CN115028364B - Glass ceramic, preparation method thereof and dental restoration material - Google Patents
Glass ceramic, preparation method thereof and dental restoration material Download PDFInfo
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- CN115028364B CN115028364B CN202210635823.6A CN202210635823A CN115028364B CN 115028364 B CN115028364 B CN 115028364B CN 202210635823 A CN202210635823 A CN 202210635823A CN 115028364 B CN115028364 B CN 115028364B
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- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 239000011521 glass Substances 0.000 claims abstract description 17
- 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 abstract description 16
- 239000010456 wollastonite Substances 0.000 claims abstract description 6
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 32
- 238000002844 melting Methods 0.000 claims description 30
- 230000008018 melting Effects 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 18
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 15
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 15
- 238000003825 pressing Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 12
- 239000003086 colorant Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 5
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 5
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000006060 molten glass Substances 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052631 glauconite Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 32
- 238000009472 formulation Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 carbonate compound Chemical class 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006121 base glass Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006112 glass ceramic composition Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003103 lithium disilicate glass Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000006017 silicate glass-ceramic Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- A61K6/70—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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Organic Chemistry (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Ceramic Engineering (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses glass ceramic, a preparation method thereof and a tooth restoration material, and belongs to the technical field of glass ceramic. The glass ceramic takes glauconite glass and lithium disilicate as main crystal phases; the content of the wollastonite is 10-30wt% and the content of the lithium disilicate is 20-35wt%; the mayenite has a rod-shaped structure, and the length-diameter ratio is 4:1-8:1. The invention is applied to the aspect of tooth restoration, solves the problem that the application of the existing glass ceramic is limited due to the strength, has high strength and toughness, can realize better aesthetic effect, and can reach 400-600MPa in final strength.
Description
Technical Field
The invention belongs to the technical field of glass ceramics, and particularly relates to glass ceramics, a preparation method thereof and a tooth restoration material.
Background
Glass ceramics are widely used as dental materials due to their adequate mechanical properties and good aesthetic effects. In dental restorations, the glass ceramics have the advantage of excellent translucency compared to zirconia ceramics, with a high degree of flexibility in simulating natural teeth. Since glass ceramics have high permeability, they are often used to make aesthetically excellent crowns, dental coverings, and the like, such as veneers, crowns, inlays, and the like.
When lithium metasilicate is used as a main crystal phase in the lithium silicate glass ceramic material, the strength of the glass ceramic is basically in the range of 100-200 MPa. After the heat treatment of the lithium metasilicate glass, the lithium metasilicate is converted into a lithium disilicate crystal phase, so that the high strength of the lithium metasilicate glass can be formed, and the strength is about 300-400 MPa. However, the strength of glass ceramics relative to zirconia ceramics is one of the main reasons that limits their applications. With the development of technology, many people increase strength by adding zirconia or other crystal phases such as quartz forming high strength to glass ceramics.
DE-A-19750794 discloses lithium disilicate glass ceramics which are produced mainly by hot-pressing processes into shaped bodies which can be milled with the aid of a computer. But has very high abrasion to the needle during the processing and longer processing time. EP-B-774993 describes an Al-based composition 2 O 3 Or ZrO(s) 2 Processed in an unsintered state to increase the strength of the article. However, these ceramic materials undergo a rapid 30% or 50% volume shrinkage upon final sintering, which can make it difficult to prepare dental restorative materials of precise dimensions, particularly multi-unit bridge dental restorative materials, with greater difficulty.
Disclosure of Invention
Aiming at the defects existing in the prior art, the technical problem to be solved by the invention is to solve the problem that the application of the existing glass ceramic is limited due to the strength, and the invention provides the glass ceramic with high strength and toughness, which can realize better aesthetic effect and the final strength can reach 400-600MPa, the preparation method thereof and the tooth repairing material.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides glass ceramic, which takes glauconite glass and lithium disilicate as main crystal phases; the content of the wollastonite is 10-30wt% and the content of the lithium disilicate is 20-35wt%; the mayenite has a rod-shaped structure, and the length-diameter ratio is 4:1-8:1.
Preferably, the component of the mayenite is K 2 O·(1.5-2.5)Na 2 O·(2.0-3.0)CaO·(10-65)SiO 2 ·(1.5-3)CaF 2 。
Preferably, the mayenite has a diameter of 100-200nm and a length of 0.5-2.5 μm.
