CN113387585A - Lithium disilicate glass ceramic and preparation method and application thereof - Google Patents
Lithium disilicate glass ceramic and preparation method and application thereof Download PDFInfo
- Publication number
- CN113387585A CN113387585A CN202110724837.0A CN202110724837A CN113387585A CN 113387585 A CN113387585 A CN 113387585A CN 202110724837 A CN202110724837 A CN 202110724837A CN 113387585 A CN113387585 A CN 113387585A
- Authority
- CN
- China
- Prior art keywords
- treatment
- glass
- lithium disilicate
- temperature
- nucleation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 41
- 239000003103 lithium disilicate glass Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 62
- 238000011282 treatment Methods 0.000 claims abstract description 44
- 239000003086 colorant Substances 0.000 claims abstract description 26
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000010899 nucleation Methods 0.000 claims abstract description 23
- 230000006911 nucleation Effects 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 18
- 230000008018 melting Effects 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000003825 pressing Methods 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical compound [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 claims description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- USEGQPUGEPSVQL-UHFFFAOYSA-N [Pr].[Zr] Chemical compound [Pr].[Zr] USEGQPUGEPSVQL-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 4
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims description 4
- 239000006136 disilicate glass ceramic Substances 0.000 claims description 4
- UMTMDKJVZSXFNJ-UHFFFAOYSA-N nickel;trihydrate Chemical compound O.O.O.[Ni] UMTMDKJVZSXFNJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- NDUKHFILUDZSHZ-UHFFFAOYSA-N [Fe].[Zr] Chemical compound [Fe].[Zr] NDUKHFILUDZSHZ-UHFFFAOYSA-N 0.000 claims description 3
- DIVGJYVPMOCBKD-UHFFFAOYSA-N [V].[Zr] Chemical compound [V].[Zr] DIVGJYVPMOCBKD-UHFFFAOYSA-N 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010902 jet-milling Methods 0.000 claims description 3
- 229910002637 Pr6O11 Inorganic materials 0.000 claims description 2
- 229910018162 SeO2 Inorganic materials 0.000 claims description 2
- 239000006121 base glass Substances 0.000 claims description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 239000002241 glass-ceramic Substances 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005452 bending Methods 0.000 description 7
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 7
- 229910052912 lithium silicate Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004040 coloring Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- HZGFMPXURINDAW-UHFFFAOYSA-N iron zirconium Chemical compound [Fe].[Zr].[Zr] HZGFMPXURINDAW-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010903 primary nucleation Methods 0.000 description 1
- 238000010900 secondary nucleation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PSUYMGPLEJLSPA-UHFFFAOYSA-N vanadium zirconium Chemical compound [V].[V].[Zr] PSUYMGPLEJLSPA-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- A61K6/15—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
- A61K6/70—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
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a lithium disilicate glass ceramic and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) uniformly mixing basic glass components, melting at high temperature, and performing water quenching treatment to obtain a glass frit; (2) crushing the glass frit obtained in the step (1) to obtain glass powder; (3) and (3) mixing the glass powder obtained in the step (2) with a coloring agent, and carrying out layered forming treatment, vacuum sintering treatment, nucleation and crystallization treatment to obtain the lithium disilicate glass ceramic. The preparation method of the invention, on one hand, avoids the problem that the decomposition and volatilization of the colorant are seriously uncontrollable in the high-temperature melting stage, on the other hand, controls the nucleation time to improve the strength of the glass ceramic, and simultaneously adopts the layered pressing to prepare the lithium disilicate glass ceramic with gradually changed color.
Description
Technical Field
The invention belongs to the technical field of dental all-ceramic materials, and relates to lithium disilicate glass ceramic and a preparation method and application thereof.
Background
The lithium disilicate glass ceramic is a material which has the high mechanical strength of the ceramic and the high-transmittance aesthetic property of the glass at the same time, and plays an important role in the dental all-ceramic repair material. The visual effect of the dental restoration is decisive to achieve the extent that the dental restoration is falsified. The influence of the semi-permeability and color of the material on the appearance of the prosthesis is of great importance. The new requirements on the performance of the all-ceramic repair material are provided, namely the repair material needs to have higher mechanical strength to bear the occlusal force without cracking; on the other hand, the optical characteristics of the hard tissues of the natural teeth can be simulated and reproduced to the maximum extent by the optical characteristics of the hard tissues of the natural teeth.
