 (sintering method CAD secondary crystallization)
Taking all raw material components of the base glass according to the component content shown in the following table 12, selecting oxide, carbonate or phosphate and the like of all raw materials, and fully and uniformly mixing; putting the mixed raw materials into a platinum crucible, putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1650 ℃ and the melting time to 40min, homogenizing glass liquid, and then pouring into cold water to obtain glass frit; coarse grinding and fine grinding to obtain a frit with a particle size of D 50 =20 μm, willMixing the ground glass powder with fluorescent powder, putting the mixture into a prepared mold, and performing dry pressing molding for one time under the pressure of 100MPa; sintering the biscuit in a vacuum atmosphere furnace at 850 ℃ and controlling the vacuum degree at 500Pa. The CAD porcelain block can be used for preparing the lithium disilicate glass material restoration with fluorescent effect through a CAD/CAM process, and crystallization treatment is not needed.
Table 12
Composition of the components Content wt%
SiO 2 64
Li 2 O 13
P 2 O 5 2
K 2 O 3.5
Al 2 O 3 2
ZrO 2 1
ZnO 3
Tb 4 O 7 0.5
BaO 3.5
MgO 1.2
SrO 0.8
La 2 O 3 1
TiO 2 1.5
Nb 2 O 5 1
WO 3 0.5
Pr 2 O 3 0.6
MnO 0.4
Fluorescent powder 0.5
TABLE 13 Crystal phases corresponding to different heat treatment temperatures in the above examples and comparative examples
Temperature of primary heat treatment Corresponding to the main crystal phase Secondary heat treatment temperature Corresponding to the main crystal phase
Example 1 900 Lithium disilicate
Example 2 850 Lithium disilicate
Example 3 500 Lithium metasilicate 900 Lithium disilicate
Example 4 840 Lithium disilicate
Example 5 880 Lithium disilicate
Example 6 680 Lithium metasilicate 860 Lithium disilicate
Example 7 850 Lithium disilicate
Example 8 900 Lithium disilicate
Example 9 660 Lithium metasilicate 840 Lithium disilicate
Comparative example 1 850 Lithium disilicate
Comparative example 2 900 Lithium disilicate
Comparative example 3 850 Lithium disilicate
Performance testing
The light transmittance, the intensity and the fluorescence of the prostheses prepared in the above examples and comparative examples were measured, and the results are shown in table 14, and the specific measurement methods are as follows:
the strength testing method comprises the following steps: the biaxial bending strength M of each specimen was calculated by the following formula with reference to the ISO6872-2015 standard.
Figure BDA0002860297810000161
Figure BDA0002860297810000162
/>
Figure BDA0002860297810000163
In the formula:
m-flexural strength, MPa;
w is the maximum load when the sample breaks, N;
d-thickness of the fracture initiation point sample, mm;
v-poisson ratio (v=0.36 for zirconia ceramic material);
r 1 -support circle radius, mm;
r 2 -radius of the ram, mm;
r 3 sample radius, mm.
The light transmittance test method comprises the following steps: reference to GBT2680-1994 standard
The test method is that the sample is made into a phi 14 multiplied by 1.0 sample wafer, and the X-Rite color i7 desk type spectrophotometer is adopted to measure the full light transmittance of the sample. The instrument is provided with a light source which is a pulse xenon lamp, a calibrated D65 light source, the spectrum range is 360-750nm, and the wavelength interval is 10nm. The resolution of the photometry was 0.001%. The transmittance in the range of 6mm in the center diameter of each test piece was measured.
Fluorescence test method:
the fluorescence effect was visualized under a UV lamp box with a wavelength of 365 nm.
TABLE 14 Performance test results of the prostheses prepared in the examples and comparative examples described above
Figure BDA0002860297810000164
Figure BDA0002860297810000171
In the above table 1, in the comparative examples 1 to 3, the comparative example 1 is a high-transmittance formulation without adding a fluorescent agent, the comparative example 2 is a low-transmittance formulation without adding a fluorescent agent, and the comparative example 3 is a formulation with external fluorescent powder, and as can be seen by comparing with the comparative examples 1 and 2, the restoration prepared in the embodiment of the present invention can achieve a fluorescence effect while the transmittance and the intensity both meet the standards, and as can be seen by comparing with the comparative example 3, the restoration prepared in the embodiment of the present invention has a more uniform fluorescence effect on the premise that the transmittance and the intensity are not reduced.

