CN113024120B - Preparation method of lithium disilicate glass ceramic with transmittance and color gradient effect - Google Patents

Preparation method of lithium disilicate glass ceramic with transmittance and color gradient effect Download PDF

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CN113024120B
CN113024120B CN202110350762.4A CN202110350762A CN113024120B CN 113024120 B CN113024120 B CN 113024120B CN 202110350762 A CN202110350762 A CN 202110350762A CN 113024120 B CN113024120 B CN 113024120B
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colorant
lithium disilicate
sintering
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CN113024120A (en
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宋锡滨
张曦
张兵
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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
    • 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
    • C03C10/0009—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 silica as main constituent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/78—Pigments
    • 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
    • A61K6/833—Glass-ceramic composites
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    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments

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Abstract

The invention provides a preparation method of lithium disilicate glass ceramic with transmittance and color gradient effects, belonging to the technical field of lithium silicate glass. The method comprises the following steps: weighing the basic glass components according to the formula, uniformly mixing, and melting at high temperature; water quenching the fully melted glass liquid into glass frits, and grinding the frits to different required particle sizes to prepare basic glass powder; uniformly mixing three or more than three glass powders with gradient particle size and corresponding colorants and/or fluorescent agents with gradient particle size, sequentially adding into a mold, and dry-pressing or dry-pressing combined isostatic pressing; and sintering the formed blank in a vacuum atmosphere to obtain the lithium disilicate glass ceramic. The method provided by the invention controls the mixing of the colorants with different contents and the glass powder with different particle sizes in a layer-by-layer overlapping mode, realizes the effect of gradual change of light transmittance, and can ensure that the gradual change effect of the transmittance and the color of the lithium disilicate glass ceramic is consistent with the optical effect of natural teeth.

Description

Preparation method of lithium disilicate glass ceramic with transmittance and color gradient effect
Technical Field
The invention belongs to the technical field of lithium silicate glass, and particularly relates to a preparation method of lithium disilicate glass ceramic with transmittance and color gradient effects.
Background
Lithium disilicate (Li) 2 O·2SiO 2 ) The glass ceramic is formed by adding a nucleating agent to a base glass and forming Li 2 Si 2 O 5 Polycrystalline material in the main crystal phase, li 2 Si 2 O 5 The crystals are uniformly distributed in the glass matrix, so that the glass ceramic has higher mechanical strength and excellent optical performance, has better aesthetic effect compared with zirconia, and is widely applied to the field of dental repair. The color of natural teeth of a person is changed in the growing process, the color gradually becomes lighter and the transmittance gradually improves from the neck to the cut end, and the corresponding lithium silicate glass ceramic restoration can better achieve the simulation effect by the layered gradual change effect.
At present, lithium disilicate glass ceramics are mainly prepared by a casting method, mixed raw materials are melted into molten glass at high temperature, then the molten glass is poured into a grinding tool for forming, and a machinable CAD/CAM block or a hot-press-cast press product is obtained through crystallization treatment, and the layering gradual change effect is difficult to realize by the method. Lithium disilicate glass ceramics can also be prepared by a sintering method, but in the sintering method, the granularity of base glass powder influences the light transmittance of the lithium disilicate glass ceramics, and within a certain granularity range, the transmittance is reduced along with the increase of the granularity.
CN 111792847A discloses a method for producing a multicolored glass-ceramic blank for dental use having lithium silicate as the main crystalline phase, in which a multicolored lithium silicate glass-ceramic is produced by introducing lithium silicate glass-ceramic powders or suspensions of different colors, which has a gradual effect in color, but the transparency of which does not change and does not very well achieve the optical effect of simulating natural teeth.
Disclosure of Invention
The invention provides a preparation method of lithium disilicate glass ceramic with transmittance and color gradient effects, which controls the mixing of colorants with different contents and glass powder with different particle sizes in a mode of powder material layer by layer superposition to realize the effect of light transmittance gradient and ensure that the transmittance and color gradient effect of the lithium disilicate glass ceramic is consistent with the optical effect of natural teeth.
In order to achieve the above purpose, the invention provides a preparation method of lithium disilicate glass ceramic with transmittance and color gradient effect, which comprises the following steps:
weighing the basic glass components according to the formula, uniformly mixing, and melting at high temperature;
water quenching the fully melted glass liquid into glass frits, and grinding the frits to different required particle sizes to prepare glass powder;
uniformly mixing three or more than three glass powders with the granularity changing in a gradient manner and corresponding colorants and/or fluorescent agents with the granularity changing in a gradient manner, then sequentially adding the mixture into a mold, and carrying out dry pressing forming or dry pressing combined isostatic pressing forming;
and sintering the formed blank in a vacuum atmosphere to obtain the lithium disilicate glass ceramic.