At present, clinically applied lithium disilicate glass ceramics are mainly used as products for tooth restoration, namely Jia IPS e.max CAD series, the product series comprises three products with different transmittances of HT, MO and LT, and all the products are single-color products. At present, glass ceramics are prepared by casting a melt of glass into a female die at a high temperature for molding. The process has the problems of poor color controllability, wherein the poor controllability comprises poor color stability controllability and incapability of realizing color gradual change, and the color material is seriously decomposed and volatilized in the melting stage at the high temperature of 1400 ℃ and 1550 ℃, so that the volatilization amount is uncontrollable, thereby causing the poor color stability of the glass ceramic blocks produced by the process in batches. In addition, the casting process is realized at high temperature, the viscosity of the glass liquid is low, and the glass liquid with different colors can not be laminated.
CN104108883A discloses a high-strength lithium disilicate glass ceramic and a preparation method thereof, wherein the preparation method of the high-strength lithium disilicate glass ceramic comprises the following steps: selecting corresponding initial raw materials to prepare a mixture, uniformly grinding the mixture, placing the mixture in a crucible, melting the mixture for 1-24 hours at 1300-1600 ℃, so that components of a glass melt are uniformly distributed and bubbles are completely escaped, quickly cooling the mixture by using a glass forming process to obtain matrix glass in a certain shape, eliminating the internal stress of the matrix glass by using pre-annealing, and performing heat treatment on the matrix glass to form nuclei and crystallize, wherein the heat treatment process comprises the steps of firstly performing nucleation treatment at 530 ℃ for 15min, and then performing second-stage heat treatment: keeping the temperature at 650 ℃ for 30min, then heating to 810 ℃ for crystallization treatment for 2h, wherein the main crystal phase of the obtained product is lithium disilicate. The prepared lithium disilicate glass ceramic has the problem of poor color controllability.
CN108751721A discloses a lithium disilicate glass ceramic for dental zirconia surface porcelain and a preparation method and application thereof, wherein the preparation method comprises the following steps: after ball milling and mixing of the raw materials, melting to obtain a molten material, pouring the molten material into a mold, and annealing to obtain a glass blank; and crystallizing and heat treating the glass body to obtain the lithium disilicate glass ceramic. The obtained lithium disilicate glass ceramic has high flexural strength, and can remarkably reduce the damage probability of the restoration body caused by the crack of the facing porcelain. However, the lithium disilicate glass ceramic prepared by the method also has the problem of poor color controllability.
CN112551894A discloses a starting glass, lithium silicate glass with a core, a preparation method and application thereof, wherein a compound of a fluorescent element is introduced into a raw material, no additional fluorescent powder is needed, the process is simple, and the fluorescent color is easy to control. The obtained fluorescent lithium silicate glass material can be effectively used in the preparation of dental prosthetic materials, and can simulate the effect of gradually changing the color of natural teeth from neck to cut off, thereby achieving the fluorescent effect similar to natural teeth and effectively improving the aesthetic effect. But the highest value of the strength of the prepared product is only 370MPa, and the risk of product fracture is large.
The above solutions all have the problems of poor color controllability or low strength of the prepared glass ceramic, so it is necessary to develop a high-strength and color-controllable graded lithium disilicate glass ceramic.
Disclosure of Invention
The invention aims to provide a lithium disilicate glass ceramic and a preparation method and application thereof, the preparation method can prepare the gradual change lithium disilicate glass ceramic with stable color, and the problems of serious decomposition and volatilization of pigments and uncontrollable volatilization in a high-temperature melting stage are avoided; the strength of the glass ceramic is improved by controlling the nucleation process.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium disilicate glass ceramic, comprising the steps of:
(1) uniformly mixing basic glass components, melting at high temperature, and performing water quenching treatment to obtain a glass frit;
(2) crushing the glass frit obtained in the step (1) to obtain glass powder;
(3) mixing the glass powder obtained in the step (2) with a colorant, and carrying out molding treatment, sintering treatment, nucleation and crystallization treatment to obtain the lithium disilicate glass ceramic;
wherein the sintering treatment temperature in the step (3) is 1000-1200 ℃.
