Aluminum silicate-based porous ceramic framework and preparation method and application thereof, resin-infiltrated ceramic material and application thereof, oral prosthesis

Abstract

This invention provides an aluminosilicate-based porous ceramic framework, its preparation method and application, resin-infiltrated ceramic materials and their applications, and dental prostheses, relating to the field of dental materials technology. Using Al2O3, SiO2, Na2O, and K2O as raw materials, the proportions of sodium, potassium, and silicon can be freely adjusted. By changing the relative content of sodium, potassium, and silicon, the porous ceramic framework prepared from aluminosilicate-based sodium-potassium salts exhibits different physicochemical properties. As a matrix, resin-infiltrated ceramic materials with different physicochemical properties and aesthetic characteristics can be prepared to meet the needs of various dental applications.

Description

Technical Field

[0001] This invention relates to the field of dental materials technology, and in particular to an aluminum silicate-based porous ceramic framework and its preparation method and application, resin-infiltrated ceramic materials and their application, and dental prostheses. Background Technology

[0002] Since the 1980s, computer-aided design and computer-aided manufacturing (CAD / CAM) technologies have developed rapidly. These technologies are widely used in dental restoration, primarily in the manufacture of ceramic, polymer, and composite dental restorations. The rapid application of these technologies, along with digital scanning and other techniques, in dentistry has led to continuous upgrades and iterations of chairside dental systems. The concept of "immediate restoration" has taken root in the minds of both doctors and patients, and the ability for patients to have their teeth put back on the same day is no longer a distant dream.

[0003] Besides the necessary equipment, the consumable materials used in chairside systems play a crucial role in the speed of restoration. In addition to meeting the basic requirements of aesthetics, durability, and function, the fabrication of restorations must also achieve rapid tooth eruption to ensure faster patient placement and improve the overall treatment experience. While ceramic dental restorations require further sintering, glazing, and polishing after CAD design and CAM cutting to obtain the final restoration, polymer-based or composite materials do not require sintering or glazing; they only need polishing before placement, making them more suitable for chairside systems. Compared to polymer-based materials, composite materials possess superior mechanical properties and more closely resemble natural teeth, leading to their rapid development in dentistry.

[0004] In dentistry, composite materials mainly refer to resin-ceramic composites, encompassing two main types. One type is resin composites, where the matrix is ​​organic, with inorganic filler particles dispersed within the organic structure primarily serving a reinforcing role. However, the aesthetic and wear-resistant properties of this type are inferior to another material known as "polymer-infiltrated ceramic network (PICN)" or "resin-infiltrated ceramic." Resin-infiltrated ceramic is obtained by preparing a porous ceramic framework, then infiltrating it with resin and curing it. It possesses mechanical and aesthetic properties closer to those of natural teeth. Over the past decade, researchers worldwide have conducted extensive technical design and optimization of resin-infiltrated ceramic materials, resulting in a series of research findings.

[0005] Among them, a relatively representative one is Chinese Patent CN115894001A, which uses potassium sodium aluminosilicate to prepare a porous ceramic matrix through ultra-high cold isostatic pressing (350 - 600 MPa). After resin infiltration and curing, a resin-infiltrated ceramic material with high hardness (2.5 - 4.5 GPa) and high wear resistance is obtained. However, the raw material system it uses is compounds with a fixed molar ratio, such as aluminum silicate, potassium sodium aluminosilicate, sodium aluminosilicate, etc., which cannot meet the usage scenario requirements of more resin-infiltrated ceramics. Summary of the Invention

[0006] The purpose of the present invention is to provide a potassium sodium aluminosilicate-based porous ceramic skeleton, its preparation method and application, a resin-infiltrated ceramic material and its application, and a dental prosthesis. The preparation method can flexibly adjust the relative content of sodium, potassium, and silicon elements, and resin-infiltrated ceramic materials with different optical transparencies and mechanical properties can be obtained, so as to be applied in different dental usage scenarios, thereby expanding the application range of potassium sodium aluminosilicate-based resin-infiltrated ceramics in the dental field.

[0007] In order to achieve the above-mentioned invention purpose, the present invention provides the following technical solutions:

[0008] The present invention provides a preparation method for a potassium sodium aluminosilicate-based porous ceramic skeleton, including the following steps:

[0009] (1) Mix various oxide raw materials according to the molar ratio shown in Formula 1 to obtain a mixed material;

[0010] The oxide raw materials are multiple of Al2O3, SiO2, Na2O, and K2O; the composition of the mixed material is shown in Formula 1: mNa2O·nK2O·Al2O3·2pSiO2 Formula 1,

[0011] In Formula 1, 0 < m + n ≤ 1, and p is an integer between 1 and 5;

[0012] (2) Melt and cool the mixed material to obtain a basic raw material;

[0013] (3) Crush the basic raw material to obtain a basic powder;

[0014] (4) Mix and ball-mill the basic powder, binder, and dispersion solvent to obtain a slurry;

[0015] (5) Granulate the slurry to obtain a granulated powder;

[0016] (6) Subject the granulated powder to dry pressing and cold isostatic pressing in sequence to obtain a green body;

[0017] (7) Sinter the green body to obtain a potassium sodium aluminosilicate-based porous ceramic skeleton.

[0018] Preferably, in step (6), the pressure of the cold isostatic pressing is 100-300 MPa, and the holding time is 0.5-5 min.