Preferably, the melting temperature of the base glass is 1200-1700 ℃, the melting time is 10-360min, the preferred melting temperature is 1350-1550 ℃, and the melting time is 30-180min.
Preferably, the obtained glass powder has a particle size in the range of 3 μm. Ltoreq.D 50 Less than or equal to 30 mu m, and the granularity of each layer differs by D 50 =2.5-3.5 μm. It is understood that when the particle size of each layer is different from the above range, the light transmittance gradual transition is ensured to be natural.
Preferably, when the particle size of the obtained glass powder is 3 μm, the corresponding light transmittance reaches 60 to 67%; at 30 μm, the corresponding light transmittance reached 30-38%. It can be understood that the effect of gradual change of transmittance can be realized by overlapping powder with different particle sizes, and the smaller the particle size, the higher the transmittance, so long as the particle size difference of each layer can be ensured within the above range, the natural transition of gradual change of transmittance can be ensured.
Preferably, the molding pressure is from 10 to 500MPa, preferably from 20 to 300MPa.
Preferably, the vacuum degree of vacuum atmosphere sintering is 50-5000Pa, the sintering temperature is 700-1000 ℃, the heat preservation time is 10-360min, preferably the vacuum degree is 500-3500Pa, the sintering temperature is 800-900 ℃, and the heat preservation time is 30-180min.
Preferably, the formed blank is sintered in a vacuum atmosphere to obtain the lithium disilicate glass ceramic, which specifically comprises the following steps:
carrying out primary sintering treatment on the molded blank in a vacuum atmosphere to obtain lithium silicate glass or glass ceramic;
and processing the obtained lithium silicate glass or glass ceramic, and then performing secondary sintering treatment to obtain the lithium disilicate glass ceramic.
Preferably, the vacuum degree of the primary sintering treatment in the vacuum atmosphere is 50-5000Pa, the sintering temperature is 320-820 ℃, and the heat preservation time is 10-360min; preferably, the vacuum degree is 500-3500Pa, the sintering temperature is 400-750 ℃, and the heat preservation time is 30-180min;
preferably, the vacuum degree of the vacuum atmosphere secondary sintering treatment is 50-5000Pa, the sintering temperature is 700-1000 ℃, the heat preservation time is 2-240min, preferably the vacuum degree is 500-3500Pa, the sintering temperature is 800-900 ℃, and the heat preservation time is 3-40min.
Preferably, the base glass consists essentially of, in weight percent:
Figure BDA0003002090370000031
wherein the other component is selected from monovalent metal oxide Na 2 O, divalent metal oxides SrO, mgO, caO, trivalent metal oxides B 2 O 3 、La 2 O 3 Tetravalent metal oxide TiO 2 The non-valent metal oxide Nb 2 O 5 And hexavalent Metal oxide WO 3 、MoO 3 At least one of (1).
Preferably, the base glass consists essentially of, in weight percent:
Figure BDA0003002090370000032
Figure BDA0003002090370000041
wherein the other component is selected from monovalent metal oxide Na 2 O, divalent metal oxides SrO, mgO, caO, trivalent metal oxides B 2 O 3 、La 2 O 3 Tetravalent metal oxide TiO 2 Nb, an oxide of an invaluable metal 2 O 5 And hexavalent Metal oxide WO 3 、MoO 3 At least one of (a).
Preferably, the dye also comprises 0 to 10.5 percent of colorant and/or fluorescent agent, preferably 1 to 7 percent by weight.
Preferably, the colorant and/or phosphor comprises a transition metal oxide and rare earth colorant, a zirconium-based colorant and/orFluorescer and spinel colourant and/or fluorescer, the transition metal oxide and rare earth colourant being selected from Fe 2 O 3 、V 2 O 5 、NiO、MnO、Cr 2 O 3 、Co 2 O 3 、CeO 2 、Pr 2 O 3 、Nd 2 O 5 、Er 2 O 3 、Tb 4 O 7 、Tm 2 O 3 、Sm 2 O 3 、Dy 2 O 3 、Bi 2 O 3 、Yb 2 O 3 The zirconium-based colorant and/or fluorescent agent is selected from at least one of zirconium iron red, zirconium praseodymium yellow and zirconium gray, and the spinel colorant and/or fluorescent agent is selected from at least one of chromium iron red colorant and/or fluorescent agent, iron chromium zinc brown colorant and/or fluorescent agent.
The invention also provides the lithium disilicate glass ceramic prepared by the preparation method according to any one of the technical schemes.
The invention also provides the application of the lithium disilicate glass ceramic as a dental material, preferably for preparing a dental restoration.
The invention also provides a dental prosthesis which is prepared by adopting the lithium disilicate glass ceramic in the technical scheme.