The invention adopts a powder pressing lamination pressing process, prepares the glass frit under the high temperature condition in advance, adds the pigment after the glass frit is crushed, and can finish coloring at a relatively low temperature, thereby solving the problem of color change caused by the volatile high temperature of the pigment. Meanwhile, a large number of nucleation sites are separated out by controlling the nucleation process, and the strength of the product is improved.
Preferably, the base glass component of step (1) comprises SiO2、Li2O、Al2O3、K2O、P2O5And an additive.
Preferably, the additive comprises ZnO, MgO, NaO, ZrO, B2O3、La2O3Or SrO, or a combination of at least two thereof.
Preferably, the SiO2、Li2O、Al2O3、K2O、P2O5And the additive in a mass ratio of (63-75): (10-18): (1-6): 1-10): 2-6): 0.1-4, for example: 63:18:5:8:5:1, 65:13:5:7:4:3, 70:12:4:6:5:3, 66:15:5:8:4:3, or 75:15:5:4:2:3, etc.
Preferably, the temperature of the high-temperature melting in the step (1) is 1400-1600 ℃, for example: 1400 deg.C, 1450 deg.C, 1480 deg.C, 1500 deg.C, 1520 deg.C, 1550 deg.C or 1600 deg.C, etc.
In the prior art, the colorant is generally added along with the basic glass components, and the pigment is seriously decomposed and volatilized in the melting stage of high temperature 1400 ℃ and 1600 ℃ and the volatilized amount is uncontrollable, so that the problem of poor batch color stability of the glass ceramic block produced by the process is caused. The invention prepares the glass frit in advance, and adds the pigment after crushing, thereby avoiding the problem of decomposition and volatilization of the pigment at high temperature.
Preferably, the time for high-temperature melting is 60-360 min, for example: 60min, 90min, 100min, 120min, 150min, 180min, 250min, 300min, 320min, 360min and the like.
Preferably, the crushing treatment of step (2) comprises ball milling and/or jet milling.
Preferably, the average particle size of the glass powder is 0.5 to 50 μm, for example: 0.5 μm, 1 μm, 5 μm, 10 μm, 20 μm, or 50 μm, preferably 5 to 30 μm.
Preferably, the colorant of step (3) comprises TiO2、CeO2、CuO、Er2O3、Nd2O3、Cr2O3、MnO、SeO2、V2O5、Pr6O11、Tb4O7Any one or the combination of at least two of zirconium praseodymium yellow, zirconium iron red, zirconium vanadium blue or nickel black.
Preferably, the mass ratio of the glass powder to the colorant is (90-99.9): (0.1-10), such as: 90:10, 92:8, 95:5, 98:2, or 99.9:0.1, etc.
Preferably, the molding treatment in the step (3) includes adding the glass powder obtained in the step (2) into colorants in different proportions, uniformly mixing, sequentially spreading the glass powder in a mold from a large colorant content to a small colorant content or from a small colorant content to a large colorant content, and performing one-time dry pressing molding to obtain blanks with different colorant contents.
Preferably, the pressure of the dry pressing is 5-20 MPa, such as: 5MPa, 10MPa, 15MPa, 18MPa or 20MPa, preferably 6-12 MPa.
Preferably, the number of the tiled layers is 2-8, for example: 2, 3, 4, 5, 6, 7 or 8 layers, preferably 3 to 6 layers.
The invention achieves the effect of gradual color change by controlling the type and content of the colorant in the blank and the number of tiled layers, and removing bubbles through layered pressing, vacuum sintering and melting.
Preferably, the sintering treatment in the step (3) is a vacuum sintering treatment.
Preferably, the vacuum degree of the vacuum sintering treatment is 100-3000 Pa, for example: 100Pa, 200Pa, 500Pa, 1000Pa, 2000Pa, 3000Pa, or the like.
