Aluminum-silicate-based porous ceramic framework and preparation method therefor and use thereof, resin-infiltrated ceramic material and use thereof, and dental prosthesis

Abstract

An aluminum-silicate-based porous ceramic framework and a preparation method therefor and the use thereof, a resin-infiltrated ceramic material and the use thereof, and a dental prosthesis. Al2O3, SiO2, Na2O and K2O are used as raw materials; by changing the relative content of sodium, potassium and silicon, porous ceramic frameworks prepared from an aluminum-silicate-based sodium-potassium salt exhibit different physical and chemical properties; and resin-infiltrated ceramic materials having different physical and chemical properties and aesthetic characteristics are prepared by using the porous ceramic frameworks as a matrix, so as to meet the use requirements of different dental scenarios.

Description

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

[0001] Cross-reference to Related Applications

[0002] The present disclosure claims priority to the Chinese patent application No. 202410536466.7, filed on April 30, 2024, and entitled "Alumina-silicate-based porous ceramic framework, preparation method and application thereof, resin-infiltrated ceramic material and application thereof, and oral restoration", the entire content of which is incorporated herein by reference. TECHNICAL FIELD

[0003] The present disclosure relates to the technical field of dental materials, and in particular to an alumina-silicate-based porous ceramic framework, a preparation method and application thereof, a resin-infiltrated ceramic material and application thereof, and an oral restoration. BACKGROUND

[0004] Since the 1980s, the development of computer-aided design and computer-aided manufacturing (CAD / CAM) technology has been very rapid, and this technology has been widely used in the field of dental restoration, mainly involving the manufacture of ceramic, polymer and composite dental restorations. The rapid application of this technology and digital scanning in the field of dentistry has promoted the continuous upgrading and iteration of chairside systems, the concept of "immediate restoration" has been deeply rooted in the hearts of doctors and patients, and patients can no longer be "luxurious" to achieve "wear teeth on the same day".

[0005] In addition to some necessary equipment, the consumable materials involved in the chairside system also play a very important role in the speed of restoration. In addition to meeting the basic requirements of high aesthetics, durability and function, the preparation of the restoration also needs to achieve fast tooth production to ensure that patients can wear teeth faster and improve the experience of medical treatment. Ceramic dental restoration materials need to be further sintered, glazed, polished and polished after CAD design and CAM cutting to obtain the final restoration, while polymer-based or composite materials do not need to be sintered and glazed, and only need to be polished and polished to perform the tooth wearing operation, which is more in line with the needs of the chairside system. Compared with polymer-based materials, composite materials have higher mechanical properties and are more similar to natural teeth, so the development of composite materials in dentistry is also very rapid.

[0006] The composite material in dentistry mainly refers to the composite of resin and ceramic, mainly including two kinds. One is resin composite material, the matrix of which is organic component, and inorganic filler particles are dispersed in the organic matrix to mainly play a reinforcing role, but the aesthetic, wear resistance and other properties of this material are lower than those of another material called "polymer infiltrated ceramic network (PICN)" or "resin infiltrated ceramic". Resin infiltrated ceramic is obtained by resin infiltration and solidification of a porous ceramic skeleton prepared, and has mechanical properties and aesthetic properties closer to natural teeth. In the past decade, researchers in various countries have carried out a large number of technical design and optimization on resin infiltrated ceramic materials, and a series of research results have also been formed.

[0007] Among them, the Chinese patent CN115894001A is more representative, which uses potassium sodium aluminum silicate to prepare a porous ceramic matrix through ultrahigh cold isostatic pressing (350-600 MPa), and after resin infiltration and solidification, a resin infiltrated ceramic material with high hardness (2.5-4.5 GPa) and high wear resistance is obtained. However, the raw material system used is a fixed molar ratio of compounds, such as aluminum silicate, potassium sodium aluminum silicate, sodium aluminum silicate, etc., which cannot meet the needs of more resin infiltrated ceramic use scenarios. SUMMARY

[0008] The purpose of the present disclosure is to provide an aluminum silicate-based porous ceramic skeleton and its preparation method and application, a resin infiltrated ceramic material and its application, and an oral prosthesis. The preparation method can flexibly adjust the relative content of sodium, potassium and silicon elements, and obtain resin infiltrated ceramic materials with different optical transmittance and mechanical properties, so as to be applied in different dental use scenarios, thereby expanding the application range of aluminum silicate-based sodium potassium salt resin infiltrated ceramic in the field of dentistry.

[0009] In order to achieve the above-mentioned purpose of the application, the present disclosure provides the following technical solutions:

[0010] The present disclosure provides a preparation method of an aluminum silicate-based porous ceramic skeleton, comprising the following steps:

[0011] (1) According to the molar ratio shown in formula 1, the oxide raw materials are mixed to obtain a mixture;

[0012] The oxide raw materials are multiple selected from Al2O3, SiO2, Na2O and K2O; the composition of the mixture is shown in formula 1: mNa2O·nK2O·Al2O3·2pSiO2 formula 1,

[0013] In formula 1, 0<m+n≤1, and p is an integer between 1 and 5;

[0014] (2) The mixture is melted and cooled to obtain a base raw material;

[0015] (3) crushing the base raw material to obtain a base powder;

[0016] (4) mixing, ball-milling the base powder, a binder and a dispersion solvent to obtain a slurry;

[0017] (5) granulating the slurry to obtain a granulated powder;

[0018] (6) sequentially dry-pressing and cold isostatic pressing the granulated powder to obtain a green body;

[0019] (7) sintering the green body to obtain an aluminum silicate-based porous ceramic framework.