Preferably, the dental restoration is selected from the group of: crowns, abutments, inlays, onlays, veneers, facets, bridges and braces.
Compared with the prior art, the invention has the advantages and positive effects that:
the invention provides a method for preparing lithium disilicate glass ceramic with transmittance and color gradient effects, which controls the mixing of colorants with different contents in each layer and glass powder with different particle sizes through a mode of powder materials with different particle sizes being superposed layer by layer so as to realize the effect of light transmittance gradient, thereby leading the transmittance and color gradient effect of the lithium disilicate glass ceramic to be consistent with the optical effect of natural teeth. In addition, the method mixes the ground powder with different granularities with the colorant, and the powder is added into the die layer by layer for dry pressing molding and is sintered in a low-temperature vacuum atmosphere, so that the complicated procedure of preparing the powder for many times can be effectively avoided. Meanwhile, the step of adding the coloring agent and/or the fluorescent agent in the high-temperature melting process is avoided, the loss of the coloring agent and/or the fluorescent agent can be effectively reduced, and the color stability is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1 (CAD secondary crystallized glass-ceramic with three-layer grading effect):
base glass composition
SiO 2 62
Li 2 O 16
K 2 O 5
Al 2 O 3 3.5
P 2 O 5 3
ZrO 2 1
ZnO 1
Na 2 O 4
MgO 2
CaO 1
B 2 O 3 1
Mo 2 O 3 0.5
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. Fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1350 ℃ for 180min, and pouring the melted glass liquid into cold water to obtain the glass frit. Drying the obtained glass frits, and respectively grinding the glass frits into 3 groups of base materials, 1# D 50 ＝3.2μm、2#D 50 ＝6.0μm、3#D 50 =8.7 μm, and then 1Wt.% of colorant and/or fluorescent agent is added and mixed uniformly with the following components:
total of 1# 2# 3#
Zirconium ash 0.1％ 0.02 0.03 0.05
Er 2 O 3 0.4％ 0.1 0.1 0.2
Fe 2 O 3 0.5％ 0.1 0.15 0.25
Adding the 1# powder mixed with the colorant and/or the fluorescent agent into the bottom of a mold, adding the 2# powder mixed with the colorant and/or the fluorescent agent into the mold after leveling, pouring the 3# powder mixed with the colorant and/or the fluorescent agent into the mold after leveling, performing dry pressing molding after leveling, wherein the molding pressure is 300MPa, obtaining a green body, sintering the green body in a vacuum furnace at 400 ℃, keeping the vacuum degree at 1200Pa and keeping the temperature for 30min, processing the obtained green body into a restoration body, performing secondary sintering, and keeping the sintering temperature at 800 ℃, the vacuum degree at 1500Pa and the keeping temperature for 3min to obtain the final lithium disilicate glass ceramic restoration body.
Example 2 (CAD secondary crystallized glass-ceramic with three-layer grading effect):
base glass composition
SiO 2 63
Li 2 O 15
K 2 O 3
Al 2 O 3 3.5
P 2 O 5 3
ZrO 2 2
ZnO 2
Na 2 O 3.5
CaO 1.5
B 2 O 3 1.5
La 2 O 3 1
Nb 2 O 5 1
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. And (3) fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1400 ℃, melting for 120min, and pouring the molten glass into cold water to obtain the glass frit. Drying the obtained glass frits, and grinding the glass frits into 1# D 50 ＝3.4μm、2#D 50 ＝6.2μm、3#D 50 =9.4 μm, and then 7Wt.% of colorant and/or fluorescent agent is added and uniformly mixed with the mixture, wherein the colorant and/or fluorescent agent comprises the following components:
total of 1# 2# 3#
MnO 0.6 0.1 0.2 0.3
Zirconium iron oxide red 2.2 0.4 0.8 1
V 2 O 5 3.6 0.6 1.2 1.8
Tm 2 O 3 0.6 0.1 0.2 0.3
Adding the No. 1 powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the No. 2 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the No. 3 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, carrying out dry pressing and forming after leveling, wherein the pressure of a forming dry pressing machine is 10MPa, the isostatic pressure is 240MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 400 ℃, keeping the vacuum degree at 1200Pa and the heat preservation time at 150min, processing the obtained green body into a restoration, then carrying out secondary sintering, wherein the sintering temperature is 800 ℃, the vacuum degree is 1500Pa, and the heat preservation time is 10min, thus obtaining the final lithium disilicate glass ceramic restoration.