[0019] Preferably, in step (7), the sintering temperature is 800-1400℃ and the holding time is 4-24h.

[0020] Preferably, in step (3), the average particle size of the base powder is 1 to 35 μm and the morphology is a non-spherical structure.

[0021] Preferably, in step (3), the crushing includes: placing the basic raw material in a crusher for preliminary crushing, and then ball milling the crushed basic raw material to achieve secondary crushing.

[0022] Preferably, in step (2), the melting temperature is 1200-1800℃ and the time is 4-24h.

[0023] Preferably, in step (6), the pressure of the dry press is 3 to 10 MPa, and the holding time is 0.5 to 5 min.

[0024] Preferably, in step (4), the adhesive includes one or more of polyvinyl alcohol, polyethylene glycol, polyvinyl butyral, and sodium carboxymethyl cellulose.

[0025] Preferably, in step (4), the adhesive is used in the form of an adhesive solution, the mass concentration of which is 1-5% and the mass of which is 5-30% of the mass of the base powder.

[0026] Preferably, in step (4), the dispersing solvent includes water or ethanol.

[0027] Preferably, in step (5), the particle size of the granulated powder is 100 to 200 mesh.

[0028] The present invention provides an aluminum silicate-based porous ceramic framework prepared by the preparation method described above.

[0029] Preferably, the porosity is 20-50%.

[0030] This invention provides the application of the aluminum silicate-based porous ceramic framework described above in resin-infiltrated ceramic materials.

[0031] The present invention provides a resin-permeable ceramic material, comprising an aluminum silicate-based porous ceramic framework and a resin material permeated in the aluminum silicate-based porous ceramic framework; wherein the aluminum silicate-based porous ceramic framework is the aluminum silicate-based porous ceramic framework described in the above-mentioned scheme.

[0032] Preferably, the resin material includes acrylic resin.

[0033] Preferably, the hardness of the resin infiltration ceramic material is ≥2.6 GPa, the flexural strength is ≥300 MPa, and the elastic modulus is ≥30 GPa.

[0034] Preferably, based on mass percentage, the raw materials for preparing the acrylic resin include: 97-99.9% of acrylate monomers and 0.1-3% of initiators.

[0035] Preferably, the acrylate monomers include main monomers and diluent monomers; the mass ratio of the main monomers to the diluent monomers is (1.5-9):1.

[0036] Preferably, the main monomers include one or more of bisphenol A-glycidyl methacrylate, bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, and urethane dimethacrylate; the diluent monomers include one or more of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, and trimethylolpropane triacrylate.

[0037] The present invention provides an application of the resin infiltration ceramic material described in the above solution in the preparation of oral restorations.

[0038] The present invention provides an oral restoration containing the resin infiltration ceramic material described in the above solution.

[0039] Preferably, the oral restoration includes dental veneers, high restorations, low restorations, single crowns, anterior teeth, or three-unit bridges.

[0040] The present invention provides a method for preparing a porous aluminosilicate ceramic framework, including the following steps:

[0041] (1) Mix various oxide raw materials according to the molar ratio shown in Formula 1 to obtain a mixture; the oxide raw materials are multiple of Al2O3, SiO2, Na2O, and K2O; the composition of the mixture is shown in Formula 1: mNa2O·nK2O·Al2O3·2pSiO2 Formula 1, in Formula 1, 0 < m + n ≤ 1, and p is an integer between 1 and 5; (2) Melt the mixture, cool it, and obtain the basic raw material; (3) Crush the basic raw material to obtain basic powder; (4) Mix and ball-mill the basic powder, binder, and dispersion solvent to obtain a slurry; (5) Granulate the slurry to obtain granulated powder; (6) Subject the granulated powder to dry pressing and cold isostatic pressing in sequence to obtain a green body; (7) Sinter the green body to obtain a porous aluminosilicate ceramic framework.

[0042] This invention uses Al2O3, SiO2, Na2O and K2O as raw materials, and can freely adjust the ratio of sodium, potassium and silicon elements. By changing the relative content of sodium, potassium and silicon elements, the porous ceramic framework prepared by aluminum silicate-based sodium potassium salt exhibits different physicochemical properties. As a matrix, resin-infiltrated ceramic materials with different physicochemical properties and aesthetic characteristics can be prepared to meet the needs of different dental scenarios.

[0043] Furthermore, the base powder of this invention is a micron-sized powder. The porous ceramics prepared from micron-sized powder have relatively large pore sizes. According to the classification of porous ceramics by pore size, they belong to the macropore level (pore size > 50 nm), which makes it easy for the resin to fully penetrate the skeleton and form an interlocking structure. They have stronger resistance to crack propagation and exhibit superior mechanical properties such as flexural strength and elastic modulus.

