A porous ceramic framework, a preparation method thereof, and a double-bionic resin-ceramic composite material

Abstract

The present invention relates to the technical field of dentures, and provides a porous ceramic framework, a preparation method thereof, and a double-bionic resin-ceramic composite material. The porous ceramic framework provided by the present invention is a three-dimensional structure formed by an array of a plurality of unit cell structures; the unit cell structure is a cube provided with through holes, the through holes are chamfered three-cylinder structures, the three cylinders in the three-cylinder structure have the same size, and the length of the cylinder in the three cylinders is the same as the side length of the cube. By changing the parameter D, the present invention controls the porosity of the pore unit and constructs a porous ceramic framework with a gradually changing porosity from the bottom to the top, achieving the bionics of resin-infiltrated ceramic materials and human teeth to the greatest extent in terms of physical properties; the porosity, pore size, and pore distribution of the porous ceramic framework provided by the present invention have strong controllability and can achieve a three-dimensional through structure, achieving the bionics of resin-infiltrated ceramic materials and human teeth to the greatest extent in terms of structure.

Description

Technical Field

[0001] The present invention relates to the technical field of dentures, and in particular to a porous ceramic skeleton and a preparation method thereof, and a double-bionic resin-ceramic composite material. Background Art

[0002] Dentures, also commonly known as "false teeth", refer to prostheses made after partial or complete loss of normal teeth in the upper and lower jaws of the human body, which can replace the missing teeth to achieve their normal chewing, vocalization, aesthetic and other functions, thereby reducing various inconveniences brought to patients by tooth loss.

[0003] Currently, denture materials used in clinical applications are ceramic-resin composite materials. Among them, a porous ceramic skeleton is prepared by combining methods such as the pore-forming agent method, freeze-drying method, foaming method, etc. with the sintering method, and a liquid resin is infiltrated and cured under vacuum to mimic the inorganic-organic composite material properties of natural teeth.

[0004] In the application document with publication number CN108743405 A, a directional porous green body with a lamellar structure is obtained through slurry preparation, freeze casting and vacuum freeze-drying, and then the surface of the skeleton is modified and infiltrated with a liquid resin monomer. After the resin is polymerized, a zirconia / resin composite material for dentures with a bionic structure is obtained. The flexural strength of this material is 118 MPa - 282 MPa, and the hardness is 1.8 - 3.4 GPa, and its physical properties are similar to those of natural teeth.

[0005] In the application document with publication number CN106830928 A, a resin / ceramic composite material is prepared through steps of pressing forming, high-temperature sintering, surface treatment, infiltration treatment and resin polymerization. The material prepared by this method has a flexural strength of not less than 130 MPa, a compressive strength of not less than 300 MPa, an elastic modulus of not less than 8.8 GPa, and a hardness of 0.6 - 5.3 GPa.

[0006] However, the porosity, pore size and pore distribution of the above composite materials have poor controllability, and a three-dimensional through structure cannot be achieved, resulting in great randomness in the infiltration of resin materials, and further resulting in insufficient performance stability of the materials, which limits their application in the actual field of denture repair. Summary of the Invention

[0007] In view of this, the purpose of the present invention is to provide a porous ceramic skeleton and a preparation method thereof, and a double-bionic resin-ceramic composite material. The present invention controls the porosity of pore units by changing parameter D, and constructs a porous ceramic skeleton with a gradually changing porosity from bottom to top. The porosity, pore size and pore distribution of this skeleton structure have strong controllability, can achieve a three-dimensional through structure, further control the permeability of resin materials, make the performance of the materials stable, and realize wide application in the actual field of denture repair.

[0008] To achieve the above-mentioned invention objectives, the present invention provides the following technical solutions:

[0009] The present invention provides a porous ceramic skeleton, which is a three-dimensional structure formed by an array of a plurality of unit cell structures; the unit cell structure is a cube provided with through holes, the through holes are chamfered three-cylinder structures, the three cylinders in the three-cylinder structure have the same size, and the length of the cylinder in the three cylinders is the same as the side length of the cube;

[0010] In the order from bottom to top, the pore diameters of the unit cell structures in the porous ceramic skeleton gradually decrease, each level is 1 to 5 layers, and the pore diameters of the unit cell structures in each level are the same; the pore diameter of the unit cell structure is measured by the diameter of the cylinder in the three cylinders;

[0011] The unit cell structures in each level are respectively arranged in an array in the x, y, and z axis directions.

[0012] Preferably, the pore diameter of the unit cell structure is 0.01 to 1 mm;

[0013] The porosity of the porous ceramic skeleton is calculated by Equation I:

[0014] P = 59.76D - 14.02 Equation I;

[0015] In Equation I: D is the pore diameter of the unit cell structure, with the unit of mm; P is the porosity of the porous ceramic skeleton, with the unit of %.

[0016] Preferably, the porosity of the porous ceramic skeleton is 3 to 70%; the difference in pore diameters between adjacent two levels is 0.01 to 1 mm.

[0017] The present invention also provides a preparation method of the porous ceramic skeleton described in the above technical solutions, including the following steps:

[0018] According to the structural design model of the porous ceramic skeleton described in any one of Claims 1 to 3, and then performing photocuring 3D printing with a ceramic resin slurry to obtain the porous ceramic skeleton.

