CN114873924A - Modified nitride-doped microcrystalline glass composite material, and preparation method and application thereof - Google Patents
Modified nitride-doped microcrystalline glass composite material, and preparation method and application thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 150000004767 nitrides Chemical class 0.000 claims abstract description 58
- 239000002241 glass-ceramic Substances 0.000 claims abstract description 21
- 238000002425 crystallisation Methods 0.000 claims description 43
- 230000008025 crystallization Effects 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000049 pigment Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical class Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 5
- -1 magnesium nitride Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 3
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 6
- WVMPCBWWBLZKPD-UHFFFAOYSA-N dilithium oxido-[oxido(oxo)silyl]oxy-oxosilane Chemical group [Li+].[Li+].[O-][Si](=O)O[Si]([O-])=O WVMPCBWWBLZKPD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910003471 inorganic composite material Inorganic materials 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- 239000002994 raw material Substances 0.000 description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 4
- 229910052912 lithium silicate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical class N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
- C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/836—Glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Epidemiology (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Glass Compositions (AREA)
Abstract
The invention provides a modified nitride-doped microcrystalline glass composite material, a preparation method and application thereof, and relates to the technical field of inorganic composite materials. The modified nitride-doped microcrystalline glass composite material comprises 1-10% of modified nitride by mass percent, and the balance of microcrystalline glass. The modified nitride-doped microcrystalline glass composite material belongs to glass ceramics, the main crystal phase is lithium disilicate, and the modified nitride-doped microcrystalline glass composite material contains a large amount of modified nitride, so that the strength is improved to be more than 540MPa due to high strength and good combination with microcrystalline glass, and the permeability is not influenced.
Description
Technical Field
The invention relates to the technical field of inorganic composite materials, in particular to a modified nitride-doped microcrystalline glass composite material, and a preparation method and application thereof.
Background
With the development of economic society and the improvement of living standard of people, oral health is widely regarded by the society. Currently, denture materials for clinical applications mainly include resin and resin-based composites, metals (including metal-containing porcelain), and ceramics and ceramic-based composites. The glass ceramic composite material composed of zirconia and lithium silicate has excellent performance and good use effect, and is an important denture material widely applied at present.
The microcrystalline glass has good physical, chemical and machinable properties, and can be widely applied to various fields. However, in the application process, the application effect of the microcrystalline glass is limited because the strength defect and the fracture toughness of the microcrystalline glass are not high, and the existing method for improving the strength of the microcrystalline glass mainly changes a crystal phase and adds inorganic powder such as zirconia, but other properties of the microcrystalline glass, such as permeability, processability, process flow and the like, are influenced while the strength is increased.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a modified nitride-doped microcrystalline glass composite material, which is used for solving the technical problems of low strength and low fracture toughness of the existing microcrystalline glass material and simultaneously does not influence the permeability of the existing microcrystalline glass material.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a modified nitride-doped microcrystalline glass composite material, which comprises 1-10% of modified nitride by mass percent, and the balance of microcrystalline glass.
Optionally, the modified nitride comprises modified beta-Si 3 N 4 At least one of modified aluminum nitride and magnesium nitride.
Preferably, the particle size of the modified nitride is 50nm to 300 nm.
Optionally, the glass-ceramic comprises SiO in mass percent 2 50.0％-60.0％、Li 2 O 10.0％-20.0％、P 2 O 5 1.0％-3.0％、Al 2 O 3 1.5％-3.5％、K 2 O3% -10% and ZrO 2 1.0％-10％。
Preferably, the material also comprises B in percentage by mass 2 O 3 0-6.0％、Na 2 0-5.0% of O and 0-5.0% of color pigment.
Preferably, the colored pigment includes at least one of iron oxide, erbium oxide, manganese oxide, terbium oxide, and neodymium oxide.
The second aspect of the invention provides a preparation method of the modified nitride-doped microcrystalline glass composite material, wherein the modified nitride and the microcrystalline glass are uniformly mixed, and are subjected to crystallization heat treatment after being pressed and formed, so that the modified nitride-doped microcrystalline glass composite material is obtained.