Preferably, the composition further comprises a colorant, wherein the colorant comprises MnO and Fe 2 O 3 、Tb 2 O 3 、Er 2 O 3 、Pr 2 O 3 、V 2 O 3 。
Preferably, other crystalline phases of lithium phosphate or lithium metasilicate are also included.
The invention also provides a preparation method of the glass ceramic, which comprises the steps of mixing and dispersing raw materials, melting, gas-powder, spraying and granulating, dry pressing, primary sintering and secondary sintering in sequence; the sintering temperature of the secondary sintering step is 800-950 ℃.
Preferably, the feedstock comprises an oxide or carbonate of Si, li, zr, P, K, ca, na.
Preferably, the raw material comprises 45-60wt% of SiO 2 10-20wt% of Li 2 O, 1-8wt% ZrO 2 1.0 to 5.0wt% of P 2 O 5 1-8wt% of K 2 O, 1-10wt% CaF 2 1-10wt% of CaO and 0-8wt% of Na 2 O, colorant 1-5wt%.
Preferably, the primary sintering step includes: heating the green body to 350-400 ℃ according to the heating rate of 2-5 ℃/min, preserving heat for 1h, and then heating to 550-650 ℃ according to the heating rate of 10-20 ℃/min, preserving heat for 2h, so as to form crystal nuclei of lithium metasilicate crystal phase and CaF.
Preferably, the mixing and dispersing step includes: mixing the raw materials by a planetary mill, dispersing for 30-60min at the rotating speed of 150-300r/min, wherein the dosage ratio of the raw materials to ethanol is 3:1-2:1, and dispersing zirconium balls until the D50 is 0.5-1.5 mu m;
the melting step includes: pouring the slurry obtained through the mixing and dispersing step into a platinum crucible, and melting at 1300-1500 ℃;
the air powder step comprises the following steps: quenching the molten glass with water, crushing, drying, and pulverizing into powder with granularity of 0.5-15 μm;
the spray granulation step comprises: adding 2-5wt% of binder into the glass powder after the gas powder, preparing slurry, and then carrying out spray granulation;
the dry pressing step comprises the following steps: and (3) carrying out one-step dry pressing under the pressure of 135-165MPa to obtain a green body.
Preferably, in the air powder step, the granularity of the air powder is 4-8 mu m; in the spray granulation step, adding 2.5-3wt% of a binder into the glass powder after gas powder, wherein the binder is selected from PVB, PVA, polyacrylic acid and polyethylene glycol; the pressure of the dry pressing step is 145-155MPa.
The invention also provides a dental restoration material which is made of the glass ceramic according to any one of the technical schemes.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a glass ceramic, the strength is 400-600MPa, the fracture toughness is more than or equal to 2.0MPa m 1/2 Has excellent aesthetic effect; the glass ceramic is used as a tooth restoration material, so that the aesthetic effect is more similar to that of natural teeth, and the glass ceramic has the function of preventing decayed teeth.
Drawings
FIG. 1 is a graph showing the results of strength test of glass ceramic prepared in example 13 of the present invention;
FIG. 2 is a graph showing the results of strength test of the glass ceramic prepared in comparative example 4 of the present invention.
Detailed Description
The following detailed description of the technical solutions in the specific embodiments of the present invention will be given with reference to the accompanying drawings. It is apparent that the described embodiments are only some specific implementations, but not all implementations, of the general technical solution of the present invention. All other embodiments, which are obtained by those skilled in the art based on the general inventive concept, fall within the scope of the present invention.