[0019] Preferably, the steps for constructing the model are:

[0020] (1) Respectively construct cylinder models with the same center point and the same diameter D1 in the x, y, and z axis directions to obtain a three-cylinder structure model, and perform a Boolean subtraction of each cylinder model with a cube with a side length of 2 mm to obtain a porous ceramic skeleton unit body with a pore diameter of D1;

[0021] (2) Chamfer the edge parts of the porous ceramic skeleton unit body with a radius R = (2 - D1) / 2 to obtain a unit cell structure with a pore diameter of D1;

[0022] (3) Array the unit cell structures in the x, y, and z-axis directions respectively to obtain a unit cell structure framework with an aperture of D1;

[0023] (4) Repeat steps (1) to (3), replace D1 with D2 to obtain a unit cell structure framework with an aperture of D2;

[0024] (5) Repeat step (4) n times. Each time when repeating, replace D1. According to the number of repetitions, successively replace D1 with D3, D4... D n , where n≥3, and D1 to D n increase or decrease successively to obtain a unit cell structure framework with apertures of D3 to D n ;

[0025] (6) Stack the multi-layer unit cell structure frameworks with apertures of D1 to D n in the order of increasing or decreasing apertures successively to obtain a porous ceramic framework model.

[0026] Preferably, the ceramic resin slurry comprises the following components in mass percentages:

[0027]

[0028] Preferably, the ceramic material includes one or more of zirconia powder, lithium disilicate ceramic particles, sodium aluminosilicate ceramic particles, alumina ceramics, feldspar ceramic powder, barium glass powder, and hydroxyapatite;

[0029] The resin material includes one or more of dimethylacrylaminoformate, triethylene glycol dimethacrylate, bisphenol A glycidyl methacrylate, ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate; the initiator includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphonate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime);

[0030] The dispersant includes one or more of polyethylene glycol, Triton X100, polycaprolactone-based dispersant, polyacrylic acid, polyethyleneimine, and sodium dodecylbenzenesulfonate;

[0031] The auxiliary agent includes one or more of a leveling agent, a defoaming agent, and a color stabilizer.

[0032] The present invention also provides a method for preparing a double-bionic resin-ceramic composite material, comprising the following steps: subjecting the porous ceramic framework to debinding treatment, pre-sintering, modification, drying, infiltration treatment and post-curing treatment in sequence to obtain the double-bionic resin-ceramic composite material; the modifier used for the modification is a silane coupling agent.

[0033] Preferably, the temperature of the debinding treatment is 300-600 °C and the time is 1-10 h; the debinding treatment is carried out in an air or nitrogen atmosphere; the modification is to soak the pre-sintered porous ceramic framework in the silane coupling agent, and the soaking time is 4-6 h; the post-curing treatment includes photo-curing and thermal curing carried out in sequence.

[0034] The present invention also provides the double-bionic resin-ceramic composite material prepared by the preparation method described in the above technical solution.

[0035] The present invention provides a porous ceramic framework, which is a three-dimensional structure formed by an array of a plurality of unit cell structures; the unit cell structure is a cube provided with through holes, the through holes are chamfered three-cylinder structures, the three cylinders in the three-cylinder structure have the same size, and the length of the cylinder in the three cylinders is the same as the side length of the cube; in the order from bottom to top, the pore diameter of the unit cell structure in the porous ceramic framework decreases step by step, each level is 1-5 layers, and the pore diameter of the unit cell structure in each level is the same; the pore diameter of the unit cell structure is measured by the diameter of the cylinder in the three cylinders; the unit cell structures in each level are arranged in an array in the x, y and z axis directions. By changing the pore diameter (D) of the unit cell structure, the present invention controls the pore units of each level of the porous ceramic framework, and further controls the porosity of the entire framework, so as to construct a porous ceramic framework with a porosity gradually changing from the bottom to the top, which maximally realizes the bionics of the resin-infiltrated ceramic material and human teeth in terms of physical properties; the porosity, pore diameter and pore distribution of the porous ceramic framework provided by the present invention have strong controllability, can realize a three-dimensional through structure, further control the permeability of the resin material, and make the performance of the material stable, which maximally realizes the bionics of the resin-infiltrated ceramic material and human teeth in terms of structure, and finally realizes wide application in the field of actual denture repair.

[0036] The present invention also provides a double-bionic resin-ceramic composite material. Through structural design, the present invention introduces parameter D, and the porosity of the porous ceramic skeleton gradually increases from the cut-off part to the neck part, realizing the outer hardness and inner toughness of the prosthetic denture, achieving double bionics of structure and physical properties, improving the service performance of the denture, and extending the service life of the prosthetic denture; the composite material provided by the present invention has moderate strength and hardness, is not prone to wear, and does not easily wear the natural teeth of humans; the composite material provided by the present invention has low brittleness and is not easily broken during the cutting process; through the inner hole surface design and the surface treatment of the porous ceramic green body, the resin and the porous ceramic green body are more closely combined, enhancing the stability of the composite material; the present invention can realize material functionalization, and different composite materials can be selected for repair according to different repair parts. According to the data of the examples, the flexural strength of the double-bionic resin-ceramic composite material provided by the present invention is 205-946 MPa, the elastic modulus is 13-80 GPa, and the hardness is 0.35-3.6 GPa. Description of the Drawings

[0037] Figure 1 It is a morphology diagram of a porous ceramic skeleton unit body with D = 0.9 mm;

[0038] Figure 2 It is a morphology diagram of a porous ceramic skeleton unit body with D = 1 mm;

[0039] Figure 3 It is a morphology diagram of a porous ceramic skeleton unit body with D = 1.1 mm;

[0040] Figure 4 It is a morphology diagram of a porous ceramic skeleton unit body with D = 1.2 mm;

[0041] Figure 5 It is a morphology diagram of a porous ceramic skeleton unit body with D = 1.3 mm;

[0042] Figure 6 It is a morphology diagram of a porous ceramic skeleton unit body with D = 1.4 mm;

[0043] Figure 7 It is a construction process diagram of the unit cell structure;

[0044] Figure 8 It is a unit cell structure skeleton diagram with D = 1 mm obtained in Example 5. Detailed Embodiments [[ID=?]] [[ID=?]]