[0020] Preferably, in step (6), the pressure of the cold isostatic pressing is 100-300 MPa, and the pressure holding time is 0.5-5 min.

[0021] Preferably, in step (7), the sintering temperature is 800-1400 ℃, and the holding time is 4-24 h.

[0022] Preferably, in step (3), the average particle size of the base powder is 1-35 μm, and the morphology is a non-spherical structure.

[0023] Preferably, in step (3), the crushing comprises: placing the base raw material in a crusher for primary crushing, and then ball-milling the crushed base raw material for secondary crushing.

[0024] Preferably, in step (2), the melting temperature is 1200-1800 ℃, and the time is 4-24 h.

[0025] Preferably, in step (6), the pressure of the dry-pressing is 3-10 MPa, and the pressure holding time is 0.5-5 min.

[0026] Preferably, in step (4), the binder comprises one or more of polyvinyl alcohol, polyethylene glycol, polyvinyl butyral and sodium carboxymethyl cellulose.

[0027] Preferably, in step (4), the binder is used in the form of a binder solution, the mass concentration of the binder solution is 1-5%, and the mass of the binder solution is 5-30% of the mass of the base powder.

[0028] Preferably, in step (4), the dispersion solvent comprises water or ethanol.

[0029] Preferably, in step (5), the particle size of the granulated powder is 100-200 mesh.

[0030] The present disclosure provides an aluminum silicate-based porous ceramic framework prepared by the preparation method described in the above scheme.

[0031] Preferably, the porosity is 20-50%.

[0032] The present disclosure provides an application of the aluminum silicate-based porous ceramic framework in the resin-infiltrated ceramic material.

[0033] The present disclosure provides a resin-infiltrated ceramic material, comprising an aluminum silicate-based porous ceramic framework and a resin material infiltrated in the aluminum silicate-based porous ceramic framework; the aluminum silicate-based porous ceramic framework is the aluminum silicate-based porous ceramic framework described in the above solution.

[0034] Preferably, the resin material comprises an acrylic resin.

[0035] Preferably, the resin-infiltrated ceramic material has a hardness ≥ 2.6 GPa, a bending strength ≥ 300 MPa, and an elastic modulus ≥ 30 GPa.

[0036] Preferably, the raw materials for preparing the acrylic resin comprise, in terms of mass percentage, 97-99.9% of an acrylate monomer and 0.1-3% of an initiator.

[0037] Preferably, the acrylate monomer comprises a main monomer and a diluent monomer; the mass ratio of the main monomer to the diluent monomer is (1.5-9):1.

[0038] Preferably, the main monomer comprises one or more of bisphenol A-glycidyl methacrylate, bisphenol A glycerol dimethacrylate, ethoxylated bisphenol A dimethacrylate, and urethane dimethacrylate; and the diluent monomer comprises one or more of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, and trimethylolpropane triacrylate.

[0039] The present disclosure provides an application of the resin-infiltrated ceramic material described in the above solution in the preparation of an oral prosthesis.

[0040] The present disclosure provides an oral prosthesis comprising the resin-infiltrated ceramic material described in the above solution.

[0041] Preferably, the oral prosthesis comprises a tooth veneer, an onlay, an inlay, a single crown, a front tooth, or a three-unit bridge.

[0042] The present disclosure provides a preparation method of an aluminum silicate-based porous ceramic framework, comprising the following steps: (1) mixing various oxide raw materials according to the molar ratio shown in formula 1 to obtain a mixture; the oxide raw materials are multiple selected from 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) melting and cooling the mixture to obtain a base raw material; (3) crushing the base raw material to obtain a base powder; (4) mixing, ball-milling and mixing the base powder, a binder and a dispersion solvent to obtain a slurry; (5) granulating the slurry to obtain a granulated powder; (6) sequentially performing dry pressing and cold isostatic pressing on the granulated powder to obtain a green compact; and (7) sintering the green compact to obtain an aluminum silicate-based porous ceramic framework.

[0043] The present disclosure uses Al2O3, SiO2, Na2O and K2O as raw materials, can freely adjust the ratio of sodium, potassium and silicon elements, and by changing the relative content of sodium, potassium and silicon elements, the porous ceramic framework prepared by the aluminum silicate-based sodium potassium salt exhibits different physical and chemical properties, and a resin-infiltrated ceramic material with different physical and chemical properties and aesthetic characteristics is prepared as a matrix, thereby meeting the use requirements of different scenes in dentistry.

[0044] Further, the base powder of the present disclosure is a micron-level powder, and the porous ceramic prepared by the micron-level powder has a relatively large pore size, belongs to the macropore level (pore size > 50 nm) according to the pore size classification of the porous ceramic, is easy to be fully infiltrated by resin, forms an interpenetrating and interlocking structure, has stronger crack propagation resistance, and has more excellent mechanical properties such as flexural strength and elastic modulus.

[0045] Compared with CN115894001A, the present disclosure only needs to use a common cold isostatic pressing pressure (≤300 MPa) to prepare a resin-infiltrated ceramic material with a hardness of ≥2.6 GPa. On the one hand, the micron-level powder (i.e., the base powder) used in the present disclosure is a non-spherical micron particle, and a porous ceramic framework with low porosity can be prepared by a proper sintering temperature. The lower the porosity, the higher the hardness of the resin-infiltrated ceramic material prepared in general. On the other hand, when the cold isostatic pressing pressure exceeds a certain limit, the density of the green compact is increased by mainly the deformation and crushing of the particles instead of the sliding between the particles, which destroys the original particle morphology and reduces the performance. The present disclosure uses a pressure value close to the theoretical packing density as the optimal isostatic pressing pressure, and does not use super-high cold isostatic pressing, so that a resin-infiltrated ceramic material with excellent hardness performance can be prepared.