Preferably, the temperature of the vacuum sintering treatment is 1000-1200 ℃, for example: 1000 deg.C, 1050 deg.C, 1100 deg.C, 1150 deg.C or 1200 deg.C, etc.
Preferably, the time of the vacuum sintering treatment is 100-240 min, for example: 100min, 110min, 120min, 130min, 140min, 150min, 180min, 210min, 240min and the like.
Preferably, the nucleation in step (3) comprises at least one nucleation treatment, preferably 2 to 4 times, for example: 2, 3 or 4 times.
Preferably, the temperature of the nucleation treatment is 400-700 ℃, for example: 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C or 700 deg.C, etc.
Preferably, the nucleation treatment time is 30-200 min independently, such as: 30min, 60min, 90min, 120min, 150min or 200min and the like.
Preferably, the temperature of the crystallization treatment is 800-860 ℃, for example: 800 deg.C, 820 deg.C, 840 deg.C, 850 deg.C or 860 deg.C.
Preferably, the time of the crystallization treatment is 1-10 min, for example: 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min and the like.
In a second aspect, the present invention provides a lithium disilicate glass-ceramic produced by the method according to the first aspect.
In a third aspect, the present invention provides a use of a lithium disilicate glass-ceramic according to the second aspect in a dental all-ceramic restorative material.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the process of adding the pigment later, prepares the glass frit under the high temperature condition in advance, adds the pigment after the glass frit is crushed and can finish coloring at a relatively low temperature, and solves the problem of color change caused by the volatile high temperature of the pigment.
(2) The invention achieves the effect of gradual color change by controlling the type and content of the colorant in the blank and the number of tiled layers, and removing bubbles through layered pressing, vacuum sintering and melting.
(3) The lithium disilicate glass ceramic prepared by the method has stable color, the transmissivity can reach more than 50 percent, the bending strength can reach more than 495MPa, and the bending strength of the lithium disilicate glass ceramic can reach 545MPa by adjusting the mixture ratio of the raw materials.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The raw material components and the formulation of examples 1 to 7 and comparative examples 1 to 3 of the present invention are shown in table 1:
TABLE 1
Example 1
This example provides a high-strength, color-graded lithium disilicate glass ceramic prepared by the following steps:
(1) blending the components of the basic formula glass shown in the table 1, melting at 1550 ℃ for 120min, and performing water quenching treatment to obtain a glass frit;
(2) performing jet milling on the glass frit obtained in the step (1) to obtain glass powder with the average particle size of 10 microns;
(3) mixing the glass powder obtained in the step (2) with a colorant CeO2、TiO2、Er2O3Respectively mixing the materials according to the mass ratio of 95:3.5:0.5:1, 98:1.5:0.25:0.15 and 99:0.7:0.2:0.1, then placing the mixture into a mould to be paved in sequence, and performing compression molding to obtain a blankAnd putting the obtained blank body into a high-temperature mold, performing vacuum sintering at the vacuum degree of 500Pa and the temperature of 1100 ℃ for 120min, performing primary nucleation at 450 ℃ for 60min, performing secondary nucleation at 550 ℃ for 60min, performing tertiary nucleation at 600 ℃ for 60min, and performing quaternary nucleation at 640 ℃. Crystallizing at 840 ℃ for 6min to obtain the lithium disilicate glass ceramic.
Example 2
This example provides a lithium disilicate glass ceramic prepared as follows:
(1) blending the components of the basic formula glass shown in the table 1, uniformly mixing, carrying out high-temperature melting at 1500 ℃ for 110min, and carrying out water quenching treatment to obtain a glass frit;
(2) ball-milling the glass frit obtained in the step (1) to obtain glass powder with the average particle size of 20 microns;
(3) mixing the glass powder obtained in the step (2) with zirconium praseodymium yellow, zirconium vanadium blue, zirconium iron red and nickel black according to the mass ratio of 96:2.5:1:0.3:0.2, 96.78:2:0.8:0.25:0.17, 97.13:1.8:0.7:0.22:0.15, 97.43:1.6:0.65:0.2:0.12, 97.62:1.5:0.6:0.18:0.1, 98.2:1.2:0.4:0.15:0.05, 98.68:1:0.2:0.1:0.02 and 99.06:0.8:0.07:0.06:0.01, then placing the mixture in a mold for flatting, pressing and molding to obtain a blank, placing the blank in a high-temperature mold, sintering the blank under the vacuum degree of 1000 ℃ and the vacuum temperature of 120 ℃ for 120min, performing primary processing at the temperature of 860 ℃ for 60 ℃ for lithium silicate nucleation at the temperature of 60 ℃ and then performing secondary lithium silicate nucleation at the temperature of 860 ℃ of 10 ℃ to obtain a secondary lithium silicate.