[0045] The present invention provides a porous ceramic skeleton, and the porous ceramic skeleton is a three-dimensional structure formed by an array of a plurality of unit cell structures; the unit cell structure is a cube provided with through holes, the through holes are chamfered three-cylinder structures, the sizes of the three cylinders in the three-cylinder structure are the same, and the length of the cylinder in the three cylinders is the same as the side length of the cube;

[0046] In the order from bottom to top, the pore diameters of the single-cell structures in the porous ceramic skeleton gradually decrease, with each level being 1 to 5 layers, and the pore diameters of the single-cell structures in each level being the same; the pore diameter of the single-cell structure is measured by the diameter of the cylinder in the three cylinders;

[0047] The single-cell structures in each level are arranged in an array in the x, y, and z-axis directions respectively.

[0048] In the present invention, the porosity of the porous ceramic skeleton is preferably 3 to 70%, more preferably 20 to 40%; the difference in pore diameter between adjacent two levels is preferably 0.01 to 1 mm, more preferably 0.1 to 0.5 mm.

[0049] In the present invention, the three cylinders are a solid formed by the intersection of three perpendicular cylinders; the diameter of the cylinder in the three cylinders is preferably 0.01 to 1 mm, more preferably 0.1 to 0.5 mm; the porosity of the porous ceramic skeleton is preferably calculated by Equation I: P = 59.76D - 14.02 Equation I; where D is the pore diameter of the single-cell structure, in mm, with a value of 0.25 to 1.9 mm; P is the porosity of the porous ceramic skeleton, in %. In a specific embodiment of the present invention, D is preferably the pore diameter corresponding to a single-cell structure with a side length of 2 mm, and the value range of D is preferably 0.25 to 1.9 mm, more preferably 0.5 to 1.5 mm.

[0050] The present invention also provides a method for preparing a porous ceramic skeleton, comprising the following steps:

[0051] According to the structural design model of the porous ceramic skeleton, then perform photocuring 3D printing using a ceramic resin slurry to obtain the porous ceramic skeleton.

[0052] In the present invention, the step of constructing the model is preferably:

[0053] (1) Respectively construct cylinder models with the same center point and the same diameter D1 in the x, y, and z-axis directions to obtain a three-cylinder structure model, and perform a Boolean subtraction of each cylinder model with a cube with a side length of 2 mm to obtain a porous ceramic skeleton unit with a pore diameter of D1;

[0054] (2) Chamfer the corner parts of the porous ceramic skeleton unit with a radius R = (2 - D1) / 2 to obtain a single-cell structure with a pore diameter of D1;

[0055] (3) Array the single-cell structures in the x, y, and z-axis directions respectively to obtain a single-cell structure skeleton with a pore diameter of D1;

[0056] (4) Repeat steps (1) to (3), and replace D1 with D2 to obtain a single-cell structure skeleton with a pore diameter of D2;

[0057] (5) Repeat step (4) n times. Each time when repeating, replace D1. According to the number of repetitions, replace D1 with D3, D4... D n , where n ≥ 3, and D1 to D n increase or decrease in sequence, to obtain a unit cell structure skeleton with pore diameter D 3～ D n ;

[0058] (6) Stack the multi-layer unit cell structure skeletons with pore diameters D1 to D n in the order of increasing or decreasing pore diameter in sequence, to obtain a porous ceramic skeleton model.

[0059] In the present invention, in the said step (1), the relationship between the parameter D of the porous ceramic skeleton unit body, the porosity P and the pore morphology is shown in Table 1. From Table 1, the change of the porosity of the porous ceramic skeleton under different D can be obtained; when D is 0.9 mm, the morphology of the porous ceramic skeleton unit body is as Figure 1 shown, when D is 1 mm, the morphology of the porous ceramic skeleton unit body is as Figure 2 shown, when D is 1.1 mm, the morphology of the porous ceramic skeleton unit body is as Figure 3 shown, when D is 1.2 mm, the morphology of the porous ceramic skeleton unit body is as Figure 4 shown, when D is 1.3 mm, the morphology of the porous ceramic skeleton unit body is as Figure 5 shown, when D is 1.4 mm, the morphology of the porous ceramic skeleton unit body is as Figure 6 shown.

[0060] Table 1 Relationship between the parameter D and the porosity P of the porous ceramic skeleton unit body

[0061] D 0.9 1 1.1 1.2 1.3 1.4 P(％) 39.73 45.73 51.77 57.77 63.59 68.47

[0062] In the present invention, the construction processes of the said step (1) and step (2) are specifically shown in Figure 7 , and it can be known from Figure 7 that the present invention uses Boolean operation to subtract a three-cylinder structure from a cube, and then chamfers the remaining part to obtain a unit cell structure.

[0063] The present invention has no special requirements for the number of arrays in the x, y, and z-axis directions in step (3), and can be adjusted according to actual needs; in a specific embodiment of the present invention, the number of arrays in the x and y-axis directions in step (3) is preferably more than 200, and the number of arrays in the z-axis direction is preferably 4 to 5. The present invention utilizes the fact that the curvature of any point within the triple-period minimal surface function is 0, which maximally ensures the absolute smoothness of the internal structure of the ceramic skeleton. Compared with the internal structure with edges and corners, it can better bond with the ceramic surface after the resin penetrates the ceramic in the later stage, improving the performance stability of the material.