[0046] In addition, the sintering temperature range of CN115894001A is narrow (600-800 DEG C), while the sintering temperature of the porous ceramic framework of the present disclosure is 800-1400 DEG C, which is more suitable for the activity of the micron-sized powder, and the particles directly form effective sintering necks, further improving the mechanical strength of the framework.

[0047] The preparation process of the present disclosure is simple, easy to industrialize, low in cost, and simple in requirements for equipment and raw materials, and can meet the needs of conventional equipment in the field.

[0048] The effects and advantages of the present disclosure include:

[0049] The present disclosure provides an aluminum silicate-based porous ceramic framework and a preparation method and application thereof, a resin-infiltrated ceramic material and an application thereof, and an oral prosthesis, which uses Al2O3, SiO2, Na2O and K2O as raw materials, can freely adjust the ratio of sodium, potassium and silicon elements, and by changing the relative content of sodium, potassium and silicon elements, the porous ceramic framework prepared by the aluminum silicate-based sodium potassium salt exhibits different physicochemical properties, and the resin-infiltrated ceramic material prepared as a matrix has different physicochemical properties and aesthetic characteristics, and the resin-infiltrated ceramic material can be used as a dental material to meet the use requirements of different scenes. BRIEF DESCRIPTION OF DRAWINGS

[0050] In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present disclosure, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0051] Fig. 1 is a trend graph of the influence of sodium and potassium content on the mechanical properties of resin-infiltrated ceramic material;

[0052] Fig. 2 is a trend graph of the influence of sodium and potassium content on the transparency and aesthetic properties of resin-infiltrated ceramic material;

[0053] Fig. 3 is an XRD graph of the base raw material of Example 1;

[0054] Fig. 4 is an XRD graph of the base raw material of Example 2;

[0055] Fig. 5 is an XRD graph of the base raw material of Example 3;

[0056] Fig. 6 is an XRD graph of the base raw material of Example 4;

[0057] Fig. 7 is an XRD graph of the base raw material of Example 5;

[0058] Fig. 8 is an XRD graph of the base raw material of Example 6;

[0059] Fig. 9 is an XRD pattern of the base raw material of Example 7;

[0060] Fig. 10 is an XRD pattern of the base raw material of Example 8;

[0061] Fig. 11 is an XRD pattern of the base raw material of Example 9;

[0062] Fig. 12 is an XRD pattern of the base raw material of Example 10;

[0063] Fig. 13 is a micrograph of micron-sized powder obtained by secondary crushing of the ball mill of Example 1. DETAILED DESCRIPTION

[0064] The embodiments of the present disclosure will be described in detail below with reference to the examples, but those skilled in the art will understand that the following examples are only for illustration of the present disclosure and should not be regarded as limiting the scope of the present disclosure. The specific conditions are not specified in the examples, and the conventional conditions or the conditions recommended by the manufacturer are used. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be obtained by commercial purchase.

[0065] The endpoints of the ranges and any values disclosed in the present disclosure are not limited to the precise values stated. The ranges or values should be construed to be approximations that are understood to include values approximately around those values. For numerical ranges, the endpoints are included in the ranges, and the endpoints and individual points are included in the ranges, and the individual points can be combined to form one or more new ranges, which are to be considered as being specifically disclosed herein.

[0066] The present disclosure provides a preparation method of a porous ceramic framework based on aluminum silicate, comprising the following steps:

[0067] (1) mixing various oxide raw materials in the molar ratio shown in Formula 1 to obtain a mixture;

[0068] The oxide raw materials are multiple selected from Al2O3, SiO2, Na2O and K2O; the composition of the mixture is shown in Formula 1: mNa2O·nK2O·Al2O3·2pSiO2 Formula 1,

[0069] In Formula 1, 0 < m+n ≤ 1, and p is an integer between 1 and 5;

[0070] (2) melting and cooling the mixture to obtain a base raw material;

[0071] (3) crushing the base raw material to obtain a base powder;

[0072] (4) mixing, ball-milling and mixing the base powder, a binder and a dispersion solvent to obtain a slurry;

[0073] (5) granulating the slurry to obtain granulated powder;

[0074] (6) sequentially performing dry pressing and cold isostatic pressing on the granulated powder to obtain a green body;

[0075] (7) sintering the green body to obtain an aluminum silicate-based porous ceramic framework.

[0076] In the present disclosure, unless otherwise specified, all raw materials used are commercially available products well known in the art.

[0077] The present disclosure mixes each oxide raw material according to the molar ratio shown in formula 1 to obtain a mixture.

[0078] In the present disclosure, the oxide raw materials are multiple selected from Al2O3, SiO2, Na2O and K2O; and the composition of the mixture is shown in formula 1: mNa2O·nK2O·Al2O3·2pSiO2 formula 1,

[0079] In formula 1, 0 < m + n ≤ 1, and p is an integer between 1 and 5; specifically, under 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; and p can specifically be 1, 2, 3, 4 or 5.