[0044] Compared to CN115894001A, which uses ultra-high cold isostatic pressing (350-600 MPa) and has high equipment requirements, this invention only requires common cold isostatic pressing pressure (≤300 MPa) to prepare resin-infiltrated ceramic materials with a hardness ≥2.6 GPa. This is because the micron-sized powder (i.e., the base powder) used in this invention is non-spherical micron particles. With appropriate sintering temperatures, a porous ceramic framework with low porosity can be prepared. Generally, the lower the porosity, the higher the hardness of the prepared resin-infiltrated ceramic material. On the other hand, because when the cold isostatic pressing pressure exceeds a certain limit, i.e., approaches the theoretical bulk density of the powder, the increase in green body density changes from being mainly due to interparticle slippage to being mainly due to particle deformation and breakage. This will destroy the original particle morphology, and the performance will actually decrease. This invention uses a pressure value close to the theoretical bulk density, which is set as the optimal isostatic pressing pressure, and can prepare resin-infiltrated ceramic materials with excellent hardness performance without using ultra-high cold isostatic pressing.

[0045] Furthermore, CN115894001A has a narrow sintering temperature range (600-800℃), while the porous ceramic skeleton of the present invention has a sintering temperature of 800-1400℃, which is more compatible with the activity of micron-sized powders. The particles directly form an effective sintering neck, further improving the mechanical strength of the skeleton.

[0046] The preparation process of this invention is simple, easy to industrialize, low in cost, and requires simple equipment and raw materials. Conventional equipment in the field can meet the requirements. Attached Figure Description

[0047] Figure 1 This is a trend diagram showing the effect of sodium and potassium content on the mechanical properties of resin-infiltrated ceramic materials.

[0048] Figure 2 A trend diagram showing the influence of sodium and potassium content on the permeability and aesthetic properties of resin-permeable ceramic materials.

[0049] Figure 3 XRD pattern of the base raw material of Example 1;

[0050] Figure 4 XRD pattern of the base raw material of Example 2;

[0051] Figure 5 XRD pattern of the base raw material of Example 3;

[0052] Figure 6 XRD pattern of the base raw material of Example 4;

[0053] Figure 7 XRD pattern of the base raw material of Example 5;

[0054] Figure 8 XRD pattern of the base raw material of Example 6;

[0055] Figure 9 XRD pattern of the base raw material of Example 7;

[0056] Figure 10 XRD pattern of the base raw material of Example 8;

[0057] Figure 11 XRD pattern of the base raw material of Example 9;

[0058] Figure 12 XRD pattern of the base raw material of Example 10;

[0059] Figure 13 Microscopic morphology diagram of the micron-sized powder obtained by secondary crushing of the ball mill in Example 1. Detailed implementation method

[0060] The present invention provides a preparation method of a porous ceramic framework based on aluminosilicate, comprising the following steps:

[0061] (1) Mix various oxide raw materials according to the molar ratio shown in Formula 1 to obtain a mixed material;

[0062] The oxide raw materials are multiple of Al2O3, SiO2, Na2O and K2O; the composition of the mixed material is shown in Formula 1: mNa2O·nK2O·Al2O3·2pSiO2 Formula 1,

[0063] In Formula 1, 0 < m + n ≤ 1, and p is an integer between 1 and 5;

[0064] (2) Melt and cool the mixed material to obtain a base raw material;

[0065] (3) Crush the base raw material to obtain a base powder;

[0066] (4) Mix the base powder, binder, and dispersion solvent by ball milling to obtain a slurry;

[0067] (5) Granulate the slurry to obtain granulated powder;

[0068] (6) Subject the granulated powder to dry pressing and cold isostatic pressing in sequence to obtain a green compact;

[0069] (7) Sinter the green compact to obtain a porous alumina-based ceramic framework.

[0070] In the present invention, without special instruction, the raw materials used are all commercially available products well-known in the art.

[0071] In the present invention, the oxide raw materials are mixed according to the molar ratio shown in Formula 1 to obtain a mixture.

[0072] In the present invention, the oxide raw materials are multiple of Al2O3, SiO2, Na2O, and K2O; the composition of the mixture is as shown in Formula 1: mNa2O·nK2O·Al2O3·2pSiO2 Formula 1,

[0073] In Formula 1, 0 < m + n ≤ 1, and p is an integer between 1 and 5; specifically, on the premise of satisfying 0 < m + n ≤ 1, m can be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1, and n can also be 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1; p can specifically be 1, 2, 3, 4, or 5.

[0074] In the present invention, the addition of sodium and potassium will change the refractive index, scattering, and absorption characteristics of the resin infiltration ceramic material. Therefore, the introduction of sodium and potassium within a certain range can reduce light scattering and improve the transparency of the glass; however, when the sodium and potassium content is too low, crystal crystals may may cause the appearance of crystal phases in the glass, thereby reducing transparency. This is mainly because the refractive indices of different phases are different, resulting in relatively serious dispersion when light propagates in this mixed-phase medium, leading to a decrease in transparency; the structure of silicon in the glass exists in the form of a silicon-oxygen tetrahedron network structure. When its relative content is relatively high, it exhibits the common characteristics of silicates. Therefore, according to the random glass network theory, when the content of silicon increases, its spatial structure becomes more stable, with fewer defects, and the corresponding mechanical properties will also be improved. Figure 1 The influence trend of sodium and potassium content on the mechanical properties of the resin infiltration ceramic material was analyzed in detail, Figure 2 The influence trend of sodium and potassium content on the transparency aesthetic properties of the resin infiltration ceramic material was analyzed.

[0075] This invention uses Al2O3, SiO2, Na2O and K2O as raw materials, and can freely adjust the ratio of sodium, potassium and silicon elements. By changing the relative content of sodium, potassium and silicon elements, the porous ceramic framework prepared by aluminum silicate-based sodium potassium salt exhibits different physicochemical properties. As a matrix, resin-infiltrated ceramic materials with different physicochemical properties and aesthetic characteristics can be prepared to meet the needs of different dental scenarios.