[0064] In the present invention, unless otherwise specified, the various substances are commercially available products well-known to those skilled in the art.

[0065] In the present invention, the ceramic resin slurry preferably comprises the following components in mass percentages:

[0066]

[0067] In the present invention, the mass fraction of the ceramic material in the ceramic resin slurry is preferably 35-86%, more preferably 50-85%, and further preferably 82-85%; the ceramic material preferably includes one or more of zirconia powder, lithium disilicate ceramic particles, sodium aluminosilicate ceramic particles, alumina ceramics, feldspar ceramic powder, barium glass powder, and hydroxyapatite; the zirconia powder is preferably single-sized zirconia powder or a mixture of multi-sized zirconia powders, and the particle size of the zirconia powder is preferably 50 nm to 5 μm; the lithium disilicate ceramic particles are preferably single-sized lithium disilicate ceramics or a mixture of multi-sized lithium disilicate ceramic particles, and the particle size of the lithium disilicate ceramic particles is preferably 50 nm to 5 μm; the sodium aluminosilicate ceramic particles are preferably single-sized sodium aluminosilicate ceramics or a mixture of multi-sized sodium aluminosilicate ceramic particles, and the particle size of the sodium aluminosilicate ceramic particles is preferably 50 nm to 5 μm; the alumina ceramics preferably include spherical alumina ceramic particles and fibrous alumina ceramics, the spherical alumina ceramic particles are preferably single-sized spherical alumina ceramic particles or a mixture of multi-sized spherical alumina ceramic particles, and the particle size of the alumina ceramics is preferably 50 nm to 5 μm; the feldspar ceramic powder preferably includes one or more of albite, anorthite, celsian, hyalophane, microcline, orthoclase, and sanidine, the feldspar ceramic powder is preferably single-sized feldspar ceramic powder or a mixture of multi-sized feldspar ceramic powders, and the particle size of the feldspar ceramic powder is preferably 50 nm to 5 μm; the particle size of the barium glass powder is preferably 0.1-0.7 μm; the particle size of the hydroxyapatite is preferably 100 nm to 1 μm.

[0068] In the present invention, the mass fraction of the resin material in the ceramic resin slurry is preferably 9-60%, more preferably 10-30%, and still more preferably 10-15%; the resin material preferably includes one or more of dimethylaminoethyl methacrylate, triethylene glycol dimethacrylate, glycidyl methacrylate bisphenol A, ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol diacrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and more preferably a mixture of dimethylaminoethyl methacrylate, triethylene glycol dimethacrylate, and glycidyl methacrylate bisphenol A. The mass ratio of dimethylaminoethyl methacrylate, triethylene glycol dimethacrylate, and glycidyl methacrylate bisphenol A in the mixture is preferably 1:0.4-0.8:0.1-0.3, and more preferably 1:0.5-0.6:0.1-0.25.

[0069] In the present invention, the mass fraction of the initiator in the ceramic resin slurry is preferably 1-4%, more preferably 1.5-3.5%, and still more preferably 2-3%; the initiator preferably includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphinate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), and more preferably 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0070] In the present invention, the mass fraction of the dispersant in the ceramic resin slurry is preferably 0.01-1%, more preferably 0.3-0.9%, and still more preferably 0.5-0.8%; the dispersant preferably includes one or more of polyethylene glycol, Triton X100, polycaprolactone type dispersant, polyacrylic acid, polyethyleneimine, and sodium dodecylbenzenesulfonate, and more preferably one or more of polyethylene glycol 200, polyethylene glycol 400, polyethylene glycol 1000, polyethylene glycol 4000, and polyethylene glycol 6000; the model of the polyethylene glycol is preferably polyethylene glycol 400.

[0071] In the present invention, the mass fraction of the additive in the ceramic resin slurry is preferably 0.01 to 1%, more preferably 0.3 to 0.9%, and further preferably 0.5 to 1%; the additive preferably includes one or more of a leveling agent, a defoaming agent, and a color stabilizer, and more preferably one or two of a leveling agent and a defoaming agent; the leveling agent preferably includes one or more of AKN-1033 leveling agent (XUHUA Company), EFKASL 3258 leveling agent (BASF Company), 616 leveling agent (Keying Chemical Company), and BYK-333 leveling agent (BYK Chemie GmbH); the defoaming agent preferably includes one or more of BYKA535 defoaming agent (BYK Chemie GmbH), TEGO FOAMEX 810 defoaming agent (Evonik Germany), X-039 defoaming agent (Guangzhou Hongtai New Materials Company), and Z-3158 defoaming agent (Shanghai Yuewan New Materials); in a specific embodiment of the present invention, the leveling agent is purchased from BYK Chemie GmbH, with the model number BYK-333, and the defoaming agent is purchased from Evonik Germany, with the model number TEGO FOAMEX 810.

[0072] In the present invention, the printing speed of the photocuring 3D printing is preferably 0.01 to 0.1 mm / min, more preferably 0.05 mm / min, the curing time is preferably 3 to 8 s, more preferably 5 to 6 s, and the light intensity is preferably 60 to 100 PWM, more preferably 70 to 80 PWM; the present invention has no special requirements for the scaling ratio of the photocuring 3D printing, and it can meet the actual application. In the present invention, the relationship between the pore diameter d (the pore diameter used in actual 3D printing) of the porous ceramic skeleton model and the pore diameter D (the pore diameter used in the design model) of the porous ceramic skeleton is d = D * λ, where λ is the scaling ratio.