Example 3 (CAD secondary crystallized glass-ceramic with three-layer grading effect):
base glass composition
SiO 2 64
Li 2 O 14
K 2 O 4
Al 2 O 3 3
P 2 O 5 2
ZrO 2 8
ZnO 1
SrO 1
MgO 1
CaO 0.5
TiO 2 0.5
Mo 2 O 3 1
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. And pouring the mixture into a platinum crucible after fully and uniformly mixing, putting the platinum crucible into a furnace for melting at 1550 ℃, wherein the melting time is 30min, and pouring the melted glass liquid into cold water to obtain the glass frit. Drying the obtained glass frits, and respectively grinding the glass frits into 1# D 50 ＝4.3μm、2#D 50 ＝6.9μm、3#D 50 =9.6 μm, and then 1.75Wt.% of colorant and/or fluorescent agent is added and uniformly mixed with the mixture, wherein the colorant and/or fluorescent agent comprises the following components:
Figure BDA0003002090370000081
adding the No. 1 powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the No. 2 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the No. 3 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, carrying out dry pressing and forming after leveling, wherein the pressure of a forming dry press is 240MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 750 ℃, keeping the vacuum degree at 1400Pa for 60min, processing the obtained green body into a restoration, then carrying out secondary sintering, wherein the sintering temperature is 800 ℃, the vacuum degree at 1600Pa and the keeping temperature for 40min, and obtaining the final lithium disilicate glass ceramic restoration.
Example 4 (CAD secondary crystallized glass-ceramic with five-layer grading effect):
base glass composition
SiO 2 65
Li 2 O 13
K 2 O 5
Al 2 O 3 3
P 2 O 5 4
ZrO 2 0.5
ZnO 4
SrO 2
MgO 1
CaO 1
La 2 O 3 1
TiO 2 0.5
The raw materials can be selected from oxide, carbonate compound, and phosphate compoundAnd the like. Fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1450 ℃ for 120min, and pouring the molten glass into cold water to obtain the glass frit. Drying the obtained glass frits, and grinding the glass frits into 1# D 50 ＝5.7μm、2#D 50 ＝8.4μm、3#D 50 ＝11.6μm、4#D 50 ＝14.5μm、5#D 50 =17.3 μm, then adding 3.45Wt.% of colorant and/or fluorescent agent, and mixing uniformly, wherein the colorant and/or fluorescent agent comprises the following components:
Figure BDA0003002090370000091
adding the 1# powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the 2# powder mixed with the colorant and/or the fluorescent agent into the mould after strickling, pouring the 3# powder mixed with the colorant and/or the fluorescent agent into the mould after strickling, sequentially adding the powder according to the above operations, carrying out dry pressing molding after all adding and strickling, wherein the pressure of a molding dry pressing machine is 180MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 600 ℃, keeping the vacuum degree of 3500Pa and keeping the temperature for 180min, processing the obtained green body into a restoration body, then carrying out secondary sintering at the sintering temperature of 900 ℃, keeping the vacuum degree of 500Pa and keeping the temperature for 30min, and obtaining the final lithium disilicate glass ceramic restoration body.
Example 5 (CAD primary crystallized glass-ceramic with five-layer grading effect):
base glass composition
SiO 2 66
Li 2 O 14
K 2 O 4
Al 2 O 3 2.5
P 2 O 5 6
ZrO 2 2
ZnO 3
Na 2 O 1
MgO 0.5
CaO 1
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. Fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1430 ℃ for 90min, and pouring the melted glass liquid into cold water to obtain the glass frit. Drying the obtained glass frits, and grinding the glass frits into 1# D 50 ＝3.6μm、2#D 50 ＝7μm、3#D 50 ＝9.8μm、4#D 50 ＝12.9μm、5#D 50 =15.6 μm, then 2.65Wt.% of coloring agent and/or fluorescent agent is added and mixed uniformly, and the coloring agent and/or fluorescent agent comprises the following components:
total of 1# 2# 3# 4# 5#
Nd 2 O 5 0.3 0.02 0.04 0.06 0.08 0.1
Zirconium iron oxide red 0.35 0.03 0.05 0.07 0.09 0.11
CeO 2 1 0.1 0.15 0.2 0.25 0.3
Yb 2 O 3 1 0.1 0.15 0.2 0.25 0.3
Adding the 1# powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the 2# powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the 3# powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, sequentially adding the powders according to the above operations, performing dry pressing after all the powders are added and leveled, performing dry pressing under the pressure of 35MPa and the isostatic pressure of 220MPa to obtain a green body, sintering the green body in a vacuum furnace at 850 ℃, keeping the vacuum degree at 3000Pa and keeping the temperature for 120min to obtain the final lithium disilicate glass ceramic restoration.
