Ceramic framework and preparation method therefor and use thereof, and resin-ceramic composite material and preparation method therefor and use thereof

Abstract

The present application relates to the technical field of composite materials, and provides a ceramic framework and a preparation method therefor and the use thereof, and a resin-ceramic composite material and a preparation method therefor and the use thereof. In the present application, ceramic frameworks having different porous structures exhibit varying hardness and strength, and can adapt to the demands of biomedical materials for different uses. In the present application, the hardness, strength and toughness of the resin-ceramic composite material can be regulated by means of the combination of the ceramic frameworks having different porous structures and different resins, and the composite material can be applied to biomedical materials such as dentures, artificial eyes or biomimetic bones.

Description

Ceramic framework, preparation method and application thereof, and resin ceramic composite material, preparation method and application thereof

[0001] The present application claims priority to the Chinese patent application No. CN202411169968.7, filed on August 23, 2024, and entitled "Ceramic framework, preparation method and application thereof, and resin ceramic composite material, preparation method and application thereof", the content of which is incorporated herein by reference in its entirety. TECHNICAL FIELD

[0002] The present application relates to the technical field of composite materials, in particular to a ceramic framework, a preparation method and application thereof, and a resin ceramic composite material, a preparation method and application thereof. BACKGROUND

[0003] Biomedical materials are materials used for diagnosing, treating, repairing or replacing damaged tissues or organs of a living body or improving the function thereof. Biomedical materials can be classified into bone, tooth, joint, tendon and other skeletal-muscular system repair materials, skin, breast, esophagus, respiratory tract, bladder and other soft tissue materials, artificial heart valve, blood vessel, cardiovascular catheter and other cardiovascular system materials, blood purification membrane and separation membrane, gas-selective permeation membrane, corneal contact lens and other medical membrane materials, tissue adhesives and suture materials, drug release carrier materials, clinical diagnosis and biosensor materials, and dental materials.

[0004] Different biomedical materials for different purposes have different requirements for mechanical properties such as strength, hardness and toughness, so that during the production and manufacturing process of biomedical materials, various production or processing methods have to be adopted to obtain various biological materials to meet the requirements of different mechanical properties, thereby increasing the labor cost and time cost of production.

[0005] SUMMARY

[0006] The present application aims to provide a ceramic framework, a preparation method and application thereof, and a resin ceramic composite material, a preparation method and application thereof. The ceramic framework provided by the present application has multiple types of porous structures, and the mechanical properties are adjustable and controllable.

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

[0008] The present application provides a ceramic framework, which has a porous structure.

[0009] The porous structure comprises one or more of a through-hole structure and a communicating-hole structure.

[0010] The communicating-hole structure is formed by a plurality of holes being communicated.

[0011] The through-hole structure comprises one or more of a unidirectional through-hole structure and a divergent through-hole structure.

[0012] Preferably, the holes in the through-hole structure are regular and / or irregular holes.

[0013] Preferably, the hole diameter of the holes in the through-hole structure increases from one end to the other end, or the hole diameter of the holes first increases and then decreases from one end to the other end, or the hole diameter of the holes first decreases and then increases from one end to the other end.

[0014] Preferably, the hole diameter of the holes in the through-hole structure is independently less than 1000 μm.

[0015] Preferably, the unidirectional through-hole structure is composed of a plurality of through-holes from one end to the other end.

[0016] Preferably, the divergent through-hole structure comprises a plurality of through-holes diverging from a starting position inside the ceramic skeleton to the surrounding.

[0017] Preferably, the divergent through-hole structure comprises a three-dimensional through-hole structure.

[0018] The three-dimensional through-hole structure is composed of a plurality of three-dimensional through-holes penetrating up, down, left, right, front and back.

[0019] Preferably, the hole diameter of each through-hole in the unidirectional through-hole structure increases from one end to the other end, or the hole diameter of each through-hole first increases and then decreases from one end to the other end, or the hole diameter of each through-hole first decreases and then increases from one end to the other end.

[0020] Preferably, the hole diameter of each through-hole in the unidirectional through-hole structure is independently less than 1000 μm.