[0073] The present invention also provides a method for preparing a double-bionic resin ceramic composite material, comprising the following steps: subjecting the porous ceramic skeleton to debinding treatment, pre-sintering, modification, drying, infiltration treatment, and post-curing treatment in sequence to obtain a double-bionic resin ceramic composite material; the modifier for the modification is preferably a silane coupling agent.

[0074] In the present invention, the temperature of the debinding treatment is preferably 300 to 600 °C, more preferably 300 °C, the time is preferably 1 to 10 h, more preferably 10 h; the debinding treatment is preferably carried out in an air or nitrogen atmosphere; the equipment for the debinding treatment is preferably a Kemei sintering furnace, and the heating and cooling rates of the debinding treatment are preferably 0.5 to 10 °C / min, more preferably 5 °C / min.

[0075] After the debinding treatment is completed, the present invention preferably further includes cooling the obtained debinding treatment product to room temperature; the present invention has no special limitation on the cooling, and any cooling method well-known to those skilled in the art can be adopted, such as natural cooling.

[0076] In the present invention, the temperature of the pre-sintering is preferably 1400-1700 °C, more preferably 1700 °C, the time is preferably 1-10 h, more preferably 10 h; the heating rate of the pre-sintering is preferably 0.5-10 °C / min, more preferably 5-8 °C / min, and the heating is preferably from room temperature to the temperature of the pre-sintering; the pre-sintering is preferably carried out in an air atmosphere. Through pre-sintering, the porous ceramic skeleton in the present invention has certain mechanical properties.

[0077] After the pre-sintering is completed, the present invention preferably further includes cooling the obtained pre-sintered product to room temperature; the present invention has no special limitation on the cooling, and a cooling method well-known to those skilled in the art can be used, such as natural cooling.

[0078] In the present invention, the modification is preferably to soak the pre-sintered porous ceramic skeleton in a silane coupling agent, the soaking time is preferably 4-6 h, more preferably 5 h; the silane coupling agent preferably includes one or more of Shuguang KH550, KH560, KH570 and Momentive A-137; the modification is preferably carried out under vacuum conditions, and the vacuum degree of the vacuum conditions is preferably -0.1 MPa; in a specific embodiment of the present invention, the silane coupling agent is preferably KH570. By modifying the porous ceramic skeleton in the present invention, an organic coating film is formed on the surface of the ceramic skeleton material, which is beneficial to the better combination of the resin and the ceramic skeleton.

[0079] In the present invention, the temperature of the drying is preferably 110-130 °C, more preferably 130 °C, the time is preferably 1-5 h, more preferably 1-3 h, and the drying atmosphere is air or nitrogen; the present invention has no special requirements for the drying method, and a method commonly used by those skilled in the art can be selected.

[0080] In the present invention, the penetration treatment is preferably carried out by vacuum-soaking the dried porous ceramic framework in a polymer solution under vacuum conditions, followed by soaking under normal pressure after releasing the vacuum, and repeating the above steps of vacuum soaking - releasing the vacuum - soaking under normal pressure for 3 to 4 times until the liquid level of the polymer solution remains unchanged and no bubbles are generated; the temperatures of the vacuum soaking and the normal pressure soaking are independently preferably 30 to 60 °C, more preferably 40 to 50 °C; the time of a single vacuum soaking is preferably 30 to 120 min, more preferably 50 to 100 min; the vacuum degree of the vacuum conditions is preferably -0.1 MPa; the time of a single normal pressure soaking is preferably 10 to 60 min, more preferably 20 to 50 min; the components of the polymer solution preferably include a resin and an initiator; the resin preferably includes one or more of PMMA, UDMA, BIS-GMA, TEGDMA, and HEMA, and the resin undergoes a cross-linking reaction under the action of the initiator, thereby realizing the filling of the ceramic framework; the initiator preferably includes one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoyl phenylphosphonate, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone; the mass fraction of the initiator in the polymer solution is preferably 1 to 3%, more preferably 2%; in a specific embodiment of the present invention, the polymer solution is composed of PMMA with a mass fraction of 98% and the initiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide with a mass fraction of 2%.

[0081] In the present invention, the post-curing treatment includes photo-curing and thermal-curing carried out in sequence; the equipment for photo-curing is preferably a photo-curing lamp box, and the photo-curing is preferably carried out by immersing the porous ceramic framework after the above penetration treatment in water and curing it in the photo-curing lamp box; the light used for photo-curing is preferably medium-high light; the wavelength of the medium-high light is preferably 385 to 460 nm, more preferably 405 nm; the time of photo-curing is preferably 20 to 60 min; photo-curing is carried out in water in the present invention, which can absorb the heat released during the curing process and relieve the stress concentration caused by excessive local heat. In the present invention, the thermal-curing is preferably carried out by sintering the porous ceramic framework after photo-curing; the temperature of the sintering is preferably 125 to 155 °C, more preferably 130 to 140 °C; the time of the sintering is preferably 12 to 14 h, more preferably 13 h; the equipment for sintering is preferably an oven. After the sintering is completed, the present invention preferably further includes cooling the obtained solid treatment system to room temperature, and the cooling rate of the cooling is preferably 0.5 to 5 °C / min, more preferably 1 to 3 °C / min.

[0082] The present invention also provides a double-bionic resin-ceramic composite material prepared by the preparation method described in the above solution. The double-bionic resin-ceramic composite material provided by the present invention has gradually increasing porosity in the porous ceramic skeleton from the incisal edge (the upper part of the tooth, the end where the teeth contact each other), the neck (the part connecting the crown and the root of the tooth), and the root (the tooth root), realizing the external hardness and internal toughness of the prosthetic denture, and achieving double bionics of structure and physical properties.