Optionally, the crystallization heat treatment is performed under a nitrogen inert atmosphere.
Preferably, the flow rate of the nitrogen is 50-120 mL/min.
Optionally, the crystallization treatment comprises a one-step crystallization heat treatment and a two-step crystallization heat treatment, preferably a one-step crystallization heat treatment.
Optionally, the temperature of the one-step crystallization heat treatment is 500-.
Optionally, the two-step crystallization heat treatment comprises: carrying out primary crystallization heat treatment at the temperature of 400-;
preferably, the time of the first crystallization heat treatment and the time of the second crystallization heat treatment are respectively and independently 1.5-3.5 h.
Optionally, the one-step crystallization heat treatment is carried out at 800 ℃ for 3 h.
A third aspect of the invention provides the use of a modified nitride doped microcrystalline glass composite for the manufacture of a denture.
Compared with the prior art, the invention has at least the following beneficial effects:
in the modified nitride-doped microcrystalline glass composite material provided by the invention, the strength of the modified nitride is very high, and the modified nitride and microcrystalline glass crystal form a synergistic effect to prevent crack propagation and improve the strength; and the modified nitride improves the bonding performance between the nitride powder and the glass powder, can effectively reduce air holes in a glass system, and enables the modified nitride-doped microcrystalline glass composite material not to affect the permeability while improving the strength. The modified nitride-doped microcrystalline glass composite material belongs to glass ceramics, the main crystal phase is lithium disilicate, and the modified nitride-doped microcrystalline glass composite material contains a large amount of modified nitride, so that the strength is improved to be more than 540MPa due to high strength and good combination with microcrystalline glass, and the permeability is not influenced.
The preparation method of the modified nitride-doped microcrystalline glass composite material provided by the invention is simple in process, easy to control, easy to burn, uniform in component distribution and suitable for large-scale industrial production.
The application of the modified nitride-doped microcrystalline glass composite material provided by the invention provides a material with excellent processability and aesthetic property for false teeth, and is suitable for large-scale popularization and use.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but it will be understood by those skilled in the art that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In recent years, much work has been done to improve the strength and fracture toughness of glass ceramics, and there are three general aspects: (1) the strength is improved by obtaining a microstructure in a directional distribution by a high-temperature pressurizing method such as hot pressing, hot extrusion and the like; (2) the interlayer binding force is improved by replacing alkali metal ions with alkaline earth metal ions: (3) using ZrO 2 To increase strength and fracture toughness. In addition, the theory research aspect will continue to deeply discuss and improve the structure forming and enhancing mechanism, and in the process aspect, the glass melting temperature will be reduced, the process conditions will be simplified, and the microcrystalline glass will develop towards the large-scale industrialization.
CN112047733A discloses a zirconia/lithium silicate or silica glass ceramic composite material with a microscopic bionic structure for false teeth and a preparation method thereof. The composite material consists of 35-90% of zirconia by volume percentage and the balance of lithium silicate or silica glass, wherein the zirconia is microscopically stacked on a glass substrate in a lamellar form. Although the strength of the dental microcrystalline glass prepared by the patent is improved, the strength is not obviously improved.
CN110291054A discloses a material composition and a method for producing translucent ZrO having ultra-high flexural strength 2 SiO 2 A method of nanocrystalline glass-ceramic (NCGC). The method comprises the following steps: (1) preparation of homogeneous ZrO via sol-gel process 2 SiO 2 A nanoscale powder; (2) pressure assisted sintering of ZrO 2 SiO 2 Nanoscale sol-gel powder to obtain translucent ZrO 2 SiO 2 NCGC. But the preparation method is complex and the production cost is high.
According to the first aspect of the invention, the modified nitride-doped microcrystalline glass composite material comprises 1-10% of modified nitride by mass percent, and the balance of microcrystalline glass.