[0080] In the present disclosure, the addition of sodium and potassium changes the refractive index, scattering and absorption characteristics of the resin-infiltrated ceramic material, so the introduction of sodium and potassium within a certain range can reduce light scattering and improve the transparency of the glass; but too low sodium and potassium content may cause crystalline phases to appear in the glass, thereby reducing the transparency, mainly because the refractive indices of different phases are different, causing severe dispersion of light when it propagates in the mixed phase medium, resulting in a decrease in transparency; the structure of silicon in the glass is a silicon-oxygen tetrahedral network structure, and when the relative content is relatively high, it exhibits the common characteristics of silicates, so according to the random glass network theory, when the content of silicon increases, its spatial structure tends to be more stable, with fewer defects, and the corresponding mechanical properties will also be improved. The influence trend of sodium and potassium content on the mechanical properties of the resin-infiltrated ceramic material is analyzed in detail in FIG. 1, and the influence trend of sodium and potassium content on the transparency and aesthetic properties of the resin-infiltrated ceramic material is analyzed in FIG. 2.

[0081] The present disclosure uses Al2O3, SiO2, Na2O and K2O as raw materials, can freely adjust the ratio of sodium, potassium and silicon elements, and by changing the relative content of sodium, potassium and silicon elements, the porous ceramic framework prepared by the aluminum silicate-based sodium potassium salt exhibits different physicochemical properties, and the resin-infiltrated ceramic material prepared as a matrix exhibits different physicochemical properties and aesthetic characteristics, meeting the use requirements of different scenes in dentistry.

[0082] In the present disclosure, the mixing is preferably performed in a mixer; the mixing time is preferably 5-120 min, more preferably 30-100 min, and further preferably 40-60 min; and the mixing rotation speed is preferably 20-60 r / min, more preferably 30-50 r / min, and further preferably 40 r / min.

[0083] After obtaining the mixture, the present disclosure melts the mixture, and cools to obtain a base material.

[0084] In the present disclosure, the melting temperature is preferably 1200-1800°C, more preferably 1300-1700°C, and further preferably 1400-1600°C; and the melting time is preferably 4-24 h, more preferably 8-20 h, and further preferably 12-16 h. The present disclosure utilizes melting to mix the powder of different components sufficiently and uniformly, melt at high temperature to homogenize, and crystallize in the crystalline phase region of the phase diagram to obtain a base material with specific crystalline phase or mixed phase of crystalline phase and glass phase.

[0085] In the present disclosure, the phase composition of the obtained base material can be glassy substance, one or more crystalline substances, or a mixture of glass phase and one or more crystalline phases, depending on the composition of the mixture. The crystalline phase of the crystalline substance includes one or more of quartz crystalline phase, mullite crystalline phase, alumina crystalline phase, albite crystalline phase, potassium feldspar crystalline phase, and sodium potassium feldspar crystalline phase.

[0086] After obtaining the base material, the present disclosure crushes the base material to obtain a base powder.

[0087] In the present disclosure, the crushing preferably includes: placing the base material in a crusher for primary crushing, and then ball milling the crushed base material for secondary crushing.

[0088] In the present disclosure, the crusher is preferably a jaw crusher; and the particle size of the base material after primary crushing is preferably millimeter level. In the present disclosure, the rotation speed of the ball mill is preferably 300-800 r / min, more preferably 400-700 r / min, and further preferably 500-600 r / min; and the ball milling time is preferably 8-24 h, more preferably 10-20 h, and further preferably 12-16 h.

[0089] In the present disclosure, 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 material is used to prepare a porous ceramic skeleton by the particle packing method, there is good mechanical interlocking force between the particles, and after being combined with resin, a structure in which the resin and the skeleton are interpenetrated and interlocked is formed, which greatly optimizes the strength in the mechanical properties.

[0090] After obtaining the base powder, the base powder, the binder and the dispersion solvent are mixed and ball milled to obtain a slurry.

[0091] In the present disclosure, 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 the binder solution is preferably 1-5%, more preferably 2-4%, and further 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 further preferably 15-20%.

[0092] In the present disclosure, the dispersion solvent is preferably water or ethanol; the mass of the dispersion solvent is preferably 1-3 times the mass of the base powder. In the present disclosure, the time of the mixed ball milling is preferably 0.5-4 h, and more preferably 1-3 h; the rotation speed of the mixed ball milling is preferably 300-800 r / min, and more preferably 400-700 r / min.

[0093] After obtaining the slurry, the slurry is granulated to obtain a granulated powder.

[0094] In the present disclosure, the granulation is preferably spray granulation or sieving after drying. In the present disclosure, the particle size of the granulated powder is preferably 100-200 mesh, and more preferably 120-180 mesh. The present disclosure does not have special requirements for the conditions of the spray granulation, and any granulated powder with the above particle size can be obtained. In the present disclosure, the temperature of the drying is preferably 60-100°C, and more preferably 70-80°C.

[0095] After obtaining the granulated powder, the granulated powder is sequentially subjected to dry pressing and cold isostatic pressing to obtain a green body.

[0096] In the present disclosure, the pressure of the dry pressing is preferably 3-10 MPa, more preferably 4-9 MPa, and further preferably 5-8 MPa; and the pressure holding time of the dry pressing is preferably 0.5-5 min, more preferably 1-4 min, and further preferably 2-3 min. In the present disclosure, the purpose of the dry pressing is twofold: one is to prepare a porous ceramic framework with a certain size specification; and the other is to give the green body certain mechanical strength during the transfer of the porous ceramic framework.

[0097] In the present disclosure, the pressure of the cold isostatic pressing is preferably 100-300 MPa, more preferably 150-250 MPa, and further preferably 180-220 MPa; and the pressure holding time of the cold isostatic pressing is preferably 0.5-5 min, more preferably 1-4 min, and further preferably 2-3 min. In the present disclosure, the cold isostatic pressing has two functions: one is to make the dry-pressed body, after being subjected to secondary isostatic pressing, bear equal force in all directions, so as to ensure that the porosity and pore size distribution of different regions of the framework are consistent to a large extent; and the other is to further reduce the porosity of the porous ceramic, so as to make the body denser, reduce the porosity, and thus increase the proportion of the inorganic framework in the resin-infiltrated ceramic, and further improve the performance.