Example 6 (CAD secondary crystallized glass-ceramic with six-layer grading effect):
base glass composition
SiO 2 67
Li 2 O 15
K 2 O 5
Al 2 O 3 2
P 2 O 5 5
ZrO 2 1
ZnO 2
SrO 1
B 2 O 3 1
WO 3 0.5
Mo 2 O 3 0.5
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. Fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1380 ℃ for 150min, and pouring the molten glass into cold water to obtain the glass frit. Drying the obtained glass frits, and grinding the glass frits into 1# D 50 ＝4.3μm、2#D 50 ＝6.9μm、3#D 50 ＝10.3μm、4#D 50 ＝13μm、5#D 50 =15.8 μm, and 5.49Wt.% of colorant and/or fluorescent agent is added and mixed uniformly, wherein the colorant and/or fluorescent agent comprises the following components:
in total 1# 2# 3# 4# 5# 6#
Zirconium ash 0.33 0.01 0.02 0.04 0.06 0.08 0.12
Er 2 O 3 0.63 0.03 0.06 0.09 0.12 0.15 0.18
Pr 2 O 3 4.2 0.2 0.4 0.6 0.8 1 1.2
Dy 2 O 3 0.33 0.01 0.02 0.04 0.06 0.08 0.12
Adding the 1# powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the 2# powder mixed with the colorant and/or the fluorescent agent into the mould after strickling, pouring the 3# powder mixed with the colorant and/or the fluorescent agent into the mould after strickling, sequentially adding the powder according to the above operations, strickling and dry-pressing for molding, wherein the pressure of a molding dry-pressing machine is 190MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 660 ℃, the vacuum degree is 2500Pa, and the heat preservation time is 90min, processing the obtained green body into a restoration body, then performing secondary sintering, wherein the sintering temperature is 870 ℃, the vacuum degree is 800Pa, and the heat preservation time is 30min, and obtaining the final lithium disilicate glass ceramic restoration body.
Example 7 (CAD secondary crystallized glass-ceramic with three-layer grading effect):
base glass composition
SiO 2 68
Li 2 O 16
K 2 O 2
Al 2 O 3 1
P 2 O 5 2
ZrO 2 4
ZnO 2
Na 2 O 2
MgO 1
La 2 O 3 1
WO 3 1
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. Fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1470 ℃ for 60min, and pouring the molten glass into cold water to obtain the glass frit. Drying the obtained glass frits, and grinding the glass frits into 1# D 50 ＝5.6μm、2#D 50 ＝8.8μm、3#D 50 =11.6 μm, and 4.3Wt.% of colorant and/or fluorescent agent is added and mixed uniformly, wherein the colorant and/or fluorescent agent comprises the following components:
total of 1# 2# 3#
Nd 2 O 5 0.7 0.1 0.25 0.35
Zirconium iron oxide red 1.2 0.3 0.4 0.5
Tb 4 O 7 0.9 0.2 0.3 0.4
V 2 O 5 1.5 0.4 0.5 0.6
Adding the No. 1 powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the No. 2 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the No. 3 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, carrying out dry pressing and forming after leveling, wherein the pressure of a forming dry press is 170MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 450 ℃, keeping the vacuum degree at 1600Pa for 80min, processing the obtained green body into a restoration, and then carrying out secondary sintering, wherein the sintering temperature is 890 ℃, the vacuum degree at 700Pa and the heat preservation time is 10min, thus obtaining the final lithium disilicate glass ceramic restoration.
Example 8 (CAD primary crystallization with three-layer grading effect):
base glass composition
SiO 2 69
Li 2 O 16
K 2 O 3
Al 2 O 3 0.5
P 2 O 5 1
ZrO 2 6
ZnO 1
Na 2 O 2
SrO 1
Nb 2 O 5 0.5
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. Fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1380 ℃ for 80min, and pouring the molten glass into cold water to obtain the glass frit. Drying the obtained glass frits, and grinding the glass frits into 1# D 50 ＝7.2μm、2#D 50 ＝10.1μm、3#D 50 =12.8 μm, and then 4.6Wt.% of colorant and/or fluorescent agent is added and uniformly mixed with the mixture, wherein the colorant and/or fluorescent agent comprises the following components:
Figure BDA0003002090370000131
adding the 1# powder mixed with the colorant and/or the fluorescent agent into the bottom of a mold, adding the 2# powder mixed with the colorant and/or the fluorescent agent into the mold after leveling, pouring the 3# powder mixed with the colorant and/or the fluorescent agent into the mold after leveling, performing dry pressing molding after leveling, wherein the pressure of a molding dry pressing machine is 200MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 840 ℃, keeping the vacuum degree at 1400Pa, and keeping the temperature for 120min to obtain the final lithium disilicate glass ceramic restoration.