The invention provides glass ceramic, which takes glauconite glass and lithium disilicate as main crystal phases; the content of the wollastonite is 10-30wt% and the content of the lithium disilicate is 20-35wt%; the mayenite has a rod-shaped structure, and the length-diameter ratio is 4:1-8:1. The embodiment specifically limits that the glass ceramic takes the glauconite glass and the lithium disilicate as main crystal phases, and the glauconite is in a rod-shaped structure, criss-cross with the lithium silicate crystal and intertwined, so that the strength and the toughness of the microcrystalline glass can be greatly improved, and the glass ceramic has better aesthetic effect. The present example specifically defines the amount of mayenite, as if the amount of mayenite is too high, it is possible thatReducing the permeability of the glass ceramic, affecting the aesthetic effect of the dental article; this example further defines the aspect ratio of the mayenite, as it is consistent with the aspect ratio range of lithium disilicate and allows for good staggering. It will be appreciated that the amount of mayenite may also be 15wt%, 20wt%, 25wt% and any point value within the range thereof, the amount of lithium disilicate may also be 25wt%, 30wt% and any point value within the range thereof, and the aspect ratio of the mayenite may also be 5:1, 6:1, 7:1 and any point value ratio within the range thereof. The proportion of calcium oxide in the mayenite does not exceed 10wt% of the total oxide. The reason is that if the CaO content is too high, the crystallization rate is too high in the crystallization process, substances such as xonotlite or calcium silicate are easy to form, the microstructure of the kenyaite is damaged, and the permeability, strength, toughness and the like of the glass ceramic are affected. The embodiment fully considers the relation of strength, aesthetic property, toughness and component content of the wollastonite, and can ensure that the strength of the glass ceramic is 400-600MPa and the fracture toughness is more than or equal to 2.0 MPa.m by limiting the composition, the consumption and the structure of each composition of the glass ceramic 1/2 Has excellent aesthetic effect. Preferably, the glass ceramic consists of 45 to 60wt% SiO 2 10-20wt% of Li 2 O, 1-8wt% ZrO 2 1.0 to 5.0wt% of P 2 O 5 1.0 to 8.0wt% of K 2 O, 1-10wt% CaF 2 1.0-10wt% of CaO and 0-8wt% of Na 2 O, 1-5wt% of coloring agent, and is prepared by taking the coloring agent as a raw material.
In a preferred embodiment, the component of the mayenite is K 2 O·(1.5-2.5)Na 2 O·(2.0-3.0)CaO·(10-65)SiO 2 ·(1.5-3)CaF 2 . The present example defines the composition of the mayenite in particular, since it produces a high purity mayenite phase, and other components have a large influence on the strength and permeability of the glass-ceramic.
In a preferred embodiment, the mayenite has a diameter of 100-200nm and a length of 0.5-2.5 μm. This example defines in particular the diameter and length of the mayenite, as it is capable of forming a highly interlocking structure with the lithium disilicate crystalline phase. It will be appreciated that the diameter of the mayenite may also be any point value within the range of 120nm, 140nm, 160nm, 180nm and the like and the length may also be any point value within the range of 1.0 μm, 1.5 μm, 2.0 μm and the like.
In a preferred embodiment, the composition further comprises a colorant comprising MnO, fe 2 O 3 、Tb 2 O 3 、Er 2 O 3 、Pr 2 O 3 、V 2 O 3 A mixture of the above materials. It should be noted that the present embodiment specifically defines the kind of the colorant, and it is understood that the colorant may be any other substance reasonably selected by those skilled in the art in combination with the common general knowledge in the art. Further, the content of the colorant is 1.0-5.0wt%.
In a preferred embodiment, other crystalline phases of lithium phosphate or lithium metasilicate are also included, preferably, the lithium phosphate is a small amount of lithium phosphate, which does not affect the permeability and is beneficial to the strength enhancement of the glass-ceramic.
The invention also provides a preparation method of the glass ceramic, which comprises the steps of mixing and dispersing raw materials, melting, gas-powder, spraying and granulating, dry pressing, primary sintering and secondary sintering in sequence; the sintering temperature of the secondary sintering step is 800-950 ℃. This example defines in particular the preparation method of the glass ceramic and in particular the sintering temperature of the secondary sintering step, since lithium disilicate and mayenite, which have a rod-shaped main crystal phase formed by sintering in this temperature range, can be better used for dental restoration. In a preferred embodiment, the sintering temperature of the secondary sintering step is 850-900 ℃. It will be appreciated that the temperature may also be any point value within 860 ℃, 870 ℃, 880 ℃, 890 ℃ and ranges thereof. After secondary sintering, the lithium metasilicate is converted into lithium disilicate, and CaF is used as crystal nucleus to form rod-shaped wollastonite, so that the final glass ceramic is formed, and the glass ceramic has good application effect when being used for dental restoration.
In a preferred embodiment, the raw materials include Si, li, zr, P, K,Ca. Oxides or carbonates of Na. Further, a nucleating agent is also included. In a preferred embodiment, the feedstock comprises 45-60wt% SiO 2 10-20wt% of Li 2 O, 1-8wt% ZrO 2 1.0 to 5.0wt% of P 2 O 5 1-8wt% of K 2 O, 1-10wt% CaF 2 1-10wt% of CaO and 0-8wt% of Na 2 O, colorant 1-5wt%. By limiting the amount of each oxide used in this example, higher purity lithium disilicate and mayenite phases can be formed with less other oxides without affecting the permeability of the glass ceramic.