[0021] Preferably, the hole diameter of each through-hole in the divergent through-hole structure gradually increases from the starting position to the surrounding to form a horn shape, or the hole diameter of each through-hole gradually decreases from the starting position to the surrounding, or the hole diameter of each through-hole first increases and then decreases from the starting position to the surrounding, or the hole diameter of each through-hole first decreases and then increases from the starting position to the surrounding.

[0022] Preferably, the hole diameter of each through-hole in the divergent through-hole structure is independently less than 1000 μm.

[0023] Preferably, the aperture of each three-dimensional through hole in the three-dimensional through hole structure is independently gradually increased from the middle to the periphery to form a horn shape, or the aperture of each three-dimensional through hole is independently gradually decreased from the middle to the periphery, or the aperture of each three-dimensional through hole is independently gradually increased from the middle to the periphery and then decreased, or the aperture of each three-dimensional through hole is independently gradually decreased from the middle to the periphery and then increased.

[0024] Preferably, the aperture of each three-dimensional through hole in the three-dimensional through hole structure is independently in the range of 1000 μm or less.

[0025] The application provides a preparation method of the ceramic framework, including the following steps:

[0026] The main raw material, the binder and the solvent are mixed to obtain a slurry; the main raw material includes one or more of a biologically inert ceramic material and a biologically active ceramic material;

[0027] The slurry is subjected to flow casting to obtain a flow cast sheet;

[0028] The flow cast sheet is subjected to lamination to obtain a laminated sheet;

[0029] The laminated sheet is subjected to sintering to obtain the ceramic framework.

[0030] The application provides a preparation method of the ceramic framework, including the following steps:

[0031] The main raw material and the solvent are mixed to obtain a ceramic slurry; the main raw material includes one or more of a biologically inert ceramic material and a biologically active ceramic material;

[0032] The ceramic slurry is subjected to freezing to obtain a frozen block;

[0033] The frozen block is subjected to drying to obtain a dried sample block;

[0034] The dried sample block is subjected to sintering to obtain the ceramic framework.

[0035] The application provides a preparation method of the ceramic framework, including the following steps:

[0036] The main raw material is mixed to obtain a ceramic powder; the main raw material includes one or more of a biologically inert ceramic material and a biologically active ceramic material;

[0037] The ceramic powder is subjected to dry pressing and / or isostatic pressing to obtain a green body;

[0038] The green body is subjected to sintering to obtain the ceramic framework.

[0039] The application provides a preparation method of the ceramic framework, including the following steps:

[0040] mixing main raw materials to obtain a mixture; the main raw materials include one or more of a bio-inert ceramic material and a bio-active ceramic material;

[0041] kneading the mixture, a binder and a solvent to obtain a kneaded material;

[0042] aging the kneaded material and then pugging to obtain a pugged block;

[0043] opening the pugged block to obtain a mud segment;

[0044] extruding the mud segment to obtain a wet blank;

[0045] drying the wet blank to obtain a dry blank;

[0046] sintering the dry blank to obtain a ceramic framework.

[0047] The application provides application of the ceramic framework in the technical solution or the ceramic framework prepared by the preparation method in the technical solution in preparation of a biomedical material.

[0048] Preferably, the biomedical material includes a false tooth, a false eye or a bionic bone.

[0049] The application provides a resin-ceramic composite material, which includes a ceramic framework and resin filled in a porous structure of the ceramic framework; the ceramic framework is the ceramic framework in the technical solution or the ceramic framework prepared by the preparation method in the technical solution.

[0050] Preferably, preparation raw materials of the resin include one or more of a monofunctional acrylate and a multifunctional acrylate.

[0051] The application provides a preparation method of the resin-ceramic composite material in the technical solution, which includes the following steps:

[0052] immersing the ceramic framework in a resin precursor solution to perform curing to obtain the resin-ceramic composite material.

[0053] Preferably, the pressure of the curing is 0.1-500 MPa; the temperature of the curing is 10-180 ℃; and the holding time of the curing is 1 min-48 h.

[0054] The application provides application of the resin-ceramic composite material in the technical solution or the resin-ceramic composite material prepared by the preparation method in the technical solution in preparation of a biomedical material.

[0055] Preferably, the biomedical material includes a false tooth, a false eye or a bionic bone.