Example 9 (CAD primary crystallization with three-layer grading effect):
base glass composition
SiO 2 70
Li 2 O 15
K 2 O 5
Al 2 O 3 3.5
P 2 O 5 2
ZrO 2 1.5
ZnO 1
Na 2 O 1
MgO 1
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. And after fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1470 ℃ for 80min, and pouring the molten glass liquid into cold water to obtain the glass frit. Drying the obtained glass frits, and respectively grinding the glass frits into 1# D 50 ＝4.8μm、2#D 50 ＝7.5μm、3#D 50 =10.8 μm, then 3.36Wt.% of colorant and/or fluorescent agent is added and mixed uniformly, the ingredients of the colorant and/or fluorescent agent are as follows:
total of 1# 2# 3#
MnO 0.06 0.01 0.02 0.03
Zirconium iron oxide red 0.9 0.1 0.3 0.5
Zirconium praseodymium yellow 2 0.4 0.7 0.9
Dy 2 O 3 0.4 0.05 0.15 0.2
Adding the 1# powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the 2# powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the 3# powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, performing dry pressing and forming after leveling, wherein the pressure of a forming dry press is 230MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 820 ℃, keeping the vacuum degree at 3000Pa for 100min, and obtaining the final lithium disilicate glass ceramic restoration.
Example 10 (CAD secondary crystallization with four-layer grading effect):
base glass composition
SiO 2 71
Li 2 O 14
K 2 O 3
Al 2 O 3 1.5
P 2 O 5 2
ZrO 2 3
ZnO 3
MgO 0.5
La 2 O 3 1
Mo 2 O 3 1
The raw materials can be selected from oxide and carbonate thereof according to the formulaCompounds, phosphate compounds, and the like. Fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1460 ℃ for 110min, and pouring the molten glass into cold water to obtain the glass frit. Drying the obtained glass frits, and respectively grinding the glass frits into 1# D 50 ＝3.4μm、2#D 50 ＝6.5μm、3#D 50 ＝9.4μm、4#D 50 =12 μm, and then 4.68Wt.% of colorant and/or fluorescent agent is added and uniformly mixed with the mixture, wherein the colorant and/or fluorescent agent comprises the following components:
total of 1# 2# 3# 4#
MnO 0.34 0.04 0.07 0.10 0.13
Er 2 O 3 1.4 0.1 0.2 0.5 0.6
Zirconium praseodymium yellow 2.6 0.3 0.4 0.7 1.2
Tm 2 O 3 0.34 0.04 0.07 0.10 0.13
Adding the No. 1 powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the No. 2 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the No. 3 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, adding the mixed No. 4 powder mixed with the colorant and/or the fluorescent agent according to the operation, performing dry pressing and forming after leveling, forming under the pressure of a dry pressing machine to be 150MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 720 ℃, keeping the vacuum degree at 1200Pa, keeping the temperature for 110min, processing the obtained green body into a restoration body, performing secondary sintering, keeping the sintering temperature at 850 ℃, keeping the vacuum degree at 1000Pa, keeping the temperature for 15min, and obtaining the final lithium disilicate glass ceramic restoration body.
Example 11 (CAD secondary crystallization with four-layer grading effect):
base glass composition
SiO 2 72
Li 2 O 13
K 2 O 4
Al 2 O 3 2
P 2 O 5 1
ZrO 2 0.5
ZnO 4
Na 2 O 2
SrO 0.5
MgO 1
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. And after fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1400 ℃, melting for 60min, and pouring the molten glass into cold water to obtain the glass frit. The obtained glass fritOven drying, and grinding glass frit into 1# D 50 ＝5.9μm、2#D 50 ＝8.9μm、3#D 50 ＝11.6μm、4#D 50 =14.5 μm, and then 1.88Wt.% of colorant and/or fluorescent agent is added and uniformly mixed with the mixture, wherein the colorant and/or fluorescent agent comprises the following components:
Figure BDA0003002090370000161
adding the powder 1 mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the powder 2 mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the powder 3 mixed with the colorant and/or the fluorescent agent into the mould after leveling, adding the powder 4 mixed with the colorant and/or the fluorescent agent according to the operation, performing dry pressing and forming after leveling, forming and performing dry pressing under the pressure of 230MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 700 ℃, the vacuum degree of 1600Pa, and the heat preservation time of 80min, processing the obtained green body into a restoration body, then performing secondary sintering, the sintering temperature of 860 ℃, the vacuum degree of 1400Pa, and the heat preservation time of 25min to obtain the final lithium disilicate glass ceramic restoration body.