Example 3
This example provides a lithium disilicate glass ceramic prepared as follows:
(1) blending the components of the basic formula glass shown in the table 1, uniformly mixing, carrying out high-temperature melting at 1500 ℃ for 110min, and carrying out water quenching treatment to obtain a glass frit;
(2) ball-milling the glass frit obtained in the step (1) to obtain glass powder with the average particle size of 20 microns;
(3) mixing the glass powder obtained in the step (2) with praseodymium zirconium yellow, vanadium zirconium blue, iron zirconium red and nickel black according to a mass ratio of 96:2.5:1:0.3:0.2, 96.78:2:0.8:0.25:0.17, 97.13:1.8:0.7:0.22:0.15, 97.43:1.6:0.65:0.2:0.12, 97.62:1.5:0.6:0.18:0.1, 98.2:1.2:0.4:0.15:0.05, 98.68:1:0.2:0.1:0.02 and 99.06:0.8:0.07:0.06:0.01, then placing the mixture in a mold, spreading the mixture in sequence, pressing and molding to obtain a blank, placing the blank in a high-temperature mold, sintering the blank at a vacuum degree of 1000 ℃, sintering the temperature of 1150 ℃ for 120min, and performing secondary lithium silicate nuclear treatment at a temperature of 180 ℃ for 8min to obtain a secondary lithium silicate core.
Example 4
This example is different from example 1 only in that the average particle size of the glass frit in step (2) is 5 μm, and other conditions and parameters are exactly the same as those in example 1.
Example 5
This example is different from example 1 only in that the average particle size of the glass frit in step (2) is 30 μm, and other conditions and parameters are exactly the same as those in example 1.
Example 6
This example is different from example 1 only in that the average particle size of the glass frit in step (2) is 0.5 μm, and other conditions and parameters are exactly the same as those in example 1.
Example 7
This example is different from example 1 only in that the average particle size of the glass frit in step (2) is 50 μm, and other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
This comparative example differs from example 1 only in that the colorant is added directly in step (1) and the other conditions and parameters are exactly the same as in example 1.
Comparative example 2
The comparative example is different from example 1 only in that the sintering temperature in step (3) is 900 deg.C, other conditions and parameters are exactly the same as those in example 1, and a lithium disilicate glass ceramic cannot be obtained.
Comparative example 3
This comparative example differs from example 1 only in that the sintering temperature in step (3) is 1250 ℃ and the other conditions and parameters are exactly the same as those in example 1.
And (3) performance testing:
the lithium disilicate glass ceramics obtained in examples 1 to 7 and comparative examples 1 to 3 were sampled to test the semi-permeability of the samples, and 10 groups of samples were respectively tested by a three-point bending method to obtain an average value of the three-point bending strength of the samples, and the test results are shown in table 2:
TABLE 2
As can be seen from Table 2, the lithium disilicate glass ceramics obtained by the method of the present invention have stable color, transmittance of 50% or more, and bending strength of 495MPa or more, and the bending strength of 545MPa can be achieved by adjusting the raw material ratio in examples 1 to 7.
The comparison between example 1 and examples 2-3 shows that the strength of the product can be obviously improved by increasing the nucleation times. Because a large number of small crystal nuclei can be fully formed through multi-stage nucleation, and the re-crystal nuclei grow up; and nucleation and grain growth can be carried out together in the one-stage temperature rise process, so that the grain size growth of crystal nuclei can be different. The grain size consistency can be ensured only by multi-section temperature rise, so that the surrounding uniformity of the product is ensured, and the aim of improving the strength is fulfilled.