[0056] The application provides a ceramic framework with a porous structure. In the application, the ceramic frameworks with different porous structures have different hardness and strength, and can meet the needs of biomedical materials for different purposes.

[0057] The application provides a preparation method of the ceramic framework. In the application, the main raw material of the ceramic framework comprises one or more of biologically inert ceramic materials and biologically active ceramic materials. As a preferred scheme, zirconium oxide, feldspar, sodium aluminum silicate, hydroxyapatite and the like can be used as denture materials, and hydroxyapatite, calcium phosphate and zirconium oxide with better biocompatibility can be used as various bionic bone materials, so as to meet the needs of biomedical materials for different purposes.

[0058] The application provides a resin-ceramic composite material comprising a ceramic framework and resin filled in the porous structure of the ceramic framework. The resin-ceramic composite material can be applied to biomedical materials such as dentures, artificial eyes or bionic bones by matching the ceramic frameworks with different porous structures and different resins, so as to control the hardness, strength and toughness of the resin-ceramic composite material.

[0059] Further preferably, the resin-ceramic composite material provided by the application has high hardness and strength on the outside and excellent toughness on the inside, so as to improve the service life of the denture. At present, mainstream full-ceramic dentures on the market are generally prepared from zirconium oxide ceramic, and have high strength, high elastic modulus, high hardness and wear resistance of ceramic. The hardness of zirconium oxide ceramic is only inferior to that of diamond, and the zirconium oxide ceramic can seriously wear normal teeth in the use process, and is not suitable for matching with normal teeth. The wear resistance of resin dentures is less than that of normal teeth, and the resin dentures can be quickly worn in the use process, thereby causing low service life and being not suitable for matching with human teeth. The resin-ceramic composite material is prepared by combining the characteristics of the two materials, and has high strength to meet the strength requirement, and the hardness and wear resistance are close to those of human teeth, so as to improve the service life of the denture. Moreover, the resin-ceramic composite material provided by the application can be directly turned according to the needs of customers, and can be used as a denture, so as to be suitable for industrialized popularization and application. BRIEF DESCRIPTION OF DRAWINGS

[0060] FIG. 1 is a schematic diagram of a ceramic framework structure with through holes with a larger pore size from one end to the other end;

[0061] FIG. 2 is a schematic diagram of a ceramic framework structure with through holes with a pore size decreasing first and then increasing from one end to the other end;

[0062] FIG. 3 is a schematic diagram of a ceramic framework structure with through holes with a pore size increasing first and then decreasing from one end to the other end;

[0063] FIG. 4 is a schematic diagram of a ceramic framework structure with through holes from one end to the other end;

[0064] Figure 5 is a schematic diagram of a ceramic framework structure with various trends of through holes (both end faces are small holes);

[0065] Figure 6 is a schematic diagram of a ceramic framework structure with through holes;

[0066] Figure 7 is a schematic diagram of a ceramic framework structure with three- dimensional through holes;

[0067] Figure 8 is a schematic diagram of a ceramic framework structure with three- dimensional through holes;

[0068] Figure 9 is a schematic diagram of a ceramic framework structure with various trends of through holes (both end faces are large holes);

[0069] Figure 10 is a schematic diagram of a ceramic framework structure with connected holes that first decrease and then increase;

[0070] Figure 11 is a schematic diagram of a ceramic framework structure with connected holes that increase in one direction;

[0071] Figure 12 is a schematic diagram of a ceramic framework structure with various trends of connected holes;

[0072] Figure 13 is a schematic diagram of a ceramic framework structure with three- dimensional through holes with hole diameters gradually increasing from the middle to the periphery;

[0073] Figure 14 is a schematic diagram of a ceramic framework structure with divergent through holes with hole diameters gradually increasing from the inside to the periphery;

[0074] Figure 15 is a schematic diagram of a ceramic framework structure with connected holes with hole diameters first increasing and then decreasing;

[0075] Figure 16 is an SEM image of a ceramic framework prepared in Example 1. DETAILED DESCRIPTION

[0076] The present application provides a ceramic framework, which has a porous structure;

[0077] The porous structure comprises one or more of a connected hole structure and a through hole structure;

[0078] The connected hole structure is formed by a plurality of connected holes;

[0079] The through hole structure comprises one or more of a unidirectional through hole structure and a divergent through hole structure.