[0083] The present invention fits according to the pore size and mechanical property data of the double-bionic resin-ceramic composite material to obtain the corresponding functional relationship. Those skilled in the art can obtain the physical properties of the composite material prepared in Example 1 according to the fitting function. The flexural strength F of the double-bionic resin-ceramic composite material is calculated by Equation II:

[0084] F = -193.1D + 1178.3 Equation II,

[0085] In Equation II: F is the flexural strength, with the unit of MPa, and D is the pore size of the unit cell structure, with the unit of mm;

[0086] The elastic modulus of the double-bionic resin-ceramic composite material is calculated by Equation III:

[0087] G = 1.3571D 2 - 25.043D + 104.8 Equation III,

[0088] In Equation II: G is the elastic modulus, with the unit of GPa, and D is the pore size of the unit cell structure, with the unit of mm;

[0089] The hardness of the double-bionic resin-ceramic composite material is calculated by Equation IV:

[0090] H = -0.81D + 4.45 Equation IV,

[0091] In Equation II: H is the hardness, with the unit of GPa, and D is the pore size of the unit cell structure, with the unit of mm.

[0092] To further illustrate the present invention, the following examples are used to describe in detail the porous ceramic skeleton provided by the present invention, its preparation method, and a double-bionic resin-ceramic composite material, but they should not be construed as limiting the protection scope of the present invention.

[0093] Example 1

[0094] Construction of the porous ceramic skeleton model:

[0095] (1) Cylindrical models with the same center point and the same diameter are constructed in the x, y, and z-axis directions. The diameter D is 0.74 mm. The cylindrical model is subjected to Boolean subtraction with a cube with a side length of 2 mm to obtain a porous ceramic skeleton unit with a pore size of 0.74 mm;

[0096] (2) Chamfer the edge parts of the porous ceramic framework unit with a radius R = 0.37 mm to obtain a unit cell structure with a pore diameter of 0.74 mm;

[0097] (3) Array the unit cell structures in the x, y, and z-axis directions respectively to obtain a unit cell structure framework with a pore diameter of 0.74 mm, where 20 - 100 are arrayed in both the x and y-axis directions (the number of arrays in the two directions is the same), and 5 are arrayed in the z-axis direction;

[0098] (4) Repeat steps (1) - (3), replace 0.74 mm with 0.57 mm to obtain a unit cell structure framework with a pore diameter of 0.57 mm;

[0099] (5) Repeat steps (1) - (3), replace 0.57 mm with 0.40 mm to obtain a unit cell structure framework with a pore diameter of 0.40 mm;

[0100] (6) Repeat steps (1) - (3), replace 0.40 mm with 0.32 mm to obtain a unit cell structure framework with a pore diameter of 0.32 mm;

[0101] (7) Repeat steps (1) - (3), replace 0.32 mm with 0.28 mm, and replace 5 arrayed in the z-axis direction with 4 to obtain a unit cell structure framework with a pore diameter of 0.28 mm;

[0102] (8) Use the unit cell structure framework with a pore diameter of 0.74 mm as the bottom layer, and stack it upwards in sequence with the unit cell structure framework with a pore diameter of 0.57 mm, the unit cell structure framework with a pore diameter of 0.40 mm, the unit cell structure framework with a pore diameter of 0.32 mm, and the unit cell structure framework with a pore diameter of 0.28 mm to obtain a porous ceramic framework model.

[0103] (i) Preparation of ceramic resin slurry:

[0104] Mix zirconia powder with a content of 82%, ethoxylated bisphenol A dimethacrylate with a content of 6%, 1,6 - hexanediol diacrylate with a content of 8%, initiator 2,4,6 - trimethylbenzoyl - diphenylphosphine oxide with a content of 2%, dispersant polyethylene glycol 400 with a content of 0.5%, Triton X100 with a content of 0.5%, leveling agent with a content of 0.5%, and defoaming agent with a content of 0.5%, and stir evenly to obtain ceramic resin slurry, where the diameter of the zirconia powder is 50 nm, the leveling agent is BYK - 333 leveling agent of BYK, and the defoaming agent is TEGO FOAMEX 810 defoaming agent of Evonik Industries AG of Germany. The above contents are mass percentages.

[0105] (ii) 3D printing of porous ceramic framework model

[0106] According to the above-mentioned porous ceramic skeleton model, the above-mentioned ceramic resin slurry is used for photocuring 3D printing, with a scaling ratio of 2:1, that is, d = 1 / 2D, to obtain a porous ceramic skeleton with dimensions of 20 - 100 mm × 20 - 100 mm × 24 mm. The pore diameters of the porous ceramic skeleton are 0.37 mm, 0.285 mm, 0.20 mm, 0.16 mm, and 0.14 mm from bottom to top in sequence, and the porosities of the porous ceramic skeleton are 30%, 20%, 10%, 5%, and 3% from bottom to top in sequence; the printing speed is 0.05 mm / min, the curing time is 5 s, and the light intensity is 80 PWM.