COMPARATIVE EXAMPLE 1 (EXAMPLE 7)
Base glass composition
SiO 2 68
Li 2 O 16
K 2 O 2
Al 2 O 3 1
P 2 O 5 2
ZrO 2 4
ZnO 2
Na 2 O 2
MgO 1
La 2 O 3 1
WO 3 1
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. Fully and uniformly mixing, pouring into a platinum crucible, putting the platinum crucible into a furnace for melting at 1470 ℃ for 60min, and pouring the molten glass into cold water to obtain the glass frit. Drying the obtained glass frits, and grinding the glass frits into 1# D 50 ＝5.6μm、2#D 50 ＝6.2μm、3#D 50 =6.9 μm, and then 4.3Wt.% of colorant and/or fluorescent agent is added and uniformly mixed with the mixture, wherein the colorant and/or fluorescent agent comprises the following components:
total of 1# 2# 3#
Nd 2 O 5 0.7 0.1 0.25 0.35
Zirconium iron oxide red 1.2 0.3 0.4 0.5
Tb 4 O 7 0.9 0.2 0.3 0.4
V 2 O 5 1.5 0.4 0.5 0.6
Adding the No. 1 powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the No. 2 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the No. 3 powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, carrying out dry pressing and forming after leveling, wherein the pressure of a forming dry press is 170MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 450 ℃, keeping the vacuum degree at 1600Pa for 80min, processing the obtained green body into a restoration, and then carrying out secondary sintering, wherein the sintering temperature is 890 ℃, the vacuum degree at 700Pa and the heat preservation time is 10min, thus obtaining the final lithium disilicate glass ceramic restoration.
COMPARATIVE EXAMPLE 2 (EXAMPLE 8)
Base glass composition
SiO 2 69
Li 2 O 16
K 2 O 3
Al 2 O 3 0.5
P 2 O 5 1
ZrO 2 6
ZnO 1
Na 2 O 2
SrO 1
Nb 2 O 5 0.5
According to the formula, the raw materials can be selected from oxides, carbonate compounds, phosphate compounds and the like. And after fully and uniformly mixing, pouring the mixture into a platinum crucible, putting the platinum crucible into a furnace for melting at 1380 ℃ for 80min, and pouring the molten glass into cold water to obtain the glass frit. Drying the obtained glass frits, and grinding the glass frits into 1# D 50 ＝7.2μm、2#D 50 ＝11.1μm、3#D 50 =15.8 μm, and then 4.6Wt.% of colorant and/or fluorescent agent is added and uniformly mixed with the mixture, wherein the colorant and/or fluorescent agent comprises the following components:
Figure BDA0003002090370000181
adding the 1# powder mixed with the colorant and/or the fluorescent agent into the bottom of a mould, adding the 2# powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, pouring the 3# powder mixed with the colorant and/or the fluorescent agent into the mould after leveling, performing dry pressing and forming after leveling, wherein the pressure of a forming dry press is 200MPa, then obtaining a green body, sintering the green body in a vacuum furnace at 840 ℃, keeping the vacuum degree at 1400Pa, and keeping the temperature for 120min to obtain the final lithium disilicate glass ceramic restoration.
And (4) performance testing:
the transmittance and color gradation effect of the lithium silicate glass ceramics obtained in the above examples and comparative examples are summarized as shown in table 1:
TABLE 1 transmittance and color gradation effect of lithium silicate glass ceramics obtained in examples and comparative examples
Figure BDA0003002090370000182
Figure BDA0003002090370000191
Figure BDA0003002090370000201

Claims (21)

1. The preparation method of the lithium disilicate glass ceramic with transmittance and color gradient effects is characterized by comprising the following steps:
weighing the basic glass components according to the formula, uniformly mixing, and melting at high temperature;
water quenching the fully melted glass liquid into glass frits, grinding the glass frits to different required particle sizes, and preparing glass powder, wherein:
the particle size range of the obtained glass powder is D which is not less than 3 mu m 50 Less than or equal to 30 mu m, and the granularity of each layer differs by D 50 =2.5-3.5 μm, particle size of the colorant and/or phosphor is 1-5 μm, and
when the granularity of the obtained glass powder is 3 mu m, the corresponding light transmittance reaches 60-67%; when the light transmittance is 30 mu m, the corresponding light transmittance reaches 30-38%;
uniformly mixing more than three kinds of glass powder with gradient change of granularity and corresponding coloring agents and/or fluorescent agents with gradient change of content, then sequentially adding the mixture into a mould, and carrying out dry pressing forming or dry pressing combined isostatic pressing forming;
and sintering the formed blank in a vacuum atmosphere to obtain the lithium disilicate glass ceramic.
2. A producing method according to claim 1, characterized in that the base glass is melted at 1200 to 1700 ℃ for 10 to 360min.
3. The method according to claim 2, wherein the base glass is melted at 1350 to 1550 ℃ for 30 to 180min.
4. The method of claim 1, wherein the molding pressure is 10 to 500Mpa.
5. The production method according to claim 4, wherein the molding pressure is 20 to 300MPa.
6. The preparation method according to claim 1, wherein the vacuum degree of vacuum atmosphere sintering is 50-5000Pa, the sintering temperature is 700-1000 ℃, and the holding time is 10-360min.