[0080] The ceramic framework provided by the present application has a porous structure; the porous structure comprises one or more of a connected hole structure and a through hole structure. In the present application, the connected hole structure is composed of interconnected pores, which are open pores or closed pores. In the present application, the through hole structure is composed of holes that pass through from one end to the other end.

[0081] In the present application, the holes in the through-hole structure are regular and / or irregular holes. In the present application, the hole diameter of the holes in the through-hole structure increases from one end to the other end, or the hole diameter of the holes increases first and then decreases from one end to the other end, or the hole diameter of the holes decreases first and then increases from one end to the other end. In the present application, the hole diameter of the holes in the through-hole structure is independently preferably 1000 μm or less, more preferably 0.1-1 μm, 1-50 μm, or 100-1000 μm.

[0082] In the present application, the through-hole structure includes one or more of a unidirectional through-hole structure and a divergent through-hole structure.

[0083] In the present application, the unidirectional through-hole structure is composed of a plurality of through-holes from one end to the other end. In specific embodiments of the present application, the hole diameter of each through-hole in the unidirectional through-hole structure independently increases from one end to the other end, or the hole diameter of each through-hole independently increases first and then decreases from one end to the other end, or the hole diameter of each through-hole independently decreases first and then increases from one end to the other end. In the present application, the hole diameter of each through-hole in the unidirectional through-hole structure is independently preferably 1000 μm or less, more preferably 0.1-1 μm, 1-50 μm, or 100-1000 μm.

[0084] In the present application, the divergent through-hole structure includes a plurality of through-holes diverging from a starting position inside the ceramic framework to the surrounding. In specific embodiments of the present application, the hole diameter of each through-hole in the divergent through-hole structure independently gradually increases from the starting position to the surrounding to form a horn shape, or the hole diameter of each through-hole independently gradually decreases from the starting position to the surrounding, or the hole diameter of each through-hole independently increases first and then decreases from the starting position to the surrounding, or the hole diameter of each through-hole independently decreases first and then increases from the starting position to the surrounding. In the present application, the hole diameter of each through-hole in the divergent through-hole structure is independently preferably 1000 μm or less, more preferably 0.1-1 μm, 1-50 μm, or 100-1000 μm.

[0085] In the present application, the divergent through-hole structure preferably comprises a three-dimensional through-hole structure; the three-dimensional through-hole structure is composed of a plurality of three-dimensional through-holes penetrating up, down, left, right, front and back. In specific embodiments of the present application, the aperture of each three-dimensional through-hole in the three-dimensional through-hole structure independently gradually increases from the middle to the periphery to form a horn shape, or the aperture of each three-dimensional through-hole independently gradually decreases from the middle to the periphery, or the aperture of each three-dimensional through-hole independently first increases and then decreases from the middle to the periphery, or the aperture of each three-dimensional through-hole independently first decreases and then increases from the middle to the periphery. In the present application, the aperture of each three-dimensional through-hole in the three-dimensional through-hole structure independently preferably ranges from 1000 μm or less, more preferably from 0.1 to 1 μm, from 1 to 50 μm, or from 100 to 1000 μm.

[0086] In specific embodiments of the present application, the structure of the ceramic framework comprises one or more of a ceramic framework with through-holes having an aperture that increases from one end to the other end as shown in FIG. 1, a ceramic framework with through-holes having an aperture that first decreases and then increases from one end to the other end as shown in FIG. 2, a ceramic framework with through-holes having an aperture that first increases and then decreases from one end to the other end as shown in FIG. 3, a ceramic framework with through-holes from one end to the other end as shown in FIG. 4, a ceramic framework with through-holes having multiple change trends (both end faces are small holes) as shown in FIG. 5, a ceramic framework with through-holes as shown in FIG. 6, a ceramic framework with three-dimensional interconnected holes as shown in FIG. 7, a ceramic framework with three-dimensional through-holes as shown in FIG. 8, a ceramic framework with through-holes having multiple change trends (both end faces are large holes) as shown in FIG. 9, a ceramic framework with interconnected holes that first decrease and then increase as shown in FIG. 10, a ceramic framework with interconnected holes that increase in one direction as shown in FIG. 11, a ceramic framework with interconnected holes having multiple change trends as shown in FIG. 12, a ceramic framework with three-dimensional through-holes having an aperture that gradually increases from the middle to the periphery as shown in FIG. 13, a ceramic framework with divergent through-holes having an aperture that gradually increases from the inside to the periphery as shown in FIG. 14, and a ceramic framework with interconnected holes having an aperture that first increases and then decreases as shown in FIG. 15.