In a preferred embodiment, the primary sintering step comprises: heating the green body to 350-400 ℃ according to the heating rate of 2-5 ℃/min, preserving heat for 1h, and then heating to 550-650 ℃ according to the heating rate of 10-20 ℃/min, preserving heat for 2h, so as to form crystal nuclei of lithium metasilicate crystal phase and CaF. The glass ceramic in this state has a relatively fine crystal phase and various forms, and thus has the characteristics of low strength and toughness, and excellent processability. The fused glass powder is subjected to dry pressing to obtain a green body, the embodiment specifically limits a primary sintering process, the green body is subjected to heat preservation for 1h under the condition that the temperature in a furnace is lower than 400 ℃ and the heating rate is 2-5 ℃/min, the heating rate is low, the binder can be completely discharged, the cracking of a formed body is avoided, and other miscellaneous phases are restrained; the temperature is not more than 400 ℃, and the formation of CaF crystal nucleus is not affected; then heating to 550-650 ℃ at a heating rate of 10-20 ℃ and preserving heat for 2 hours, so as to form more CaF crystal nuclei and lithium metasilicate, and enable the CaF crystal nuclei and the lithium metasilicate to have certain processability.
In a preferred embodiment, the step of mixing and dispersing includes: mixing the raw materials by a planetary mill, dispersing for 30-60min at the rotating speed of 150-300r/min, wherein the dosage ratio of the raw materials to ethanol is 3:1-2:1, and dispersing zirconium balls until the D50 is 0.5-1.5 mu m;
the melting step includes: pouring the slurry obtained through the mixing and dispersing step into a platinum crucible, and melting at 1300-1500 ℃;
the air powder step comprises the following steps: quenching the molten glass with water, crushing, drying, and pulverizing into powder with granularity of 0.5-15 μm;
the spray granulation step comprises: adding 2-5wt% of binder into the glass powder after the gas powder, preparing slurry, and then carrying out spray granulation;
the dry pressing step comprises the following steps: and (3) carrying out one-step dry pressing under the pressure of 135-165MPa to obtain a green body.
In a preferred embodiment, the air powder in the air powder step has an air powder particle size of 4-8 μm; in the spray granulation step, adding 2.5-3wt% of a binder into the glass powder after gas powder, wherein the binder is selected from PVB, PVA, polyacrylic acid and polyethylene glycol; the pressure of the dry pressing step is 145-155MPa.
The invention also provides a dental restoration material which is made of the glass ceramic according to any one of the technical schemes. The dental restoration material not only has aesthetic effect more similar to natural teeth, but also has caries preventing function due to F contained in glass ceramic.
In order to more clearly and in detail describe the glass ceramic, the preparation method thereof and the dental restoration material provided by the embodiments of the present invention, the following description will be made with reference to specific embodiments.
Example 1
The ingredients of the raw materials of the base glass (the carbonate compound, the phosphate compound, and the like of the raw materials may be selected) were blended according to the oxide content shown in example 1 in table 1. Dispersing the raw materials by a dispersing planetary mill for 35min at the rotating speed of 200 r/min: the mass ratio of the ethanol is 3:1; and (3) putting the mixed raw materials into a platinum crucible, then putting the platinum crucible into a furnace for melting, controlling the melting temperature to 1350 ℃ and the melting time to 2 hours, and then pouring the platinum crucible into cold water to obtain the glass frit.
The glass frit obtained was dried and ground to a powder with a D50 of 5 μm, then PVB glue 2.5wt% of the powder mass was added and the resulting mixed powder was spray granulated.
Placing the sprayed glass into a prepared mold, performing dry press molding, controlling the molding pressure to 145MPa, obtaining a green body, preserving the temperature of the green body at a heating rate of 3 ℃/min for 1h at 380 ℃ for discharging glue, and then preserving the temperature of the green body at a temperature of 10 ℃/min to 550 ℃ for 2h to obtain a glass ceramic product with excellent processability; and (3) performing secondary sintering at 890 ℃ to obtain a final glass ceramic product, which can be used for dental restoration.
Example 2
The raw material formulation was mixed according to example 2 in the table with a melting temperature of 1450 ℃; otherwise, the same as in example 1 was used.
Example 3
The raw material formulation was mixed according to example 3 in the table, the melting temperature was 1530℃and the same as in example 1.
Example 4
The raw material formulation was mixed according to example 4 in the table, with a melting temperature of 1450℃and the other components being identical to those of example 1.