[0107] (iii) Preparation of double-bionic resin ceramic composite material:

[0108] The above-mentioned porous ceramic skeleton is subjected to debinding treatment and then naturally cooled to room temperature. The debinding equipment is a Kemei sintering furnace, the debinding temperature is 300 °C, the debinding time is 10 h, the heating rate is 5 °C / min, and the debinding atmosphere is air;

[0109] Then the debound porous ceramic skeleton is pre-sintered and then naturally cooled to room temperature. The pre-sintering temperature is 1700 °C, the time is 10 h, the heating rate is 5 °C / min, and the sintering atmosphere is air;

[0110] Then the pre-sintered porous ceramic skeleton is modified by soaking the pre-sintered porous ceramic skeleton in a silane coupling agent for 5 h. The soaking temperature is 40 °C, the vacuum degree is -0.1 MPa, and the silane coupling agent is KH570;

[0111] Then the modified porous ceramic skeleton is dried. The drying temperature is 130 °C, the time is 3 h, and the drying atmosphere is air;

[0112] Then the dried porous ceramic skeleton is subjected to infiltration treatment. The infiltration treatment is to vacuum soak the dried porous ceramic skeleton in a polymer solution at 40 °C and -0.1 MPa for 30 min, then continue to soak at normal pressure for 10 min after releasing the vacuum degree, and repeat the vacuum soaking - releasing the vacuum degree - normal pressure soaking steps 4 times; the polymer solution is composed of PMMA with a mass fraction of 98% and the initiator 2,4,6-trimethylbenzoyl-diphenylphosphine oxide with a mass fraction of 2%;

[0113] Finally, post-curing treatment is performed on the porous ceramic skeleton after infiltration treatment. The post-curing treatment includes first performing photocuring and then thermocuring. The photocuring equipment is a Kemei photocuring lamp box. Specifically, the porous ceramic skeleton after infiltration treatment and the lamp box are immersed in water, and ultraviolet light with a wavelength of 405 nm is used for treatment for 60 min. The thermocuring equipment is an oven. The porous ceramic skeleton after photocuring is placed in the oven. The thermocuring temperature is 155 °C, the time is 12 h, and the cooling rate is 5 °C / min, obtaining a double-bionic resin-ceramic composite material.

[0114] By changing the pore diameter D and the scaling ratio λ, the present invention can control the porosity, pore diameter, and pore morphology of the pore unit, construct a porous ceramic skeleton with a gradually decreasing porosity from the bottom to the top, and achieve a three-dimensional through structure. Therefore, the double-bionic resin-ceramic composite material provided by the present invention maximally realizes the bionics of resin-infiltrated ceramic materials and human teeth in terms of structure.

[0115] Example 2

[0116] Construction of the porous ceramic skeleton model:

[0117] The double-bionic resin-ceramic composite material is prepared according to the steps of constructing the porous ceramic skeleton model, preparing the ceramic resin slurry, 3D printing the porous ceramic skeleton model, and preparing the double-bionic resin-ceramic composite material provided in Example 1. The difference is that the zirconia powder is changed to lithium disilicate ceramic, and the pre-sintering temperature is 820 °C.

[0118] Example 3

[0119] Construction of the porous ceramic skeleton model:

[0120] The double-bionic resin-ceramic composite material is prepared according to the steps of constructing the porous ceramic skeleton model, preparing the ceramic resin slurry, 3D printing the porous ceramic skeleton model, and preparing the double-bionic resin-ceramic composite material provided in Example 1. The difference is that the zirconia powder is changed to sodium aluminosilicate ceramic, and the pre-sintering temperature is 850 °C.

[0121] Example 4

[0122] Construction of the porous ceramic skeleton model:

[0123] The double-bionic resin-ceramic composite material is prepared according to the steps of constructing the porous ceramic skeleton model, preparing the ceramic resin slurry, 3D printing the porous ceramic skeleton model, and preparing the double-bionic resin-ceramic composite material provided in Example 1. The difference is that the zirconia powder is changed to feldspar porcelain ceramic, and the pre-sintering temperature is 850 °C.

[0124] Example 5

[0125] Construction of Porous Ceramic Skeleton Model:

[0126] (1) Cylindrical models with the same center point and the same diameter are constructed in the x, y, and z-axis directions. The diameter D is 1 mm. The cylindrical models are subjected to Boolean subtraction with a cube having a side length of 2 mm to obtain a porous ceramic skeleton unit with a pore diameter of 1 mm;

[0127] (2) The angular parts of the porous ceramic skeleton unit are chamfered with a radius R = 0.5 mm to obtain a unit cell structure with a pore diameter of 1 mm;

[0128] (3) The unit cell structures are arrayed in the x, y, and z-axis directions respectively to obtain a unit cell structure skeleton with a pore diameter of 1 mm, where 5 are arrayed in the x and y-axis directions respectively, and 4 are arrayed in the z-axis direction.

[0129] Figure 8 It is the skeleton diagram of the unit cell structure with D = 1 mm obtained in Example 5. This skeleton can achieve a three-dimensional through structure.

[0130] Test Example

[0131] Performance Test of Double Bionic Resin-Ceramic Composite Material

[0132] The performance of each unit cell structure skeleton layer of the double bionic resin-ceramic composite materials prepared in Examples 1 to 4 is tested. The test results are shown in Tables 2 to 5:

[0133] Table 2 Performance Test Results of the Double Bionic Resin-Ceramic Composite Material Prepared in Example 1

[0134]

[0135] Table 3 Performance Test Results of the Double Bionic Resin-Ceramic Composite Material Prepared in Example 2

[0136]

[0137] Table 4 Performance Test Results of the Double Bionic Resin-Ceramic Composite Material Prepared in Example 3

[0138]

[0139] Table 5 Performance Test Results of the Double Bionic Resin-Ceramic Composite Material Prepared in Example 4

[0140]

[0141] As can be seen from Tables 2 to 5, the double bionic resin-ceramic composite material provided by the present invention realizes soft and tough at the bottom and strong and hard at the top, and maximally realizes the bionics of resin-infiltrated ceramic materials and human teeth in terms of physical properties.