[0087] The present application provides a preparation method of the ceramic framework described in the above technical solution, comprising the following steps:

[0088] Mixing the main raw material, the binder and the solvent to obtain a slurry; the main raw material comprises one or more of a bio-inert ceramic material and a bioactive ceramic material;

[0089] Performing flow casting on the slurry to obtain a flow-cast sheet;

[0090] Stacking the flow-cast sheet to obtain a stacked sheet;

[0091] Sintering the stacked sheet to obtain a ceramic framework.

[0092] The present application mixes the main raw material, the binder and the solvent to obtain a slurry. In the present application, the main raw material includes one or several of the bioinert ceramic material and the bioactive ceramic material. In the present application, the slurry preferably further includes one or several of the dispersant, the plasticizer and the pore-forming agent.

[0093] In the present application, the bioinert ceramic material preferably includes one or several of the zirconium oxide, the aluminum oxide, the quartz, the lithium disilicate, the glass powder, the magnesium aluminum spinel, the sodium aluminum silicate, the feldspar, the silicon carbide, the carbon nanostructure and the nitride; the carbon nanostructure preferably includes the carbon nanotube; the nitride preferably includes one or several of the titanium nitride, the zirconium nitride and the chromium nitride. In the present application, the bioactive ceramic material preferably includes one or several of the hydroxyapatite, the fluorapatite, the bioglass ceramic (Na-Ca-Si based glass), the A-W glass ceramic, the calcium phosphate, the calcium carbonate and the calcium sulfate; the bioglass ceramic preferably includes the Na-Ca-Si based glass. In the present application, the feldspar preferably includes one or several of the sodium feldspar, the potassium feldspar and the potassium sodium feldspar. In the present application, the D50 particle size of the main raw material is preferably 0.05-1500 μm. In the present application, the particle size of the raw material refers to the value of D50. In the present application, the binder preferably includes one or several of the polyvinyl alcohol (PVA) aqueous solution and the hydroxypropyl methyl cellulose; the concentration of the PVA aqueous solution is preferably 1-10%, more preferably 3-5%; the average molecular weight of the polyvinyl alcohol is preferably 155000-182000; the viscosity range of the hydroxypropyl methyl cellulose is preferably 3500-5600. In the present application, the dispersant preferably includes one or several of the triammonium citrate, the sodium polyacrylate and the glycerol; the molecular weight of the sodium polyacrylate is preferably 4000-10000. In the present application, the plasticizer preferably includes the polyethylene glycol (PEG); the molecular weight of the polyethylene glycol is preferably 380-420, more preferably 400. In the present application, the pore-forming agent preferably includes one or several of the polymethyl methacrylate (PMMA), the corn starch and the potato powder. In the present application, the molecular weight of the PMMA is preferably 90000-120000, more preferably 100000-120000. In the present application, the particle size of the pore-forming agent is preferably 0.5-1200 μm. In the present application, the solvent is preferably water or anhydrous ethanol.

[0094] In the present application, the mass ratio of the main raw material, the binder and the solvent is preferably (60-120):(6-20):(70-120), more preferably (60-105):(6-20):(72-120). In the present application, when the slurry comprises a dispersant, a plasticizer and a pore-forming agent, the mass ratio of the main raw material, the binder, the dispersant, the plasticizer, the pore-forming agent and water is preferably (60-120):(6-20):(0.1-12):(0.1-15):(2-50):(70-120), more preferably (60-105):(6-20):(0.1-10):(0.1-15):(2-45):(72-120).

[0095] In the present application, the mixing is preferably wet ball milling. In the present application, the rotation speed of the wet ball milling is preferably 10-1000 r / min, more preferably 10-900 r / min; the time of the wet ball milling is preferably 0.5-30 h, more preferably 1-24 h; the grinding ball used in the wet ball milling is preferably an alumina ball or a zirconia ball, more preferably a zirconia ball; the mass ratio of the ball to the material is preferably 1:(0.5-1.2), more preferably 1:(0.8-1.2). In the specific embodiments of the present application, the grinding ball used in the wet ball milling is a zirconia ball; the mass ratio of the ball to the material is 1:0.8.