Example 5
The raw material formulation was mixed according to example 5 in the table, with a melting temperature of 1500℃and the other steps being the same as in example 1.
Example 6
The raw material formulation was mixed according to example 6 in the table, the melting temperature was 1500 ℃, the binder was selected as PVA, and the other was the same as in example 1.
Example 7
The raw material formulation was mixed according to example 7 in the table, with a melting temperature of 1450℃and the other components being identical to those of example 1.
Example 8
The raw material formulation was mixed according to example 8 in the table, with a melting temperature of 1500℃and the other steps being identical to those of example 1.
Example 9
The raw material formulation was mixed according to example 9 in the table, with a melting temperature of 1450 ℃, the binder was selected as polyethylene glycol, and the other materials were the same as in example 1.
Example 10
The raw material formulation was mixed according to example 10 in the table, with a melting temperature of 1450℃and the other components being identical to those of example 1.
Example 11
The raw material formulation was mixed according to example 11 in the table, with a melting temperature of 1450℃and the other components being identical to those of example 1.
Example 12
The raw material formulation was mixed according to example 12 in the table, with a melting temperature of 1450℃and the other components being identical to those of example 1.
Example 13
The raw material formulation was mixed with example 1, and the melting temperature was adjusted to 1450 ℃, and the other was the same as in example 1.
Example 14
The raw material formulation was mixed with example 1, and the melting temperature was adjusted to 1450 ℃, and the other was the same as in example 1.
Example 15
The raw material formulation was mixed with example 1, and the melting temperature was adjusted to 1450 ℃, and the other was the same as in example 1.
Example 16
The raw material formulation was mixed with example 1, and the grinding particle size was 1. Mu.m, and the other was the same as in example 1.
Example 17
The raw material formulation was mixed with example 1 and the grinding particle size was 15. Mu.m, the other being the same as in example 1.
Example 18
The raw material formulation was mixed with example 1, and the amount of gum added was adjusted to 5wt%; the green body was warmed to 380℃at a warming rate of 2℃per minute and then incubated for 1 hour, and then warmed to 600℃at a warming rate of 15℃per minute, the other being the same as in example 1.
Example 19
The raw material formulation was mixed with example 1, the amount of gum added was adjusted to 1wt%, the green body was warmed up to 350℃at a warming rate of 4℃per minute and kept at that temperature for 1 hour, and then warmed up to 650℃at a warming rate of 20℃per minute, the other being the same as in example 1.
Comparative example 1
The raw material formulation was mixed in accordance with comparative example 1, and the other was the same as in example 1.
Comparative example 2
The raw material formulation was mixed in accordance with comparative example 2, and the other was the same as in example 1.
Comparative example 3
The raw material formulation was mixed in accordance with comparative example 3, the melting temperature was 1550℃and the other was the same as in example 1.
Comparative example 4
The raw material formulation was mixed according to comparative example 4, the melting temperature was 1450 ℃, and the other was the same as in example 1.
Comparative example 5
The raw material formulation was mixed according to comparative example 5, the melting temperature was 1450 ℃, and the other was the same as in example 1.
Comparative example 6
The raw material formulation was mixed as in example 1, the secondary sintering temperature was 800 ℃, and the other was the same as in example 1.
Comparative example 7
The raw material formulation was mixed as in example 1, the secondary sintering temperature was 980 ℃, and the other was the same as in example 1.
Table 1 raw material amounts of examples and comparative examples
Performance testing
The glass ceramics prepared in examples 1 to 19 and comparative examples 1 to 5 described above were subjected to performance tests, respectively, with test items including strength and toughness, and the results are shown in table 2 and fig. 1 and 2.
TABLE 2 results of product Performance test
| Examples | strength/MPa | toughness/MPa.m 1/2 | Examples | strength/MPa | toughness/MPa.m 1/2 |
| Example 1 | 430 | 2.20 | Example 14 | 477 | 2.49 |
| Example 2 | 425 | 2.17 | Example 15 | 420 | 2.16 |
| Example 3 | 463 | 2.36 | Example 16 | 522 | 2.82 |
| Example 4 | 468 | 2.38 | Example 17 | 507 | 2.69 |
| Example 5 | 475 | 2.44 | Example 18 | 557 | 2.98 |
| Example 6 | 476 | 2.47 | Example 19 | 533 | 2.91 |
| Example 7 | 435 | 2.23 | Comparative example 1 | 320 | 1.75 |
| Example 8 | 453 | 2.32 | Comparative example 2 | 335 | 1.8 |
| Example 9 | 427 | 2.18 | Comparative example 3 | 343 | 1.86 |
| Example 10 | 441 | 2.28 | Comparative example 4 | 322 | 1.78 |
| Example 11 | 491 | 2.6 | Comparative example 5 | 352 | 1.91 |
| Example 12 | 488 | 2.54 | Comparative example 6 | 285 | 1.62 |
| Example 13 | 568 | 3.05 | Comparative example 7 | 326 | 1.73 |
From the above results, it can be found that the glass ceramic prepared by the examples of the present invention has particularly high strength and toughness, and thus, the glass ceramic material has excellent tooth restoration effect.