Claims (17)

1. The lithium silicate glass with the core is characterized in that a nucleating agent is added into a basic glass component of initial glass for melting and water quenching, and after water quenching, the glass is remelted in an air atmosphere but no reducing atmosphere, and then the glass is subjected to heat treatment to obtain the lithium silicate glass;
wherein the starting glass comprises the following components in percentage by weight: 97% -99.9% of base glass component and 0.1% -3% of fluorescent component;
the fluorescent component is selected from oxide, carbonate, nitrate or phosphate of at least two elements in Sm, dy, er, yb, nd, tm, eu;
the base glass component comprises the following components in percentage by weight:
SiO 2 48-78%
Li 2 O12-20.5%
P 2 O 5 0.5-12.5%
K 2 O0.5-8%
Al 2 O 3 0.5-6%
ZrO 2 0-16%
ZnO0.5-8.5%
Tb 4 O 7 0.2-3.2%。
2. the lithium silicate glass with core according to claim 1, wherein the base glass component comprises, in weight percent:
SiO 2 60-72%
Li 2 O13-18%
P 2 O 5 2-7%
K 2 O2-6%
Al 2 O 3 1-4%
ZrO 2 0.5-10%
ZnO2-6%
Tb 4 O 7 0.3-1.8%。
3. the lithium silicate glass with core according to claim 1, comprising the following components in weight percent: 98.5 to 99.8 percent of basic glass component and 0.2 to 1.5 percent of fluorescent component.
4. The lithium silicate glass with core according to claim 1, wherein the nucleating agent is selected from the group consisting of P 2 O 5 、TiO 2 、Nb 2 O 5 、ZrO 2 At least one of the above and any mixture thereof, and the addition amount of the nucleating agent is 2-10wt%.
5. The lithium silicate glass with core according to claim 1, wherein the heat treatment is performed at a temperature of 500-950 ℃ for a time of 3-360min.
6. The method for producing a lithium silicate glass having a core according to any one of claims 1 to 5, comprising the steps of:
uniformly mixing a basic glass component, a nucleating agent and a fluorescent component, melting and water quenching, and remelting the water quenched glass frit in an air atmosphere but no reducing atmosphere to obtain glass liquid;
pouring the obtained glass liquid into a specific mold for molding, cooling the molded ceramic block, and performing heat treatment to obtain the lithium silicate glass with the core.
7. The method according to claim 6, further comprising the step of adding additives and/or colorants during the melting of the base glass component and the fluorescent component.
8. The preparation method according to claim 7, wherein the additive is added in an amount of 0 to 17.5% by weight and the colorant is added in an amount of 0 to 5.5% by weight.
9. The method of claim 7, wherein the additive is selected from the group consisting of alkaline earth oxides, oxides of trivalent elements, oxides of tetravalent elements, oxides of pentavalent elements, and/or oxides of hexavalent elements.
10. The method of claim 9, wherein the alkaline earth metal oxide is selected from at least one of CaO, baO, mgO, srO and any mixtures thereof; the oxide of trivalent element is other than Al 2 O 3 Oxides of other trivalent elements, selected from B 2 O 3 、Y 2 O 3 、La 2 O 3 、Bi 2 O 3 At least one of (a) and any mixtures thereof; the oxide of tetravalent element is SiO-removed 2 、ZrO 2 Oxides of tetravalent elements other than SnO 2 、TiO 2 、GeO 2 At least one of (a) and (b); the oxides of the pentavalent elements are other than P 2 O 5 Oxides of pentavalent elements other than Nb 2 O 5 The method comprises the steps of carrying out a first treatment on the surface of the The oxides of hexavalent elements are selected from WO 3 And/or MoO 3 。
11. The method of preparing according to claim 7, wherein the colorant is at least one selected from the group consisting of yellow colorant, red colorant and gray colorant.
12. The method of claim 11, wherein the yellow colorant is selected from CeO 2 、Pr 2 O 3 、V 2 O 5 At least one of zirconium vanadium yellow and zirconium praseodymium yellow; the red colorant is selected from Er 2 O 3 At least one of chrome-tin red and spinel red; the grey color isThe colour agent is selected from MnO, niO, nd 2 O 3 At least one of them.
13. The method according to claim 6, wherein the temperature at which the base glass component and the fluorescent component are uniformly mixed and melted is 1350-1650 ℃ and the holding time is 30-120min.
14. The method according to claim 6, wherein the glass frit is remelted at 1350 ℃ to 1650 ℃ for 30 to 120 minutes.
15. The method of any one of claims 6 to 14, wherein the resulting lithium silicate glass having a core comprises lithium silicate glass and/or lithium silicate glass ceramic.
16. Use of a lithium silicate glass with a core according to any one of claims 1-5 or a lithium silicate glass with a core prepared by a preparation method according to any one of claims 6-14 in the preparation of dental restorative materials.
17. Dental restoration, characterized in that it is made of a lithium silicate glass with a core according to any one of claims 1 to 5 or a lithium silicate glass with a core according to any one of claims 6 to 14.
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