In the modified nitride-doped microcrystalline glass composite material provided by the invention, the strength of the modified nitride is very high, and the modified nitride and microcrystalline glass crystal form a synergistic effect to prevent crack propagation and improve the strength; and the modified nitride improves the bonding performance between the nitride powder and the glass powder, can effectively reduce air holes in a glass system, and enables the modified nitride-doped microcrystalline glass composite material not to affect the permeability while improving the strength. The modified nitride-doped microcrystalline glass composite material belongs to glass ceramics, the main crystal phase is lithium disilicate, and the modified nitride-doped microcrystalline glass composite material contains a large amount of modified nitride, so that the strength is improved to be more than 540MPa due to high strength and good combination with microcrystalline glass, and the permeability is not influenced.
Optionally, the modified nitride comprises modified beta-Si 3 N 4 At least one of modified aluminum nitride and magnesium nitride.
When the addition amount of the modified nitride is less than 1%, the effect of improving the strength cannot be achieved; when the addition amount of the modified nitride is more than 10%, the network structure of the glass is affected, thereby affecting the strength of the glass-ceramic.
The nitride powder is modified, and if the nitride is not modified, the interfacial bonding property between the nitride powder and the glass powder is deteriorated, which increases pores in the glass ceramic, and conversely, reduces the permeability and strength of the glass ceramic. In some embodiments of the present invention, the shape of the nitride is not fixed, and may be spherical, rod-like, five-pointed star, or the like.
Preferably, the particle size of the modified nitride is 50nm to 300 nm.
In some embodiments of the invention, the modified nitride typically has a particle size of, but not limited to, 50nm, 100nm, 150nm, 200nm, 250nm, or 300 nm.
Optionally, the glass-ceramic comprises SiO in mass percent 2 50.0％-60.0％、Li 2 O 10.0％-20.0％、P 2 O 5 1.0％-3.0％、Al 2 O 3 1.5％-3.5％、K 2 O3% -10% and ZrO 2 1.0％-10％。
In some embodiments of the invention, SiO is in the glass-ceramic 2 Is typically but not limited to 50.0%, 51.0%, 52.0%, 53.0%, 54.0%, 55.0%, 56.0%, 57.0%, 58.0%, 59.0% or 60.0%; li 2 The mass percentage of O is typically but not limited to 10.0%, 11.0%, 12.0%, 13.0%, 14.0%, 15.0%, 16.0%, 17.0%, 18.0%, 19.0%, or 20.0%; p 2 O 5 Is typically but not limited to 1.0%, 1.5%, 2.0%, 2.5% or 3%; al (Al) 2 O 3 Is typically but not limited to 1.5%, 2.0%, 2.5%, 3.0% or 3.5%; k 2 The mass percentage of O is typically but not limited to 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%; ZrO (ZrO) 2 Is typically but not limited to 1.0%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
Preferably, the material also comprises B in percentage by mass 2 O 3 0-6.0％、Na 2 0-5.0% of O and 0-5.0% of color pigment.
In some embodiments of the invention, B 2 O 3 Is typically but not limited to 0%, 1.0%, 2%, 3%, 4%, 5% or 6%; na (Na) 2 The mass percentage of O is typically but not limited to 0%, 1.0%, 2%, 3%, 4%, or 5.0%; the mass percentage of the colored pigment is typically but not limited to 0%, 1.0%, 2%, 3%4% or 5.0%.
Preferably, the colored pigment includes at least one of iron oxide, erbium oxide, manganese oxide, terbium oxide, and neodymium oxide.
According to the preparation method of the modified nitride-doped microcrystalline glass composite material provided by the second aspect of the invention, the modified nitride and the microcrystalline glass powder are uniformly mixed, and are subjected to crystallization heat treatment after being pressed and molded to obtain the modified nitride-doped microcrystalline glass composite material.
The preparation method of the modified nitride-doped microcrystalline glass composite material provided by the invention is simple in process, easy to control, easy to burn, uniform in component distribution and suitable for large-scale industrial production.