[0076] In this invention, the mixing is preferably carried out in a mixer; the mixing time is preferably 5 to 120 min, more preferably 30 to 100 min, and even more preferably 40 to 60 min; the mixing speed is preferably 20 to 60 r / min, more preferably 30 to 50 r / min, and even more preferably 40 r / min.

[0077] After obtaining the mixture, the present invention melts and cools the mixture to obtain the basic raw material.

[0078] In this invention, the melting temperature is preferably 1200–1800°C, more preferably 1300–1700°C, and even more preferably 1400–1600°C; the melting time is preferably 4–24 h, more preferably 8–20 h, and even more preferably 12–16 h. This invention utilizes melting to allow raw material powders of different compositions to be fully and uniformly mixed, melted at high temperature until homogenized, and crystallized within the crystalline phase region of the phase diagram to obtain a basic raw material with a specific crystalline phase or a mixture of crystalline and glassy phases.

[0079] In this invention, depending on the composition of the mixture, the resulting basic raw material phase composition can be a glassy substance, one or more crystalline substances, or a mixture of a glassy phase and one or more crystalline phases. The crystalline phases of the crystalline substances include one or more of the following: quartz, mullite, alumina, albite, potassium feldspar, and sodium-potassium feldspar.

[0080] After obtaining the basic raw materials, the present invention crushes the basic raw materials to obtain basic powder.

[0081] In this invention, the crushing preferably includes: placing the basic raw material in a crusher for preliminary crushing, and then ball milling the crushed basic raw material to achieve secondary crushing.

[0082] In this invention, the crusher is preferably a jaw crusher; the particle size of the base raw material after primary crushing is preferably in the millimeter range. In this invention, the rotational speed of the ball mill is preferably 300–800 r / min, more preferably 400–700 r / min, and even more preferably 500–600 r / min; the ball milling time is preferably 8–24 h, more preferably 10–20 h, and even more preferably 12–16 h.

[0083] In this invention, the average particle size of the base powder obtained after crushing is preferably 1-35 μm, and the morphology is a non-spherical structure. When this powder raw material is used to prepare a porous ceramic skeleton by particle packing, there is good mechanical interlocking force between the particles, and after it is compounded with resin, it forms a structure in which the resin and skeleton interlock, which plays a significant role in optimizing the strength of the mechanical properties.

[0084] After obtaining the base powder, the present invention mixes and ball-mills the base powder, binder and dispersing solvent to obtain a slurry.

[0085] In this invention, the binder preferably comprises one or more of polyvinyl alcohol, polyethylene glycol, polyvinyl butyral, and sodium carboxymethyl cellulose; the binder is preferably used in the form of a binder solution, the mass concentration of which is preferably 1-5%, more preferably 2-4%, and even more preferably 3%; the solvent of the binder solution is preferably water or ethanol; when the binder is polyvinyl butyral, the solvent is preferably ethanol; the mass of the binder solution is preferably 5-30% of the mass of the base powder, more preferably 10-25%, and even more preferably 15-20%.

[0086] In this invention, the dispersing solvent is preferably water or ethanol; the mass of the dispersing solvent is preferably 1 to 3 times the mass of the base powder. In this invention, the mixing and ball milling time is preferably 0.5 to 4 hours, more preferably 1 to 3 hours; the mixing and ball milling speed is preferably 300 to 800 r / min, more preferably 400 to 700 r / min.

[0087] After obtaining the slurry, the present invention granulates the slurry to obtain granulated powder.

[0088] In this invention, the granulation is preferably spray granulation or drying followed by sieving. In this invention, the particle size of the granulated powder is preferably 100-200 mesh, more preferably 120-180 mesh. This invention does not have special requirements for the spray granulation conditions; it is sufficient to obtain granulated powder with the above-mentioned particle size. In this invention, the drying temperature is preferably 60-100℃, more preferably 70-80℃.

[0089] After obtaining the granulated powder, the present invention sequentially performs dry pressing and cold isostatic pressing on the granulated powder to obtain a green body.

[0090] In this invention, the pressure of the dry pressing is preferably 3-10 MPa, more preferably 4-9 MPa, and even more preferably 5-8 MPa; the holding time of the dry pressing is preferably 0.5-5 min, more preferably 1-4 min, and even more preferably 2-3 min. The purpose of the dry pressing in this invention is twofold: first, to prepare a porous ceramic framework with specific dimensions; and second, to ensure the green body has sufficient mechanical strength during the transfer of the porous ceramic framework.

[0091] In this invention, the pressure of the cold isostatic pressing is preferably 100-300 MPa, more preferably 150-250 MPa, and even more preferably 180-220 MPa; the holding time of the cold isostatic pressing is preferably 0.5-5 min, more preferably 1-4 min, and even more preferably 2-3 min. In this invention, the cold isostatic pressing serves two purposes: first, to ensure that the dry-pressed green body experiences uniform stress in all directions after the second isostatic pressing, thus largely ensuring consistent porosity and pore size distribution in different regions of the framework; second, to further reduce the porosity of porous ceramics. Dry pressing results in higher porosity, and using higher pressure isostatic pressing makes the green body more compact, reducing porosity and thereby increasing the proportion of the inorganic framework in the resin-infiltrated ceramic, thus improving performance.