[0098] The prior art CN115894001A adopts ultra-high cold isostatic pressing with a pressure of 350-600 MPa, which requires a high-performance equipment. In the present disclosure, a resin-infiltrated ceramic material with a hardness of ≥2.6 GPa can be prepared by using a common cold isostatic pressing pressure (≤300 MPa). On the one hand, the micron-sized powder used in the present disclosure is a non-spherical micron particle, and a porous ceramic framework with a low porosity can be prepared by using a proper sintering temperature. Generally speaking, the lower the porosity, the higher the hardness of the resin-infiltrated ceramic material. On the other hand, when the cold isostatic pressing pressure exceeds a certain limit, the density of the body increases mainly by the deformation and crushing of the particles instead of the sliding of the particles, which destroys the original particle morphology and thus reduces the performance. In the present disclosure, the cold isostatic pressing pressure is close to the theoretical packing density, which is the optimal isostatic pressing pressure. Therefore, the resin-infiltrated ceramic material with excellent hardness can be prepared without using ultra-high cold isostatic pressing.

[0099] After obtaining the green body, the green body is sintered to obtain an aluminum silicate-based porous ceramic framework.

[0100] In the present disclosure, the sintering temperature is preferably 800-1400℃, more preferably 900-1300℃, and further preferably 1000-1200℃; the holding time is preferably 4-24 h, more preferably 8-20 h, and further preferably 12-16 h; and the sintering is preferably performed in an air atmosphere.

[0101] In the present disclosure, the sintering is preferably two-stage heating, and the green body is preferably heated at a rate of 2-5℃ / min to 400-600℃, and then heated at a rate of 1-3℃ / min to the sintering temperature.

[0102] The sintering in the present disclosure is for two purposes: one is to remove the organic components in the green body, mainly the binder and part of the combined water, etc.; the other is to combine the particles in the porous ceramic framework, which not only enhances the strength of the porous ceramic framework, but also further reduces the porosity.

[0103] The present disclosure provides an aluminum silicate-based porous ceramic framework prepared by the preparation method described in the above scheme.

[0104] In the present disclosure, the porosity of the aluminum silicate-based porous ceramic framework is preferably 20-50%, preferably 25-45%, and more preferably 30-40%.

[0105] The present disclosure provides an application of the aluminum silicate-based porous ceramic framework described in the above scheme in resin-infiltrated ceramic materials.

[0106] The present disclosure provides a resin-infiltrated ceramic material, comprising the aluminum silicate-based porous ceramic framework described in the above scheme and a resin material infiltrated in the aluminum silicate-based porous ceramic framework.

[0107] In the present disclosure, the resin material preferably comprises an acrylic resin.

[0108] In the present disclosure, the raw materials for preparing the acrylic resin, in terms of mass percentage, preferably comprise: 97-99.9% of an acrylate monomer and 0.1-3% of an initiator; more preferably 97.5-99.5% of an acrylate monomer and 0.5-2.5% of an initiator, and further preferably 98-99% of an acrylate monomer and 1-2% of an initiator.

[0109] In the present disclosure, the acrylate monomer preferably comprises a main monomer and a diluent monomer; and the mass ratio of the main monomer to the diluent monomer is preferably (1.5-9):1, more preferably (1.5-4):1, and further preferably (2-3):1.

[0110] In the present disclosure, the main monomer preferably comprises one or more of Bisphenol A-glycidyl methacrylate (Bis-GMA), Bisphenol A glyceryl dimethacrylate (BIS-EMA), ethoxylated bisphenol A dimethacrylate (BIS-MEPP) and urethane dimethacrylate (UDMA); and the diluent monomer preferably comprises one or more of triethylene glycol dimethacrylate (TEGDMA), ethylene glycol dimethacrylate (EGDMA) and trimethylolpropane triacrylate (TMPTMA).

[0111] In the present disclosure, the initiator preferably comprises a thermal initiator, which preferably comprises one or more of benzoyl peroxide (BPO), t-butyl peroxy acetate, dicumyl peroxide (DCP), t-butyl peroxy-2-ethylhexanoate (TBPO) and t-butyl peroxybenzoate.

[0112] The resin-infiltrated ceramic material prepared by the above-mentioned aluminum silicate-based porous ceramic framework has a hardness of preferably ≥2.6 GPa, a bending strength of preferably ≥300 MPa and an elastic modulus of preferably ≥30 GPa; and by further adjusting the molar ratio of each oxide raw material of the aluminum silicate-based porous ceramic framework within the above-mentioned dosage range of the oxide raw material, a higher hardness, bending strength and elastic modulus can be achieved.

[0113] The present disclosure provides a preparation method of the resin-infiltrated ceramic material described in the above-mentioned scheme, comprising the following steps: coupling modification of the aluminum silicate-based porous ceramic framework to obtain a modified porous ceramic framework;

[0114] immersing the modified porous ceramic framework in a resin liquid, curing to obtain the resin-infiltrated ceramic material.

[0115] The present disclosure performs coupling modification on the porous ceramic framework to obtain a modified porous ceramic framework.

[0116] In the present disclosure, the preparation of the modification liquid used in the coupling modification preferably comprises: mixing water and ethanol, adjusting the pH value of the obtained mixture to 4-5 with an acid, adding a silane coupling agent to obtain a modification liquid.