[0142] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A preparation method of a double bionic resin ceramic composite material, characterized in that, It includes the following steps: Subject the porous ceramic framework to debinding treatment, pre-sintering, modification, drying, infiltration treatment, and post-curing treatment in sequence to obtain a double-bionic resin ceramic composite material; the modifier used for the modification is a silane coupling agent; The infiltration treatment is to vacuum soak the dried porous ceramic framework in a polymer solution under vacuum conditions, soak it under normal pressure after releasing the vacuum degree, and repeat the above steps of vacuum soaking - releasing the vacuum degree - soaking under normal pressure for 3 to 4 times until the liquid level of the polymer solution remains unchanged and no bubbles are generated; the components of the polymer solution include resin and initiator; The post-curing treatment includes photo-curing and thermal curing carried out in sequence. The photo-curing is to immerse the porous ceramic framework after the infiltration treatment in water and cure it in a photo-curing light box; The porous ceramic framework is a three-dimensional structure formed by an array of several unit cell structures; the unit cell structure is a cube provided with through holes, the through holes are chamfered three-cylinder structures, the three-cylinder is an entity formed by the intersection of three perpendicular cylinders, the sizes of the three cylinders in the three-cylinder structure are the same, and the length of the cylinder in the three-cylinder and the side length of the cube are the same; In the order from bottom to top, the pore diameters of the unit cell structures in the porous ceramic framework decrease step by step, each level is 1 to 5 layers, and the pore diameters of the unit cell structures in each level are the same; the pore diameter of the unit cell structure is measured by the diameter of the cylinder in the three-cylinder; the difference in pore diameter between adjacent two levels is 0.01 to 1 mm; the diameter of the cylinder in the three-cylinder is 0.01 to 1 mm; the porosity of the porous ceramic framework is P = 59.76D - 14.02, D is the pore diameter of the unit cell structure, the unit is mm, the value range is 0.25 to 1.9 mm, and P is the porosity of the porous ceramic framework, the unit is %; The unit cell structures in each level are arrayed in the x, y, and z-axis directions respectively.

2. The preparation method according to claim 1, characterized in that, The porosity of the porous ceramic framework is 3 to 70%.

3. The preparation method according to any one of claims 1 to 2, characterized in that, The preparation method of the porous ceramic framework includes the following steps: According to the structural design model of the porous ceramic framework, then carry out photo-curing 3D printing using a ceramic resin slurry to obtain the porous ceramic framework.

4. The preparation method according to claim 3, characterized in that, The steps for constructing the model are: (1) Respectively construct cylindrical models with the same center point and the same diameter D1 in the x, y, and z-axis directions to obtain a three-cylinder structure model. Subtract each cylindrical model from a cube with a side length of 2 mm through Boolean operation to obtain a porous ceramic framework unit body with a pore diameter of D1; (2) Chamfer the edge parts of the porous ceramic framework unit body with a radius R = (2 - D1) / 2 to obtain a unit cell structure with a pore diameter of D1; (3) Array the unit cell structures in the x, y, and z-axis directions respectively to obtain a unit cell structure framework with a pore diameter of D1; (4) Repeat steps (1) to (3), and replace D1 with D2 to obtain a unit cell structure framework with a pore diameter of D2; (5) Repeat step (4) n times. Each time it is repeated, replace D1. According to the number of repetitions, replace D1 with D3, D4... D n , where n ≥ 3, and D1 to D n increase or decrease successively, to obtain a single-cell structure skeleton with pore sizes of D3 to D n ; (6) Stack the multi-layer single-cell structure skeletons with pore diameters ranging from D1 to D n in the order of increasing or decreasing pore diameters successively to obtain a porous ceramic skeleton model.

5. The preparation method according to claim 3, characterized in that, The ceramic resin slurry contains the following components in mass percentages: Ceramic material 35 to 86%; Resin material 9 to 60%; Initiator ​ ​ 6. The preparation method according to claim 5, wherein, The ceramic material includes one or more of zirconia powder, lithium disilicate ceramic particles, sodium aluminosilicate ceramic particles, alumina ceramics, feldspar ceramic powder, barium glass powder, and hydroxyapatite; The resin material includes one or more of dimethylacryloyl carbamate, triethylene glycol dimethacrylate, bisphenol A glycidyl methacrylate, ethoxylated bisphenol A dimethacrylate, 1,6 - hexanediol diacrylate, 2 - hydroxyethyl methacrylate, and 2 - hydroxypropyl methacrylate; The initiator includes one or more of 2,4,6 - trimethylbenzoyl - diphenylphosphine oxide, ethyl 2,4,6 - trimethylbenzoyl phenylphosphinate, 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinophenyl)butanone, and 1 - [4 - (phenylthio)phenyl] - 1,2 - octanedione 2 - (O - benzoyloxime); The dispersant includes one or more of polyethylene glycol, Triton X100, polycaprolactone - type dispersant, polyacrylic acid, polyethyleneimine, and sodium dodecylbenzenesulfonate; The auxiliary agent includes one or more of a leveling agent, a defoaming agent, and a color stabilizer.

7. The preparation method according to claim 1, wherein The temperature of the debinding treatment is 300 - 600 °C, and the time is 1 - 10 h; The debinding treatment is carried out in an air or nitrogen atmosphere; The modification is to soak the pre - sintered porous ceramic skeleton in a silane coupling agent, and the soaking time is 4 - 6 h; The post - curing treatment includes photo - curing and thermal - curing carried out in sequence.

8. The double - bionic resin - ceramic composite material prepared by the preparation method according to any one of claims 1 - 7.

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