As can be seen from the comparison between example 1 and examples 4-7, the average particle size of the glass powder in step (2) affects the performance of the lithium disilicate glass ceramic, and controlling the average particle size of the glass powder to be 5-30 μm can produce the lithium disilicate glass ceramic with good semi-permeability and high bending strength.
By comparing the example 1 with the comparative example 1, the invention adopts the process of adding the pigment, prepares the glass frit under the high temperature condition in advance, finishes the coloring at a relatively low temperature by adding the pigment after the glass frit is crushed, solves the problem of color change caused by the volatile high temperature of the pigment, and can prepare the lithium disilicate glass ceramic with good semi-permeability and high bending strength.
As can be seen from comparison between example 1 and comparative examples 2-3, the sintering temperature in step (3) affects the performance of the lithium disilicate glass ceramic, and the sintering temperature is controlled to 1000-1200 deg.C, so that the lithium disilicate glass ceramic with good semi-permeability and high bending strength can be obtained.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of lithium disilicate glass ceramics is characterized by comprising the following steps:
(1) uniformly mixing basic glass components, melting at high temperature, and performing water quenching treatment to obtain a glass frit;
(2) crushing the glass frit obtained in the step (1) to obtain glass powder;
(3) mixing the glass powder obtained in the step (2) with a colorant, and carrying out molding treatment, sintering treatment, nucleation and crystallization treatment to obtain the lithium disilicate glass ceramic;
wherein the sintering treatment temperature in the step (3) is 1000-1200 ℃.
2. As claimed in claim 1The production method is characterized in that the base glass component in the step (1) comprises SiO2、Li2O、Al2O3、K2O、P2O5And an additive;
preferably, the additive comprises ZnO, MgO, Na2O、ZrO2、B2O3、La2O3Or any one of or a combination of at least two of SrO;
preferably, the SiO2、Li2O、Al2O3、K2O、P2O5The mass ratio of the additive to the additive is (63-75): (10-18): (1-6): 1-10): 2-6): 0.1-4.
3. The method according to claim 1 or 2, wherein the high-temperature melting in the step (1) is performed at 1400 to 1600 ℃;
preferably, the high-temperature melting time is 60-360 min.
4. The production method according to any one of claims 1 to 3, wherein the crushing treatment of step (2) comprises ball milling and/or jet milling;
preferably, the average particle size of the glass powder is 0.5-50 μm, preferably 5-30 μm.
5. The method according to any one of claims 1 to 4, wherein the colorant in the step (3) comprises TiO2、CeO2、CuO、Er2O3、Nd2O3、Cr2O3、MnO、SeO2、V2O5、Pr6O11、Tb4O7Any one or the combination of at least two of zirconium praseodymium yellow, zirconium iron red, zirconium vanadium blue or nickel black;
preferably, the mass ratio of the glass powder to the colorant is (90-99.9): (0.1-10).
6. The preparation method according to any one of claims 1 to 5, wherein the molding treatment in step (3) comprises adding the glass powder obtained in step (2) with colorants in different proportions, uniformly mixing, paving the glass powder in a mold in sequence from a large colorant content to a small colorant content or from a small colorant content to a large colorant content, and performing one-time dry pressing to obtain blanks with different colorant contents;
preferably, the pressure of the dry pressing is 5-20 MPa, preferably 6-12 MPa;
preferably, the number of the tiled layers is 2-8, and preferably 3-6.
7. The production method according to any one of claims 1 to 6, wherein the sintering treatment in the step (3) is a vacuum sintering treatment;
preferably, the vacuum degree of the vacuum sintering treatment is 100-3000 Pa;
preferably, the temperature of the vacuum sintering treatment is 1000-1200 ℃;
preferably, the time of the vacuum sintering treatment is 100-240 min.
8. The method according to any one of claims 1 to 7, wherein the nucleation in step (3) comprises at least one nucleation treatment, preferably 2 to 4:
preferably, the temperature of the nucleation treatment is 400-700 ℃;
preferably, the nucleation treatment time is independently 30-200 min;
preferably, the temperature of the crystallization treatment is 800-860 ℃;
preferably, the time of the crystallization treatment is 1-10 min.