[0117] In the present disclosure, the mass ratio of the water and ethanol is preferably 1:1; the present disclosure does not have special requirements for the type of the acid, which can be either an organic acid or an 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; and the inorganic acid can be hydrochloric acid, phosphoric acid or sulfuric acid.

[0118] In the present disclosure, the silane coupling agent is preferably one or more of γ-(methacryloxy)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).

[0119] In the present disclosure, the mass content of the silane coupling agent in the modification liquid is preferably 0.5-10%, more preferably 2-8%, and further preferably 4-6%.

[0120] In the present disclosure, the coupling modification preferably comprises: placing the aluminum silicate-based porous ceramic framework in the modification liquid for impregnation under vacuum conditions, and taking out the porous ceramic framework after impregnation is completed and drying.

[0121] In the present disclosure, the temperature of the coupling modification is preferably 40-120°C, more preferably 50-100°C, and further preferably 70-80°C; and the time of the coupling modification is preferably 0.5-24h, more preferably 5-20h, and further preferably 10-15h.

[0122] The present disclosure improves the adhesion of the porous ceramic framework and the resin by coupling modification, strengthens the mutual combination of the composite material, and optimizes the performance.

[0123] After obtaining the modified porous ceramic framework, the present disclosure places the modified porous ceramic framework in the resin liquid for impregnation, solidification, and obtains the resin-infiltrated ceramic material.

[0124] The present disclosure does not have special requirements for the preparation process of the resin liquid, and a preparation process well known in the art can be used. In the present disclosure, when the resin material in the resin-infiltrated ceramic material is an acrylic resin, the present disclosure directly mixes an acrylic ester monomer and an initiator to obtain a resin liquid.

[0125] In the present disclosure, the mixing time is preferably 30-600min; and the mixing is preferably carried out under stirring, and the stirring speed is preferably 100-600r / min.

[0126] In the present disclosure, the impregnation is preferably carried out under vacuum conditions; and the impregnation is preferably half-impregnation followed by full-impregnation. In the present disclosure, the total time of the impregnation is preferably 3-240h, and the specific impregnation time is related to the viscosity of the resin liquid, the porosity of the porous ceramic framework, and the pore size, and can only ensure that the pore components between the porous ceramic frameworks are completely infiltrated by the resin.

[0127] In the present disclosure, the temperature of the curing is preferably 80-160℃, more preferably 90-150℃; the pressure of the curing is preferably 100-300MPa, more preferably 150-250MPa; the total time of the curing is preferably 0.5-24h, more preferably 5-20h. In the present disclosure, the curing is preferably one-stage curing or two-stage curing; the present disclosure does not make special requirements on the specific procedures of the one-stage curing and the two-stage curing, and curing procedures well known in the art can be adopted. In the embodiments of the present disclosure, two-stage curing is specifically adopted, i.e., first curing at 300MPa and 70℃ for 2h, and then curing at 200MPa and 120℃ for 4h.

[0128] The present disclosure provides the use of the resin-infiltrated ceramic material described in the above scheme in the preparation of an oral restoration.

[0129] The present disclosure provides an oral restoration comprising the resin-infiltrated ceramic material described in the above scheme.

[0130] In the present disclosure, the oral restoration preferably comprises a dental veneer, an onlay, an inlay, a single crown, a front tooth, or a three-unit bridge.

[0131] The aluminum silicate-based porous ceramic framework, the preparation method and application thereof, the resin-infiltrated ceramic material and the application thereof, and the oral restoration provided by the present disclosure will be described in detail below in conjunction with the embodiments, but they should not be understood as limiting the protection scope of the present disclosure.

[0132] Example 1

[0133] Preparation of the porous ceramic framework:

[0134] ①The aluminum silicate-based sodium-potassium salt adopts the chemical formula Na2O·Al2O3·4SiO2, and the inorganic raw materials are weighed according to the molar ratio shown in Table 1 and then put into a mixer for uniform mixing, with a mixing time of 30min and a mixing speed of 30r / min;

[0135] ②The uniformly mixed inorganic raw materials are put into a high-temperature furnace for melting at 1650℃ for 15h, and the base raw material is obtained after cooling;

[0136] ③The base raw material is put into a jaw crusher for primary crushing, and then the crushed millimeter-level base raw material is put into a ball mill for secondary crushing, with a speed of 600r / min and a time of 8h, to obtain a micron-level powder (the microscopic morphology is shown in FIG. 13, which shows a non-spherical structure), with an average particle size of 1-30μm;

[0137] (4) 6 g of a 3% by mass polyvinyl alcohol (PVA) aqueous solution was ball-milled with 60 g of micron-sized powder and 80 g of ethanol at 300 r / min for 4 h to obtain a uniform slurry, and the slurry was then dried at 80°C for 12 h. The dried raw material was sieved through 100 mesh and 120 mesh to obtain granulated powder. 10 g of the granulated powder was placed in a dry-pressing mold, and the green compact was obtained by pressing at 4 MPa for 2 min and then cold isostatic pressing at 260 MPa for 2 min;

[0138] (5) The green compact obtained in the pressing was sintered in an electric furnace to obtain a porous ceramic skeleton. The sintering curve was as follows: the temperature was raised to 600°C at a rate of 3°C / min, and then raised to 850°C at a rate of 1°C / min, and then cooled to room temperature after holding for 3 h. The porous ceramic skeleton was obtained.