The mixing method of the modified nitride and the glass powder is not fixed, and dry mixing and wet mixing are both possible, and the modified nitride powder and the glass powder are mixed uniformly.
Optionally, the crystallization heat treatment is performed under a nitrogen inert atmosphere.
Preferably, the flow rate of the nitrogen is 50-120 mL/min.
In some embodiments of the invention, the flow rate of nitrogen is typically, but not limited to, 50mL/min, 60mL/min, 70mL/min, 80mL/min, 90mL/min, 100mL/min, 110mL/min, or 120 mL/min.
Optionally, the crystallization treatment comprises a one-step crystallization heat treatment and a two-step crystallization heat treatment, preferably a one-step crystallization heat treatment.
The one-step crystallization heat treatment process is simple, and the production efficiency can be improved; the lithium metasilicate obtained by the two-step crystallization heat treatment has better processability and smaller abrasion degree to needles.
Optionally, the temperature of the one-step crystallization heat treatment is 500-.
In some embodiments of the present invention, the temperature of the one-step crystallization heat treatment is typically, but not limited to, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, or 1000 ℃.
Optionally, the two-step crystallization heat treatment comprises: carrying out primary crystallization heat treatment at the temperature of 400-;
preferably, the time of the first crystallization heat treatment and the time of the second crystallization heat treatment are respectively and independently 1.5-3.5 h.
In some embodiments of the present invention, the time of the first crystallization heat treatment and the second crystallization heat treatment is typically, but not limited to, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 3h or 3.5 h.
Optionally, the one-step crystallization heat treatment is carried out at 800 ℃ for 3 h.
The modified nitride-doped microcrystalline glass composite material provided by the third aspect of the invention is applied to the preparation of false teeth.
The application of the modified nitride-doped microcrystalline glass composite material provided by the invention provides a material with excellent processability and aesthetic property for false teeth, and is suitable for large-scale popularization and use.
The invention is further illustrated by the following specific examples and comparative examples, but it should be understood that these examples are for purposes of illustration only and are not to be construed as limiting the invention in any way. The raw materials used in the examples and comparative examples of the present invention, those having no particular reference to conditions, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
This example provides a modified nitride-doped glass ceramic composite material, in which the modified nitride is modified beta-Si 3 N 4 The content is 2 percent, and the rest is microcrystalline glass. The microcrystalline glass powder comprises the following formula: SiO 2 2 58％、Li 2 O 16.7％、P 2 O 5 1.7％、Al 2 O 3 3.2％、K 2 O 4.8％、B 2 O 3 2.5％、ZrO 2 6.9％、Na 2 O2.6 percent and 3.6 percent of colored pigment, and the specific preparation method comprises the following steps:
1. and uniformly mixing the microcrystalline glass powder and the modified nitride, and performing dry pressing at 80MPa to obtain a blocky glass powder blank.
2. And (3) carrying out heat treatment on the blank obtained in the step (1) at 800 ℃ under normal pressure for 3h, introducing nitrogen to form an inert atmosphere during the heat treatment, wherein the flow rate of the nitrogen is 85mL/min, so as to obtain the modified nitride-doped microcrystalline glass composite material block.
Example 2
The present embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from embodiment 1 in that the addition amount of the modified nitride is 5%, and the remaining raw materials and steps are the same as those in embodiment 1, and are not described herein again.
Example 3
The present embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from embodiment 1 in that the addition amount of the modified nitride is 7%, and the remaining raw materials and steps are the same as those in embodiment 1, and are not described herein again.
Example 4
The present embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from embodiment 1 in that the addition amount of the modified nitride is 10%, and the remaining raw materials and steps are the same as those in embodiment 1, and are not described herein again.
Example 5
The embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from the embodiment 3 in that the formula of the microcrystalline glass powder is as follows: SiO 2 2 53％、Li 2 O 19.6％、P 2 O 5 1.6％、Al 2 O 3 1.7％、K 2 O 5.6％、B 2 O 3 4.6％、ZrO 2 7.6％、Na 2 O1.9% and colored pigment 4.4%, and the rest raw materials and steps are the same as those in example 3 and are not repeated herein.