9. A lithium disilicate glass-ceramic produced by the method according to any one of claims 1 to 8.
10. Use of a lithium disilicate glass-ceramic according to claim 9 in a dental all-ceramic restorative material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110724837.0A CN113387585A (en) | 2021-06-29 | 2021-06-29 | Lithium disilicate glass ceramic and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110724837.0A CN113387585A (en) | 2021-06-29 | 2021-06-29 | Lithium disilicate glass ceramic and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113387585A true CN113387585A (en) | 2021-09-14 |
Family
ID=77624367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110724837.0A Pending CN113387585A (en) | 2021-06-29 | 2021-06-29 | Lithium disilicate glass ceramic and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113387585A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114149256A (en) * | 2021-12-30 | 2022-03-08 | 爱迪特（秦皇岛）科技股份有限公司 | Ceramic material and repair material for improving surface adhesiveness of dental zirconia, preparation method and bonding method thereof |
| CN114477774A (en) * | 2022-03-01 | 2022-05-13 | 山东国瓷功能材料股份有限公司 | Lithium disilicate glass ceramic with color gradient effect and preparation method thereof |
| CN114835402A (en) * | 2022-04-19 | 2022-08-02 | 山东国瓷功能材料股份有限公司 | Preparation method and application of glass ceramic structure body with good semi-transparency and excellent mechanical properties |
| CN116177884A (en) * | 2023-03-13 | 2023-05-30 | 爱迪特（秦皇岛）科技股份有限公司 | Glass ceramic matrix and preparation method and application thereof |
| CN116199416A (en) * | 2021-11-30 | 2023-06-02 | 深圳市微思腾新材料科技有限公司 | Preparation method of high-strength glass |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050098064A1 (en) * | 2003-08-07 | 2005-05-12 | Marcel Schweiger | Lithium silicate materials |
| CN104108883A (en) * | 2014-08-11 | 2014-10-22 | 中国地质大学（北京） | High-strength lithium disilicate glass ceramic and preparation method thereof |
| US20170128174A1 (en) * | 2014-06-23 | 2017-05-11 | 3M Innovative Properties Company | Process for producing a sintered lithium disilicate glass ceramic dental restoration and kit of parts |
| CN110981204A (en) * | 2019-12-27 | 2020-04-10 | 深圳爱尔创口腔技术有限公司 | Fluorescent lithium silicate glass material and preparation method and application thereof |
| CN112551894A (en) * | 2020-12-25 | 2021-03-26 | 山东国瓷功能材料股份有限公司 | Starting glass, lithium silicate glass with core, preparation method and application thereof |
| CN113024120A (en) * | 2021-03-31 | 2021-06-25 | 山东国瓷功能材料股份有限公司 | Preparation method of lithium disilicate glass ceramic with transmittance and color gradient effect |
-
2021
- 2021-06-29 CN CN202110724837.0A patent/CN113387585A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050098064A1 (en) * | 2003-08-07 | 2005-05-12 | Marcel Schweiger | Lithium silicate materials |
| US20170128174A1 (en) * | 2014-06-23 | 2017-05-11 | 3M Innovative Properties Company | Process for producing a sintered lithium disilicate glass ceramic dental restoration and kit of parts |
| CN104108883A (en) * | 2014-08-11 | 2014-10-22 | 中国地质大学（北京） | High-strength lithium disilicate glass ceramic and preparation method thereof |
| CN110981204A (en) * | 2019-12-27 | 2020-04-10 | 深圳爱尔创口腔技术有限公司 | Fluorescent lithium silicate glass material and preparation method and application thereof |
| CN112551894A (en) * | 2020-12-25 | 2021-03-26 | 山东国瓷功能材料股份有限公司 | Starting glass, lithium silicate glass with core, preparation method and application thereof |
| CN113024120A (en) * | 2021-03-31 | 2021-06-25 | 山东国瓷功能材料股份有限公司 | Preparation method of lithium disilicate glass ceramic with transmittance and color gradient effect |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116199416A (en) * | 2021-11-30 | 2023-06-02 | 深圳市微思腾新材料科技有限公司 | Preparation method of high-strength glass |
| CN114149256A (en) * | 2021-12-30 | 2022-03-08 | 爱迪特（秦皇岛）科技股份有限公司 | Ceramic material and repair material for improving surface adhesiveness of dental zirconia, preparation method and bonding method thereof |