[0092] Compared to CN115894001A, which uses ultra-high cold isostatic pressing (350-600 MPa) and requires sophisticated equipment, this invention only needs to use common cold isostatic pressing pressure (≤300 MPa) to prepare resin-infiltrated ceramic materials with a hardness ≥2.6 GPa. This is because the micron-sized powder used in this invention is non-spherical micron-sized particles. With appropriate sintering temperatures, a porous ceramic framework with low porosity can be prepared. Generally, the lower the porosity, the higher the hardness of the prepared resin-infiltrated ceramic material. On the other hand, because when the cold isostatic pressing pressure exceeds a certain limit, i.e., approaches the theoretical bulk density of the powder, the increase in green body density changes from being mainly due to interparticle slippage to being mainly due to particle deformation and breakage. This will destroy the original particle morphology, and the performance will actually decrease. This invention uses a pressure value close to the theoretical bulk density, which is set as the optimal isostatic pressing pressure, and can prepare resin-infiltrated ceramic materials with excellent hardness performance without using ultra-high cold isostatic pressing.

[0093] After obtaining the green blank, the present invention sinters the green blank to obtain an aluminum silicate-based porous ceramic framework.

[0094] In this invention, the sintering temperature is preferably 800-1400℃, more preferably 900-1300℃, and even more preferably 1000-1200℃; the holding time is preferably 4-24h, more preferably 8-20h, and even more preferably 12-16h; the sintering is preferably carried out in an air atmosphere.

[0095] In this invention, the sintering is preferably carried out in two stages of heating. Preferably, the green blank is heated to 400-600°C at a rate of 2-5°C / min, and then heated to the sintering temperature at a rate of 1-3°C / min.

[0096] The sintering process in this invention serves two purposes: firstly, it removes the binder, burning off the organic components in the green body, mainly the binder and some bound water; secondly, it allows the porous ceramic skeleton particles to bond together, which not only enhances the strength of the porous ceramic skeleton but also further reduces the porosity.

[0097] The present invention provides an aluminum silicate-based porous ceramic framework prepared by the preparation method described above.

[0098] In this invention, the porosity of the aluminosilicate-based porous ceramic skeleton is preferably 20-50%, more preferably 25-45%, and even more preferably 30-40%.

[0099] This invention provides the application of the aluminum silicate-based porous ceramic framework described above in resin-infiltrated ceramic materials.

[0100] The present invention provides a resin-permeable ceramic material, comprising the aluminum silicate-based porous ceramic framework described above and a resin material permeating the aluminum silicate-based porous ceramic framework.

[0101] In this invention, the resin material preferably includes acrylic resin.

[0102] In this invention, the raw materials for preparing the acrylic resin preferably include, by weight percentage: 97-99.9% acrylate monomers and 0.1-3% initiator; more preferably, 97.5-99.5% acrylate monomers and 0.5-2.5% initiator; even more preferably, 98-99% acrylate monomers and 1-2% initiator.

[0103] In this invention, the acrylate monomer preferably includes a main monomer and a diluent monomer; the mass ratio of the main monomer to the diluent monomer is preferably (1.5-9):1, more preferably (1.5-4):1, and even more preferably (2-3):1.

[0104] In this invention, the main monomer preferably includes one or more of bisphenol A-glycidyl methacrylate (Bis-GMA), bisphenol A glycerol dimethacrylate (BIS-EMA), ethoxylated bisphenol A dimethacrylate (BIS-MEPP), and urethane dimethacrylate (UDMA); the diluent monomer preferably includes one or more of triethylene glycol dimethacrylate (TEGDMA), ethylene glycol dimethacrylate (EGDMA), and trimethylolpropane triacrylate (TMPTMA).

[0105] In this invention, the initiator preferably includes a thermal initiator, which preferably includes a peroxide initiator, and the peroxide initiator preferably includes one or more of benzoyl peroxide (BPO), tert-butyl peracetate, dicumyl peroxide (DCP), tert-butyl peroxide-2-ethylhexanoate (TBPO), and tert-butyl peroxide.

[0106] The resin-infiltrated ceramic material prepared using the above-mentioned aluminosilicate-based porous ceramic framework has a preferred hardness of ≥2.6 GPa, a preferred flexural strength of ≥300 MPa, and a preferred elastic modulus of ≥30 GPa. Furthermore, by further adjusting the molar ratio of each oxide raw material in the aluminosilicate-based porous ceramic framework within the above-mentioned oxide raw material dosage range, higher hardness, flexural strength, and elastic modulus can be obtained.

[0107] This invention provides a method for preparing the resin-infiltrated ceramic material described above, comprising the following steps: coupling modification of the aluminosilicate-based porous ceramic framework to obtain a modified porous ceramic framework;

[0108] The modified porous ceramic framework is immersed in a resin solution and cured to obtain the resin-infiltrated ceramic material.

[0109] The present invention performs coupling modification on the porous ceramic framework to obtain a modified porous ceramic framework.

[0110] In this invention, the preparation of the modified solution used for coupling modification preferably includes: mixing water and ethanol, adjusting the pH of the resulting mixture to 4-5 with acid, adding a silane coupling agent, and obtaining the modified solution.