Example 6
The embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from the embodiment 3 in that the formula of the microcrystalline glass powder is as follows: SiO 2 2 55％、Li 2 O 12.6％、P 2 O 5 2.5％、Al 2 O 3 2.6％、K 2 O 8.1％、B 2 O 3 5.5％、ZrO 2 5.8％、Na 2 3.6 percent of O and 3.3 percent of colored pigment, and the rest raw materials and steps are the same as those in example 3 and are not described again.
Example 7
The embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from the embodiment 3 in that the formula of the microcrystalline glass powder is as follows: SiO 2 2 58％、Li 2 O 15.6％、P 2 O 5 2.2％、Al 2 O 3 2.8％、K 2 O 7.3％、B 2 O 3 2.3％、ZrO 2 6.4％、Na 2 O2.8% and colored pigment 2.6%, and the rest raw materials and steps are the same as those in example 3, and are not described again.
Example 8
The embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from the embodiment 3 in that the formula of the microcrystalline glass powder is as follows: SiO 2 2 52％、Li 2 O 13.8％、P 2 O 5 2.7％、Al 2 O 3 2.2％、K 2 O 8.9％、B 2 O 3 5.1％、ZrO 2 7.1％、Na 2 O4.1% and colored pigment 4.1%, and the rest raw materials and steps are the same as those in example 3, and are not described again.
Example 9
The present embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from embodiment 3 in that the modified nitride is modified aluminum nitride, and the remaining raw materials and steps are the same as those in embodiment 3, and are not described herein again.
Example 10
The present embodiment provides a modified nitride-doped microcrystalline glass composite material, which is different from embodiment 3 in that the modified nitride is modified magnesium nitride, and other raw materials and steps are the same as those in embodiment 3, and are not described herein again.
Example 11
This example provides a modified nitride-doped microcrystalline glass composite material, which is different from example 3 in that, in step 2, first crystallization heat treatment is performed at 500 ℃ for 2 hours, and then second crystallization heat treatment is performed at 750 ℃ for 2 hours, and the remaining raw materials and steps are the same as those in example 3, and are not repeated herein.
Comparative example 1
The comparative example provides a modified nitride-doped microcrystalline glass composite material, which is different from the example 3 in that no modified nitride is added, and other raw materials and steps are the same as those in the example 3, and are not repeated herein.
Comparative example 2
The comparative example provides a modified nitride-doped microcrystalline glass composite material, which is different from the example 5 in that no modified nitride is added, and other raw materials and steps are the same as those in the example 5, and are not repeated herein.
Comparative example 3
The comparative example provides a modified nitride-doped glass-ceramic composite material, which is different from example 3 in that the added nitride is non-modified silicon nitride, and the rest of the raw materials and steps are the same as those in example 3 and are not repeated herein.
Comparative example 4
The comparative example provides a modified nitride-doped microcrystalline glass composite material, which is different from example 3 in that the addition amount of the modified nitride is 0.5%, and the rest raw materials and steps are the same as those in example 3 and are not repeated herein.
Comparative example 5
The comparative example provides a modified nitride-doped microcrystalline glass composite material, which is different from example 3 in that the addition amount of the modified nitride is 15%, and the rest raw materials and steps are the same as those in example 3 and are not repeated herein.
Test examples
The following property measurements were made on the modified nitride-doped microcrystalline glass composites obtained in examples 1 to 11 and comparative examples 1 to 5.
(1) Biaxial bending strength: the reference standard of the test method is GB 30367-2013.
(2) Light transmittance: the testing method is to select a ceramic chip with the thickness of 1mm, and polish the two sides until the smoothness Ra is less than 0.04.
And (3) placing the processed ceramic chip in an detection method of Eschollian spectrophotometer equipment reference standard JCT 2020-2010.