[0096] In the specific embodiments of the present application, different casting slurries are obtained by adjusting the type, the added amount and the pore size of the pore-forming agent.

[0097] After obtaining the slurry, the present application performs casting molding on the casting slurry to obtain a casting sheet. In the present application, the casting molding is preferably performed in a casting machine. In the specific embodiments of the present application, different thicknesses of the casting sheet can be obtained by adjusting the doctor blade height.

[0098] After obtaining the casting sheet, the present application performs lamination on the casting sheet to obtain a laminated sheet. In the present application, the lamination is preferably performed in a warm isostatic pressing machine; the pressure of the lamination is preferably 8-260 MPa, more preferably 20-200 MPa, further preferably 90-150 MPa; the temperature of the lamination is preferably 30-60℃, more preferably 35-55℃, further preferably 40-50℃; the holding time under pressure is preferably 0.5-25 min, more preferably 1-15 min. In the present application, the lamination is adjusted according to the pore structure of the ceramic skeleton. In the specific embodiments of the present application, the casting sheets formed from the same casting slurry are laminated to obtain a casting sheet layer, and then the casting sheet layers formed from different casting slurries are laminated according to the pore structure of the ceramic skeleton; the thicknesses of the casting sheet layers are the same or different.

[0099] After the laminated sheet is obtained, the laminated sheet is sintered to obtain the ceramic framework. In the present application, the laminated sheet is preferably cut into a cuboid before sintering. In the present application, the sintering is preferably performed in a high-temperature furnace. In the present application, the procedure of the sintering preferably comprises: increasing the temperature from room temperature to 290℃ for 240 min, keeping the temperature at 290℃ for 60 min, increasing the temperature to 410℃ for 120 min, keeping the temperature at 410℃ for 1 h, increasing the temperature to 700-1650℃ for 180-300 min, and keeping the temperature at 700-1650℃ for 1-5 h. The present application does not have special requirements for the atmosphere of the sintering, and any sintering atmosphere known in the art can be used. In the specific embodiments of the present application, the atmosphere of the sintering is air. The present application is sufficiently degassed before the temperature reaches 500℃, and the final sintering is performed at 700-1650℃. In the sintering process of the present application, the pore-forming agent is decomposed to form pores, and by adjusting the type, addition amount and pore size of the pore-forming agent, ceramic frameworks with different porous structures can be obtained.

[0100] The present application also provides a preparation method of the ceramic framework described in the above technical solutions, comprising the following steps:

[0101] The main raw material and the solvent are mixed to obtain a ceramic slurry; the main raw material comprises one or more of a bio-inert ceramic material and a bioactive ceramic material;

[0102] The ceramic slurry is frozen to obtain a frozen block;

[0103] The frozen block is dried to obtain a dried sample block;

[0104] The dried sample block is sintered to obtain a ceramic framework.

[0105] The present application mixes the main raw material and the solvent to obtain a ceramic slurry. In the present application, the ceramic slurry preferably further comprises one or more of a binder, a dispersant, a plasticizer and a pore-forming agent. In the present application, the compositions of the main raw material, the solvent, the binder, the dispersant, the plasticizer and the pore-forming agent are consistent with the above description, which will not be repeated here; the preparation method of the ceramic slurry is consistent with the preparation method of the slurry described above, which will not be repeated here. In the specific embodiments of the present application, different ceramic slurries are obtained by adjusting the addition amount and pore size of the pore-forming agent.

[0106] After the ceramic slurry is obtained, the ceramic slurry is frozen to obtain a frozen block. In the present application, the freezing temperature is preferably -20 to -150℃, and more preferably -20 to -120℃. In the present application, the freezing mode of different ceramic slurries during the freezing process is adjusted according to the pore structure of the ceramic framework.