[0111] In this invention, the preferred mass ratio of water to ethanol is 1:1. This invention does not have specific requirements regarding the type of acid used; it can be either an organic or inorganic acid, as long as it can adjust the mixture to the target pH value. Specifically, the organic acid can be citric acid or acetic acid; the inorganic acid can be hydrochloric acid, phosphoric acid, or sulfuric acid.

[0112] In this invention, the silane coupling agent is preferably one or more of γ-(methacryloyloxy)propyltrimethoxysilane (A-174 or KH-570), γ-mercaptopropyltriethoxysilane (KH-580), γ-mercaptopropyltrimethoxysilane (A189 or KH590), γ-(3,2-epoxypropoxy)methyltrimethoxysilane (KH-560), and γ-aminopropyltriethoxysilane (KH-550).

[0113] In this invention, the mass content of the silane coupling agent in the modified liquid is preferably 0.5-10%, more preferably 2-8%, and even more preferably 4-6%.

[0114] In this invention, the coupling modification preferably includes: immersing an aluminum silicate-based porous ceramic framework in a modification solution under vacuum conditions, and after the immersion is completed, removing the porous ceramic framework and drying it.

[0115] In this invention, the coupling modification temperature is preferably 40-120°C, more preferably 50-100°C, and even more preferably 70-80°C; the coupling modification time is preferably 0.5-24h, more preferably 5-20h, and even more preferably 10-15h.

[0116] This invention utilizes coupling modification to improve the adhesion between the porous ceramic skeleton and the resin, strengthen the bonding of the composite material, and optimize its performance.

[0117] After obtaining the modified porous ceramic framework, the present invention places the modified porous ceramic framework into the resin liquid for impregnation and curing to obtain the resin-infiltrated ceramic material.

[0118] The present invention does not have special requirements for the preparation process of the resin solution; a preparation process well known in the art can be used. In the present invention, when the resin material in the resin-permeated ceramic material is an acrylic resin, the present invention directly mixes the acrylate monomer and the initiator to obtain the resin solution.

[0119] In this invention, the mixing time is preferably 30 to 600 minutes; the mixing is preferably carried out under stirring conditions, and the stirring speed is preferably 100 to 600 r / min.

[0120] In this invention, the impregnation is preferably carried out under vacuum conditions; the impregnation is preferably performed by first partially impregnating and then fully impregnating. In this invention, the total impregnation time is preferably 3 to 240 hours, and the specific impregnation time is related to the resin viscosity, the porosity and pore size of the porous ceramic skeleton, and can be ensured that the pore components between the porous ceramic skeletons are completely penetrated by the resin.

[0121] In this invention, the curing temperature is preferably 80–160°C, more preferably 90–150°C; the curing pressure is preferably 100–300 MPa, more preferably 150–250 MPa; and the total curing time is preferably 0.5–24 h, more preferably 5–20 h. In this invention, the curing is preferably a one-stage curing or a two-stage curing. This invention does not impose special requirements on the specific procedures for the one-stage and two-stage curing; curing procedures well known in the art can be used. In an embodiment of this invention, a two-stage curing is specifically used: first, curing at 300 MPa and 70°C for 2 h, followed by curing at 200 MPa and 120°C for 4 h.

[0122] This invention provides the application of the resin-infiltrated ceramic material described above in the preparation of dental prostheses.

[0123] The present invention provides an oral prosthesis containing the resin-infiltrated ceramic material described in the above-described scheme.

[0124] In this invention, the oral prosthesis preferably includes dental veneers, high inlays, low inlays, single crowns, anterior teeth, or three-unit bridges.

[0125] The following detailed descriptions, in conjunction with embodiments, illustrate the aluminum silicate-based porous ceramic framework, its preparation method and application, resin-infiltrated ceramic materials and their applications, and dental prostheses provided by this invention. However, these descriptions should not be construed as limiting the scope of protection of this invention.

[0126] Example 1

[0127] Preparation of porous ceramic framework:

[0128] ①The sodium potassium salt based on aluminum silicate is prepared by chemical formula Na2O·Al2O3·4SiO2. After weighing the inorganic raw materials according to the molar ratio shown in Table 1, they are put into a mixer for mixing. The mixing time is 30 min and the mixing speed is 30 r / min.

[0129] ② Place the mixed inorganic raw materials into a high-temperature furnace and melt them at 1650℃ for 15 hours. After cooling, the basic raw materials are obtained.

[0130] ③ After the basic raw materials are initially crushed in a jaw crusher, the crushed millimeter-sized basic raw materials are then subjected to secondary crushing in a ball mill at a speed of 600 r / min for 8 hours to obtain micron-sized powder (microscopic morphology image as shown). Figure 13 As shown, the particles have a non-spherical structure and an average particle size of 1–30 μm.

[0131] ④ A 3% (w / w) polyvinyl alcohol (PVA) aqueous solution, 60g of micron-sized powder, and 80g of ethanol were ball-milled at 300r / min for 4h to obtain a uniform slurry. The slurry was then dried at 80℃ for 12h. The dried raw material was then passed through 100-mesh and 120-mesh sieves to obtain granulated powder. 10g of granulated powder was weighed and placed in a dry pressing mold, held at 4MPa pressure for 2min, and then held at 260MPa cold isostatic pressing pressure for 2min to obtain a green body.