(3) Fracture toughness: the sample was supported by 1.2 x 4 x 21mm test specimen, U plus V slits were made through the sample and left blank, the maximum force to break was measured at a universal tester loading speed of 0.5mm/min, and the fracture toughness was calculated, referenced against standard 30367 and 2013. The data obtained from the tests are shown in table 1.
Table 1 table of performance data for modified nitride-doped glass-ceramic composite materials
As can be seen from table 1, compared with the microcrystalline glass ceramics provided in comparative examples 1 to 3 without adding modified nitride, the strength of the microcrystalline glass provided in examples 1 to 11, comparative example 4 and comparative example 5 after doping modified nitride is obviously improved, and the strength of the microcrystalline glass is improved differently according to the addition amount of modified silicon nitride in examples 1 to 4; however, the strength of the modified nitride is not improved as expected when the addition amount of the modified nitride is insufficient as compared with comparative example 4, and the permeability of the composite glass ceramic is affected when the addition amount of the modified nitride is too large as compared with comparative example 5; compared with different glass system examples 5-8, the strength of the glass is improved by adding the modified nitride; when different modified nitrides are added in the examples 3, 9 and 10, the improvement effects of the modified silicon nitride, the modified aluminum nitride and the modified magnesium nitride are similar to those of the microcrystalline glass; comparing the addition effects of the modified nitride example 3 and the unmodified nitride comparative example 3, the permeability of the composite glass ceramics when the unmodified nitride is doped is greatly affected, and the effect is not achieved due to the improvement of the strength due to the lack of tight bonding. Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The modified nitride-doped microcrystalline glass composite material is characterized by comprising 1-10% of modified nitride by mass percent, and the balance being microcrystalline glass.
2. The modified nitride doped microcrystalline glass composite of claim 1, wherein the modified nitride comprises modified β -Si 3 N 4 At least one of modified aluminum nitride and magnesium nitride;
preferably, the particle size of the modified nitride is 50nm to 300 nm.
3. The modified nitride doped microcrystalline glass composite of claim 1, wherein the microcrystalline glass comprises SiO in mass percent 2 50.0％-60.0％、Li 2 O 10.0％-20.0％、P 2 O 5 1.0％-3.0％、Al 2 O 3 1.5％-3.5％、K 2 O3% -10% and ZrO 2 1.0％-10％；
Preferably, the material also comprises B in percentage by mass 2 O 3 0-6.0％、Na 2 At least one of 0 to 5.0% of O and 0 to 5.0% of a color pigment;
preferably, the colored pigment includes at least one of iron oxide, erbium oxide, manganese oxide, terbium oxide, and neodymium oxide.
4. The method for preparing a modified nitride-doped microcrystalline glass composite material according to any one of claims 1 to 3, wherein the modified nitride and the microcrystalline glass are uniformly mixed, and subjected to crystallization heat treatment after being subjected to compression molding to obtain the modified nitride-doped microcrystalline glass composite material.
5. The method according to claim 4, wherein the crystallization heat treatment is performed in a nitrogen inert gas atmosphere;
preferably, the flow rate of the nitrogen is 50-120 mL/min.
6. The method according to claim 4, wherein the crystallization heat treatment comprises a one-step crystallization heat treatment and a two-step crystallization heat treatment, preferably a one-step crystallization heat treatment.
7. The method as claimed in claim 6, wherein the temperature of the one-step crystallization heat treatment is 500-1000 ℃.
8. The method of claim 6, wherein the two-step crystallization heat treatment comprises: carrying out primary crystallization heat treatment at the temperature of 400-;
preferably, the time of the first crystallization heat treatment and the time of the second crystallization heat treatment are respectively and independently 1.5-3.5 h.
9. The method according to claim 6, wherein the one-step crystallization heat treatment is performed at 800 ℃ for 3 hours.
10. Use of the modified nitride-doped glass-ceramic composite material according to any one of claims 1 to 3 or the modified nitride-doped glass-ceramic composite material prepared by the preparation method according to any one of claims 4 to 9 for preparing dentures.
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