| CN114477774A (en) * | 2022-03-01 | 2022-05-13 | 山东国瓷功能材料股份有限公司 | Lithium disilicate glass ceramic with color gradient effect and preparation method thereof |
| CN114477774B (en) * | 2022-03-01 | 2023-10-31 | 山东国瓷功能材料股份有限公司 | Lithium disilicate glass ceramic with color gradient effect and preparation method thereof |
| CN114835402A (en) * | 2022-04-19 | 2022-08-02 | 山东国瓷功能材料股份有限公司 | Preparation method and application of glass ceramic structure body with good semi-transparency and excellent mechanical properties |
| CN114835402B (en) * | 2022-04-19 | 2023-11-21 | 山东国瓷功能材料股份有限公司 | Preparation method and application of glass ceramic structure with good semi-permeability and excellent mechanical properties |
| CN116177884A (en) * | 2023-03-13 | 2023-05-30 | 爱迪特（秦皇岛）科技股份有限公司 | Glass ceramic matrix and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113387585A (en) | Lithium disilicate glass ceramic and preparation method and application thereof | |
| CN112694253B (en) | Starting glass, lithium silicate glass with core, preparation method and application thereof | |
| CN113501668B (en) | High-strength and high-permeability lithium disilicate glass ceramic and preparation method and application thereof | |
| EP2662342B1 (en) | Lithium silicate glass ceramic and glass with ZrO2 content | |
| CN113024120B (en) | Preparation method of lithium disilicate glass ceramic with transmittance and color gradient effect | |
| CN113264684A (en) | Lithium silicate glass ceramic for dentistry, preparation method thereof and lithium silicate glass ceramic restoration | |
| CN112551894A (en) | Starting glass, lithium silicate glass with core, preparation method and application thereof | |
| CN110255911B (en) | Colored lithium disilicate glass-ceramic and preparation method thereof | |
| CN113087389A (en) | Method for preparing lithium silicate glass or lithium silicate glass ceramic body with different light transmittances | |
| EP4194415A1 (en) | High-transparency fluorescent glass-ceramic, and preparation method therefor and application thereof | |
| CN113461336A (en) | Lithium silicate glass ceramic for dentistry, preparation method thereof and lithium silicate glass ceramic restoration | |
| CN108328932A (en) | A kind of gear division devitrified glass that Ce, Er, Tb, Y are co-doped with and its preparation and application | |
| CN114524616A (en) | Lithium disilicate glass-ceramic body with different transmittances and preparation method thereof | |
| JP2019064912A (en) | High-strength lithium silicate glass composition having high shielding property | |
| CN114477774A (en) | Lithium disilicate glass ceramic with color gradient effect and preparation method thereof | |
| CN103910489A (en) | Glass used as dental veneering porcelain, preparation method and application thereof | |
| CN103086603A (en) | Colored glass ceramic for manufacturing dental prosthesis and preparation method for colored glass ceramic | |
| CN109824351A (en) | A kind of high-strength tooth family reparation ceramic composite and preparation method thereof | |
| CN111908795A (en) | Rapid coloring process of lithium disilicate glass ceramics | |
| CN113860743A (en) | Multilayer glass ceramic blank and preparation method and application thereof | |
| WO2020210958A1 (en) | Pre-sintered ceramic block for dental restoration, preparation method therefor and use thereof | |
| CN114716149B (en) | Lithium disilicate glass ceramic with gradually changed color and transmittance for dentistry as well as preparation method and application thereof | |
| CN114538780B (en) | Front tooth facing ceramic material and preparation method thereof | |
| CN114644459B (en) | Lithium silicate glass ceramic, preparation method thereof and obtained prosthesis | |
| WO2020210956A1 (en) | Pre-sintered porcelain block for dental restoration, preparation method therefor and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210914 |
|
| RJ01 | Rejection of invention patent application after publication |