Claims (10)
1. A glass ceramic, characterized in that the glass ceramic takes wollastonite and lithium disilicate as main crystal phases; the content of the mayenite is 10-30wt percent, and the content of the lithium disilicate is 20-35wt percent; the mayenite has a rod-shaped structure, and the length-diameter ratio is 4:1-8:1;
the glass ceramic is prepared by a raw material mixing and dispersing step, a melting step, a gas powder step, a spray granulation step, a dry pressing step, a primary sintering step and a secondary sintering step; the sintering temperature of the secondary sintering step is 850-900 ℃;
the raw material is composed of 45-60wt% of SiO 2 10-20wt% Li 2 O, zrO 1-8wt% 2 1.0-5.0wt% P 2 O 5 1-6.5wt% of K 2 O, caF of 1-10wt% 2 1-10wt% CaO, 2.7-8 wt% Na 2 O, 1-5wt% of colorant;
the primary sintering step comprises the following steps: heating the green body obtained by dry pressing to 350-400 ℃ at a heating rate of 2-5 ℃/min, preserving heat for 1h, and then heating to 550-650 ℃ at a heating rate of 10-20 ℃/min, preserving heat for 2h to form a lithium metasilicate crystal phase and CaF 2 Is not limited to the crystal nuclei.
2. The glass-ceramic according to claim 1, wherein the component of the mayenite is K 2 O·（1.5-2.5）Na 2 O·（2.0-3.0）CaO·（10-65）SiO 2 ·（1.5-3）CaF 2 。
3. The glass-ceramic according to claim 1, wherein the mayenite has a diameter of 100-200nm and a length of 0.5-2.5 μm.
4. The glass-ceramic according to claim 1, wherein the colorant comprises MnO, fe 2 O 3 、Tb 2 O 3 、Er 2 O 3 、Pr 2 O 3 、V 2 O 3 。
5. The glass-ceramic according to claim 1, further comprising other crystalline phases of lithium phosphate or lithium metasilicate.
6. The method for producing a glass ceramic according to any one of claims 1 to 5, comprising a raw material mixing and dispersing step, a melting step, a gas-powder step, a spray granulation step, a dry pressing step, a primary sintering step, a secondary sintering step in this order; the sintering temperature of the secondary sintering step is 850-900 ℃.
7. The method for producing a glass ceramic according to claim 6, wherein the raw material comprises an oxide or a carbonate of Si, li, zr, P, K, ca, na.
8. The method for producing a glass ceramic according to claim 5, wherein the step of mixing and dispersing comprises: mixing the raw materials by a planetary mill, dispersing for 30-60min at the rotating speed of 150-300r/min, wherein the dosage ratio of the raw materials to ethanol is 3:1-2:1, and dispersing zirconium balls until the D50 is 0.5-1.5 mu m;
the melting step includes: pouring the slurry obtained through the mixing and dispersing step into a platinum crucible, and melting at 1300-1500 ℃;
the air powder step comprises the following steps: quenching the molten glass with water, crushing, drying, and pulverizing into powder with granularity of 0.5-15 μm;
the spray granulation step comprises: adding 2-5-wt% of binder into the glass powder after the gas powder, preparing slurry, and then carrying out spray granulation;
the dry pressing step comprises the following steps: and (3) carrying out one-step dry pressing under the pressure of 135-165MPa to obtain a green body.
9. The method for producing a glass ceramic according to claim 8, wherein the gas-powder step has a gas-powder particle size of 4 to 8 μm; in the spray granulation step, adding 2.5-3wt% of a binder into the glass powder after gas powder, wherein the binder is selected from PVB, PVA, polyacrylic acid and polyethylene glycol; the pressure of the dry pressing step is 145-155MPa.
10. A dental restoration material, characterized by being made of the glass-ceramic according to any one of claims 1 to 5.
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