7. The preparation method of claim 6, wherein the vacuum degree of vacuum atmosphere sintering is 500-3500Pa, the sintering temperature is 800-900 ℃, and the holding time is 30-180min.
8. The preparation method according to claim 1, wherein the formed body is sintered in a vacuum atmosphere to obtain the lithium disilicate glass ceramic specifically comprising:
carrying out primary sintering treatment on the formed blank in a vacuum atmosphere to obtain lithium silicate glass or glass ceramic;
and processing the obtained lithium silicate glass or glass ceramic, and then carrying out secondary sintering treatment to obtain the lithium disilicate glass ceramic.
9. The preparation method of claim 8, wherein the vacuum degree of the primary sintering treatment in the vacuum atmosphere is 50-5000Pa, the sintering temperature is 320-820 ℃, and the holding time is 10-360min.
10. The preparation method of claim 9, wherein the vacuum degree of the primary sintering treatment in the vacuum atmosphere is 500-3500Pa, the sintering temperature is 400-750 ℃, and the holding time is 30-180min.
11. The preparation method according to claim 8, wherein the vacuum degree of the secondary sintering treatment in the vacuum atmosphere is 50-5000Pa, the sintering temperature is 700-1000 ℃, and the holding time is 2-240min.
12. The preparation method of claim 11, wherein the vacuum degree of the vacuum atmosphere secondary sintering treatment is 500 to 3500Pa, the sintering temperature is 800 to 900 ℃, and the holding time is 3 to 40min.
13. A method of manufacturing as claimed in any one of claims 1 to 12, wherein the base glass consists essentially of, in weight percent:
SiO 2 51-79%
Li 2 O 6-22%
K 2 O 0.5-10%
Al 2 O 3 0.5-5.5%
P 2 O 5 0.5-10.5%
ZrO 2 0-5%
ZnO 0.5-5.5%
other components 0-10.5%;
wherein the other component is selected from monovalent metal oxide Na 2 O, divalent metal oxides SrO, mgO, caO, trivalent metal oxides B 2 O 3 、La 2 O 3 Tetravalent metal oxide TiO 2 The non-valent metal oxide Nb 2 O 5 And hexavalent metal oxide WO 3 、MoO 3 At least one of (1).
14. A method of making according to claim 13 wherein the base glass consists essentially of, in weight percent:
SiO 2 62-72%
Li 2 O 13-16%
K 2 O 2-5%
Al 2 O 3 0.5-3.5%
P 2 O 5 1-6%
ZrO 2 0.5-8%
ZnO 1-4%
2 to 8.5 percent of other components;
wherein the other component is selected from monovalent metal oxide Na 2 O, divalent metal oxides SrO, mgO, caO, trivalent metal oxides B 2 O 3 、La 2 O 3 Tetravalent metal oxide TiO 2 Nb, an oxide of an invaluable metal 2 O 5 And hexavalent Metal oxide WO 3 、MoO 3 At least one of (1).
15. The method of claim 14, further comprising 0-10.5% by weight of a colorant and/or a fluorescer.
16. The method of claim 15, wherein the colorant and/or phosphor comprises a transition metal oxide and rare earth colorant selected from Fe, a zirconium-based colorant and/or phosphor, and a spinel colorant and/or phosphor 2 O 3 、V 2 O 5 、NiO、MnO、Cr 2 O 3 、Co 2 O 3 、CeO 2 、Pr 2 O 3 、Nd 2 O 5 、Er 2 O 3 、Tb 4 O 7 、Tm 2 O 3 、Sm 2 O 3 、Dy 2 O 3 、Bi 2 O 3 、Yb 2 O 3 The zirconium-based colorant and/or fluorescent agent is selected from at least one of zirconium iron red, zirconium praseodymium yellow and zirconium gray, and the spinel colorant and/or fluorescent agent is selected from at least one of chromium iron red colorant and/or fluorescent agent, iron chromium zinc brown colorant and/or fluorescent agent.
17. Lithium disilicate glass-ceramics prepared according to the preparation process of any one of claims 1-16.
18. Use of the lithium disilicate glass-ceramic according to claim 17 as dental material.
19. Use of a lithium disilicate glass-ceramic according to claim 17 for the preparation of a dental restoration.
20. Dental restoration, characterized in that it is produced using a lithium disilicate glass-ceramic according to claim 17.
21. The dental restoration according to claim 20, wherein the dental restoration is selected from the group consisting of: crowns, abutments, inlays, onlays, veneers, facets, bridges and braces.
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