[0139] Preparation of resin-infiltrated ceramic:

[0140] (1) Modification of the porous ceramic skeleton: a modification solution was prepared by mixing pure water and ethanol at a mass ratio of 1:1, adjusting the pH of the solution to 5 with acetic acid titration, and then adding 5 wt% of KH-570 and stirring for at least 15 min until the silane was completely dissolved, to obtain a uniform modification solution. The porous ceramic skeleton prepared in Example 1-1 was placed in a container, and the skeleton was fully immersed in the modification solution and placed in a vacuum drying oven for 5 h. The modified porous ceramic skeleton was obtained after drying.

[0141] (2) Preparation of resin solution: 0.5 wt% of BPO and 99.5 wt% of acrylate monomers (a mixture of Bis-GMA and TEGDMA at a mass ratio of 1.5:1) were stirred at a speed of 300 r / min for 240 min to obtain a uniform resin solution.

[0142] (3) Resin infiltration: the modified porous ceramic skeleton was placed in the resin solution and subjected to half-immersion and then full-immersion under vacuum (-0.1 MPa). The resin-infiltrated porous ceramic skeleton was obtained after a total infiltration time of 120 h.

[0143] (4) Resin curing: the resin-infiltrated porous ceramic skeleton was cured at 300 MPa and 70°C for 2 h, and then at 200 MPa and 120°C for 4 h, to obtain a resin-infiltrated ceramic material.

[0144] Example 2

[0145] In Example 1, the ratio of sodium potassium salt of aluminum silicate was changed to Na2O·Al2O3·6SiO2, the maximum sintering temperature of the skeleton was changed to 1150°C, and the other process parameters remained unchanged.

[0146] Example 3

[0147] The sodium potassium salt ratio of the aluminum silicate base in Example 1 was adjusted to 0.1 Na2O-Al2O3-4SiO2, the maximum sintering temperature of the skeleton was changed to 1200°C, and other process parameters were unchanged.

[0148] Example 4

[0149] The sodium potassium salt ratio of the aluminum silicate base in Example 1 was adjusted to 0.5Na2O-0.5K2O-Al2O3-4SiO2, the maximum sintering temperature of the skeleton was changed to 830°C, and other process parameters were unchanged.

[0150] Example 5

[0151] The sodium potassium salt ratio of the aluminum silicate base in Example 1 was adjusted to 0.1Na2O-0.1K2O-Al2O3-4SiO2, the maximum sintering temperature of the skeleton was changed to 1150°C, and other process parameters were unchanged.

[0152] Example 6

[0153] The sodium potassium salt ratio of the aluminum silicate base in Example 1 was adjusted to 0.5K2O-Al2O3-6SiO2, the maximum sintering temperature of the skeleton was changed to 1100°C, and other process parameters were unchanged.

[0154] Example 7

[0155] The sodium potassium salt ratio of the aluminum silicate base in Example 1 was adjusted to 0.9Na2O-0.1K2O-Al2O3-8SiO2, the maximum sintering temperature of the skeleton was changed to 1020°C, and other process parameters were unchanged.

[0156] Example 8

[0157] The sodium potassium salt ratio of the aluminum silicate base in Example 1 was adjusted to 0.1Na2O-0.9K2O-Al2O3-8SiO2, the maximum sintering temperature of the skeleton was changed to 1020°C, and other process parameters were unchanged.

[0158] Example 9

[0159] The sodium potassium salt ratio of the aluminum silicate base in Example 1 was adjusted to 0.99Na2O-Al2O3-10SiO2, the maximum sintering temperature of the skeleton was changed to 1050°C, and other process parameters were unchanged.

[0160] Example 10

[0161] The sodium potassium salt ratio of the aluminum silicate base in Example 1 was adjusted to 0.99K2O-Al2O3-10SiO2, the maximum sintering temperature of the skeleton was changed to 1050°C, and other process parameters were unchanged.

[0162] The base raw materials of Examples 1-10 were characterized by XRD, and the results are shown in Figures 3-12, and the specific phase composition is listed in Table 1.

[0163] Table 1: Raw material ratio of examples

[0164] Performance test of resin-infiltrated ceramic material

[0165] The resin-infiltrated ceramic material prepared in each example was subjected to performance testing, and the testing method was as follows:

[0166] ①Flexural strength and fracture toughness: GB 30367 2013 Dental Science Ceramic Materials;

[0167] ②Elastic modulus: GB / T 10700-2006 Fine Ceramic Elastic Modulus Test Sample Method - Bending Method;

[0168] ③Vickers hardness: GB / T 4340.1-2009;

[0169] ④Linear transmittance: calibrated haze meter was used for testing.

[0170] The test results are shown in Table 2.

[0171] Table 2: Performance of resin-infiltrated ceramic material prepared in each example

[0172] As can be seen from the above examples, the present disclosure 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 from the sodium potassium salt of aluminum silicate exhibits different physicochemical properties. As a matrix, resin-infiltrated ceramic materials with different physicochemical properties and aesthetic characteristics are prepared to meet the use requirements of different scenes in dentistry. For example, the resin-infiltrated ceramic material obtained in Example 3 of the present disclosure has a flexural strength of 338 MPa and an elastic modulus of 32.1 GPa. This material can be used in the field of dentistry, not only as a single crown, but also as a front tooth restoration, and can also be used as a three-bridge restoration with higher strength requirements, and has a wider application space.