[0132] ⑤ The pressed green body is placed in an electric furnace for sintering to obtain a porous ceramic skeleton. The sintering curve is as follows: the temperature is raised to 600℃ at room temperature at a heating rate of 3℃ / min, and then raised to 850℃ at a heating rate of 1℃ / min. After holding at this temperature for 3 hours, the temperature is cooled to room temperature with the furnace to obtain a porous ceramic skeleton.

[0133] Preparation of resin-infiltrated ceramics:

[0134] ① Modification of porous ceramic framework: The modification solution was prepared by mixing pure water and ethanol in a 1:1 mass ratio, and then adjusting the pH of the solution to 5 by titration with acetic acid. Finally, 5 wt% KH-570 was added and stirred for at least 15 minutes until the silane was completely dissolved to obtain a homogeneous modification solution. The porous ceramic framework prepared in Example 1-1 was placed in a container, and the framework was first fully impregnated with the modification solution and placed in a vacuum drying oven for 5 hours. After that, it was taken out and dried to obtain the modified porous ceramic framework.

[0135] ② Resin solution preparation: 0.5 wt% BPO and 99.5 wt% acrylate monomer (bisphenol A-glycidyl methacrylate (Bis-GMA) and diluent monomer triethylene glycol dimethacrylate (TEGDMA) mixed at a mass ratio of 1.5:1) were stirred at 300 r / min for 240 min to obtain a homogeneous resin solution;

[0136] ③ Resin infiltration: The modified porous ceramic skeleton is then placed in the resin liquid and partially and then fully impregnated under vacuum conditions (-0.1MPa). After a total infiltration time of 120 hours, a porous ceramic skeleton with complete resin infiltration is obtained.

[0137] ④ Resin curing: Finally, the resin-infiltrated porous ceramic skeleton is cured at 300MPa and 70℃ for 2 hours, and then cured at 200MPa and 120℃ for 4 hours to obtain the resin-infiltrated ceramic material.

[0138] Example 2

[0139] The proportion of sodium potassium aluminum silicate in Example 1 was adjusted to Na2O·Al2O3·6SiO2, the maximum sintering temperature of the skeleton was changed to 1150℃, and other process parameters remained unchanged.

[0140] Example 3

[0141] The proportion of sodium potassium aluminum silicate in Example 1 was adjusted to 0.1Na2O·Al2O3·4SiO2, the maximum sintering temperature of the skeleton was changed to 1200℃, and other process parameters remained unchanged.

[0142] Example 4

[0143] The ratio of sodium potassium aluminum silicate in Example 1 was adjusted to 0.5Na2O·0.5K2O·Al2O3·4SiO2, the maximum sintering temperature of the skeleton was changed to 830℃, and other process parameters remained unchanged.

[0144] Example 5

[0145] The ratio of sodium potassium aluminum silicate in Example 1 was adjusted to 0.1Na2O·0.1K2O·Al2O3·4SiO2, the maximum sintering temperature of the skeleton was changed to 1150℃, and other process parameters remained unchanged.

[0146] Example 6

[0147] The proportion of sodium potassium aluminum silicate in Example 1 was adjusted to 0.5K2O·Al2O3·6SiO2, the maximum sintering temperature of the skeleton was changed to 1100℃, and other process parameters remained unchanged.

[0148] Example 7

[0149] The ratio of sodium potassium aluminum silicate in Example 1 was adjusted to 0.9Na2O·0.1K2O·Al2O3·8SiO2, the maximum sintering temperature of the skeleton was changed to 1020℃, and other process parameters remained unchanged.

[0150] Example 8

[0151] The ratio of sodium potassium aluminum silicate in Example 1 was adjusted to 0.1Na2O·0.9K2O·Al2O3·8SiO2, the maximum sintering temperature of the skeleton was changed to 1020℃, and other process parameters remained unchanged.

[0152] Example 9

[0153] The ratio of sodium potassium aluminum silicate in Example 1 was adjusted to 0.99Na2O·Al2O3·10SiO2, the maximum sintering temperature of the skeleton was changed to 1050℃, and other process parameters remained unchanged.

[0154] Example 10

[0155] The proportion of sodium potassium aluminum silicate in Example 1 was adjusted to 0.99K2O·Al2O3·10SiO2, the maximum sintering temperature of the skeleton was changed to 1050℃, and other process parameters remained unchanged.

[0156] The basic raw materials of Examples 1-10 were characterized by XRD, and the results are shown in the figure. Figures 3-12 The specific phase composition is listed in Table 1.

[0157] Table 1 Raw material ratios for the embodiments

[0158]

[0159] Performance testing of resin-infiltrated ceramic materials

[0160] The performance of the resin-infiltrated ceramic materials prepared in each embodiment was tested, and the test methods are as follows: ① Flexural strength and fracture toughness: GB30367-2013 Dental Ceramic Materials;

[0161] ② Elastic modulus: GB / T 10700-2006 Method for testing elastic modulus of fine ceramics - bending method; ③ Vickers hardness: GB / T 4340.1-2009;

[0162] ④ Linear transmittance: Tested using a calibrated haze meter.

[0163] The test results are shown in Table 2.

[0164] Table 2. Properties of the resin-infiltrated ceramic materials prepared in each example.