[0173] The above description is only a preferred embodiment of the present disclosure, and it should be pointed out that, for those skilled in the art, without departing from the principles of the present disclosure, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present disclosure. Industrial applicability

[0174] The present disclosure provides a porous aluminum silicate ceramic framework and a preparation method and application thereof, a resin-infiltrated ceramic material and application thereof, and a dental restoration. The present disclosure uses Al2O3, SiO2, Na2O and K2O as raw materials, can freely adjust the ratio of sodium, potassium and silicon elements, changes the relative content of sodium, potassium and silicon elements, so that the porous ceramic framework prepared by the aluminum silicate-based sodium potassium salt exhibits different physical and chemical properties, and the resin-infiltrated ceramic material prepared as a matrix exhibits different physical and chemical properties and aesthetic characteristics, so as to be applied in different dental use scenarios, thereby expanding the application range of the aluminum silicate-based sodium potassium salt resin-infiltrated ceramic in the dental field.

Claims

1. A method for producing a porous ceramic skeleton of aluminum silicate-based, characterized by, The method comprises the following steps: (1) mixing oxide raw materials according to the molar ratio shown in formula 1 to obtain a mixture; The oxide raw materials are multiple selected from Al2O3, SiO2, Na2O and K2O; the composition of the mixture is shown in formula 1: mNa2O·nK2O·Al2O3·2pSiO2 formula 1, wherein 0 < m + n ≤ 1 and p is an integer between 1 and 5; (2) melting and cooling the mixture to obtain a base raw material; (3) crushing the base raw material to obtain a base powder; (4) mixing, ball-milling and mixing the base powder, a binder and a dispersion solvent to obtain a slurry; (5) granulating the slurry to obtain a granulated powder; (6) sequentially performing dry pressing and cold isostatic pressing on the granulated powder to obtain a green body; (7) sintering the green body to obtain an aluminum silicate-based porous ceramic framework. In step (6), the pressure of the cold isostatic pressing is 100-300 MPa, and the pressure holding time is 0.5-5 min.

2. The production method according to claim 1, characterized by, In step (7), the sintering temperature is 800-1400 ℃, and the holding time is 4-24 h.

3. The production method according to any one of claims 1 to 2, characterized by, In step (3), the average particle size of the base powder is 1-35 μm, and the morphology is a non-spherical structure.

4. The production method according to any one of claims 1 to 3, characterized by, In step (3), the crushing comprises: placing the base raw material in a crusher for primary crushing, and then ball-milling the crushed base raw material for secondary crushing.

5. The production method according to any one of claims 1 to 4, characterized by, In step (2), the melting temperature is 1200-1800 ℃, and the time is 4-24 h.

6. The production method according to any one of claims 1 to 5, characterized by, In step (6), the pressure of the dry pressing is 3-10 MPa, and the pressure holding time is 0.5-5 min.

7. The production method according to any one of claims 1 to 6, characterized by, In step (4), the binder comprises one or more of polyvinyl alcohol, polyethylene glycol, polyvinyl butyral and sodium carboxymethyl cellulose.

8. The production method according to any one of claims 1 to 7, characterized by, In step (4), the binder is used in the form of a binder solution, the mass concentration of the binder solution is 1-5%, and the mass of the binder solution is 5-30% of the mass of the base powder.

9. The production method according to any one of claims 1 to 8, characterized by, In step (4), the dispersion solvent comprises water or ethanol.

10. The production method according to any one of claims 1 to 9, characterized by, In step (5), the particle size of the granulated powder is 100-200 mesh.

11. The production method according to any one of claims 1 to 10, characterized by, 12. The aluminum silicate-based porous ceramic framework prepared by the preparation method of any one of claims 1-11. The porosity is 20-50%.

13. The aluminum silicate-based porous ceramic skeleton according to claim 12, characterized by 14. The use of the aluminum silicate-based porous ceramic framework of claim 12 or 13 in resin-infiltrated ceramic materials. The resin-infiltrated ceramic material comprises an aluminum silicate-based porous ceramic framework and a resin material infiltrated in the aluminum silicate-based porous ceramic framework; the aluminum silicate-based porous ceramic framework is the aluminum silicate-based porous ceramic framework of claim 12 or 13.

15. A resin-infiltrated ceramic material, characterized by, The resin material comprises an acrylic resin.

16. The resin-infiltrated ceramic material of claim 15, wherein, The resin-infiltrated ceramic material has a hardness of ≥2.6 GPa, a bending strength of ≥300 MPa and an elastic modulus of ≥30 GPa.

17. The resin-infiltrated ceramic material of claim 15 or 16, wherein, The raw materials for preparing the acrylic resin comprise, in terms of mass percentage, 97-99.9% of an acrylate monomer and 0.1-3% of an initiator.

18. The resin-infiltrated ceramic material of any one of claims 15-17, wherein, The acrylate monomer comprises a main monomer and a diluent monomer; the mass ratio of the main monomer to the diluent monomer is (1.5-9):

1.

19. The resin-infiltrated ceramic material of any one of claims 15-18, wherein, ​ 20. The resin-infiltrated ceramic material of any one of claims 15-19, wherein, The main monomer includes one or more of bisphenol A-glycidyl methacrylate, bisphenol A glyceryl dimethacrylate, ethoxylated bisphenol A dimethacrylate, and urethane dimethacrylate; the diluent monomer includes one or more of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, and trimethylolpropane triacrylate.

21. Use of the resin-infiltrated ceramic material according to any one of claims 15 to 20 for the manufacture of a dental restoration.

22. A dental restoration comprising the resin-infiltrated ceramic material according to any one of claims 15 to 20.

23. The dental restoration of claim 22, wherein, The dental restoration includes a dental veneer, an onlay, an inlay, a single crown, a front tooth, or a three-unit bridge.

Images