[0165]

[0166] As can be seen from the above embodiments, this invention uses Al2O3, SiO2, Na2O, and K2O as raw materials, and can freely adjust the ratio of sodium, potassium, and silicon elements. By changing the relative content of sodium, potassium, and silicon elements, the porous ceramic framework prepared by aluminum silicate-based sodium potassium salt exhibits different physicochemical properties. As a matrix, resin-infiltrated ceramic materials with different physicochemical properties and aesthetic characteristics can be prepared to meet the needs of different dental scenarios. For example, the resin-infiltrated ceramic material obtained in Example 3 of this invention has a flexural strength of 338 MPa and an elastic modulus of 32.1 GPa. This material can be used in the dental field not only as a single crown and anterior tooth restoration, but also as a three-bridge restoration with higher strength requirements, and has a wider range of applications.

[0167] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing an aluminosilicate-based porous ceramic framework, characterized in that, It includes the following steps: (1) Mix various oxide raw materials according to the molar ratio shown in Formula 1 to obtain a mixed material; The oxide raw materials are multiple ones of Al2O3, SiO2, Na2O and K2O; the composition of the mixed material is shown in Formula 1: mNa2O·nK2O·Al2O3·2pSiO2 Formula 1, In Formula 1, 0 < m + n ≤ 1, and p is an integer between 1 and 5; (2) Melt the mixed material and then cool it to obtain a basic raw material; the melting temperature is 1200~1800 °C, and the time is 4~24 h; (3) Crush the basic raw material to obtain a basic powder; the morphology of the basic powder is a non-spherical structure; (4) Mix and ball-mill the basic powder, a binder and a dispersion solvent to obtain a slurry; (5) Granulate the slurry to obtain a granulated powder; (6) Subject the granulated powder to dry pressing and cold isostatic pressing in sequence to obtain a green body; the pressure of the cold isostatic pressing is 100~300 MPa, and the pressure holding time is 0.5~5 min; (7) Sinter the green body to obtain a porous ceramic framework based on aluminum silicate; the sintering temperature is 800~1400 °C, and the heat preservation time is 4~24 h; the porosity of the porous ceramic framework based on aluminum silicate is 20~50%.

2. The preparation method according to claim 1, characterized in that, In step (3), the average particle size of the basic powder is 1~35 μm.

3. The preparation method according to claim 1 or 2, characterized in that, In step (3), the crushing includes: placing the basic raw material in a crusher for preliminary crushing, and then ball-milling the crushed basic raw material to achieve secondary crushing.

4. The preparation method according to claim 1, characterized in that, In step (6), the pressure of the dry pressing is 3~10 MPa, and the pressure holding time is 0.5~5 min.

5. The preparation method according to claim 1, characterized in that, In step (4), the binder includes one or more of polyvinyl alcohol, polyethylene glycol, polyvinyl butyral and sodium carboxymethyl cellulose.

6. The preparation method according to claim 1 or 5, characterized in that, In step (4), the binder is used in the form of a binder solution, and the mass concentration of the binder solution is 1~5%; the mass of the binder solution is 5~30% of the mass of the basic powder.

7. The preparation method according to claim 1, characterized in that, In step (4), the dispersion solvent includes water or ethanol.

8. The preparation method according to claim 1, characterized in that, In step (5), the particle size of the granulated powder is 100~200 mesh.

9. A porous ceramic framework based on aluminum silicate prepared by the preparation method according to any one of claims 1 to 8; the porosity is 20~50%.

10. Application of the porous ceramic framework based on aluminum silicate according to claim 9 in a resin infiltration ceramic material.

11. A resin-infiltrated ceramic material, characterized in that, It includes a porous ceramic framework based on aluminum silicate and a resin material infiltrated in the porous ceramic framework based on aluminum silicate; the porous ceramic framework based on aluminum silicate is the porous ceramic framework based on aluminum silicate according to claim 9.

12. The resin-infiltrated ceramic material according to claim 11, characterized in that, The resin material includes an acrylic resin.

13. The resin-infiltrated ceramic material according to claim 11 or 12, characterized in that, The hardness of the resin infiltration ceramic material ≥ 2.6 GPa, the flexural strength ≥ 300 MPa, and the elastic modulus ≥ 30 GPa.

14. The resin-permeable ceramic material according to claim 12, characterized in that, By mass percentage, the preparation raw materials of the acrylic resin include: 97~99.9% of acrylate monomers and 0.1~3% of an initiator.

15. The resin-permeable ceramic material according to claim 14, characterized in that, The acrylate monomers include a main monomer and a diluent monomer; the mass ratio of the main monomer to the diluent monomer is (1.5~9):

1.

16. The resin-infiltrated ceramic material according to claim 15, characterized in that, The main monomer includes one or more of bisphenol A-glycidyl methacrylate, bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, and carbamate dimethacrylate; the diluent monomer includes one or more of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, and trimethylolpropane triacrylate.

17. The use of the resin-infiltrated ceramic material according to any one of claims 11 to 16 in the preparation of dental prostheses.

18. A dental prosthesis comprising the resin-infiltrated ceramic material according to any one of claims 11 to 16.

19. The oral prosthesis according to claim 18, characterized in that, The oral prostheses include dental veneers, high inlays, low inlays, single crowns, anterior teeth, or three-unit bridges.

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