[0107] After obtaining the frozen block, the present application dries the frozen block to obtain a dried sample block. In the present application, the drying is preferably vacuum freeze-drying; the temperature of the drying is preferably -20-50°C, more preferably -20-35°C; the pressure of the drying is preferably 20-5000 Pa, more preferably 20-1000 Pa; the time of the drying is preferably 0.5-48 h, more preferably 1-36 h. In the process of the vacuum freeze-drying, the water evaporation forms pores, and by adjusting the moisture of the slurry and the number of pouring and the shape of the mold, frozen and dried sample blocks with different pore structures can be obtained.

[0108] After obtaining the dried sample block, the present application sintering the dried sample block to obtain a ceramic framework. In the present application, the sintering procedure preferably includes: from room temperature to 290°C for 240 min, holding at 290°C for 60 min, heating to 410°C for 120 min, holding at 410°C for 1 h, heating to 700-1650°C for 180-300 min, holding at 700-1650°C for 1-5 h. The present application does not have special requirements for the atmosphere of the sintering, and any sintering atmosphere known in the art can be used. In the specific embodiments of the present application, the sintering atmosphere is air. The present application performs sufficient degassing before the temperature reaches 500°C and performs final sintering at 700-1650°C. In the sintering process, the pore-forming agent decomposes to form pores, and by adjusting the type, addition amount and pore size of the pore-forming agent and the moisture of the slurry, ceramic frameworks with different porous structures can be obtained.

[0109] The present application also provides a preparation method of the ceramic framework described in the above technical solutions, comprising the following steps:

[0110] Mixing the main raw material with other raw materials to prepare a ceramic powder; the main raw material includes one or more of a bio-inert ceramic material and a bioactive ceramic material;

[0111] Dry pressing and / or isostatic pressing the ceramic powder to obtain a green body;

[0112] Sintering the green body to obtain a ceramic framework.

[0113] The present application mixes the main raw material with other raw materials to prepare a ceramic powder. In the present application, the other raw materials of the ceramic powder in addition to the main raw material preferably include one or more of a binder, a pore-forming agent and a solvent. In the present application, the composition of the main raw material, the binder, the pore-forming agent and the solvent is consistent with the foregoing description, which is not repeated here.

[0114] In the present application, the binder is preferably a PVA aqueous solution with a concentration of 3wt%; the mass of the binder is preferably 5-30% of the mass of the main raw material, more preferably 5-29%; the solvent is preferably water or anhydrous ethanol; the mass ratio of the solvent to the main raw material is preferably 1-3:1. In the present application, the mixing preferably comprises wet ball milling. In the present application, when the raw material for preparing the ceramic powder comprises a solvent, the mixing is preferably followed by drying the obtained wet mixture to obtain the ceramic powder. In the present application, the rotation speed of the wet ball mill is preferably 10-1000r / min, more preferably 10-900r / min; the time of the wet ball milling is preferably 0.5-30h, more preferably 1-24h; the grinding balls used in the wet ball milling are preferably alumina balls or zirconia balls, more preferably zirconia balls; the mass ratio of the balls to the material is preferably 1:(0.5-1.2), more preferably 1:(0.8-1.2). In a specific embodiment of the present application, the grinding balls used in the wet ball milling are zirconia balls; the mass ratio of the balls to the material is 1:0.8. In the present application, the temperature of the drying is preferably 45-110°C, more preferably 47-105°C.

[0115] After obtaining the ceramic powder, the ceramic powder is subjected to dry pressing and / or isostatic pressing to obtain a green body. In the present application, the pressure of the dry pressing is preferably 2-30MPa, more preferably 2-28MPa; the time of the dry pressing is preferably 10-180s, more preferably 20-150s. In the present application, the pressure of the isostatic pressing is preferably 50-300MPa; the isostatic pressing is preferably cold isostatic pressing or hot isostatic pressing; the temperature of the isostatic pressing is preferably room temperature; the time of the isostatic pressing is preferably 30-1800s, more preferably 30-1200s. In the present application, when the ceramic powder is subjected to dry pressing and isostatic pressing, the dry pressing and the isostatic pressing are preferably performed sequentially.

[0116] After obtaining the green body, the green body is subjected to sintering to obtain a ceramic framework. In the present application, the sintering process is consistent with the foregoing description, which is not repeated here.

[0117] The present application also provides a method for preparing the ceramic framework described in the above technical solution, comprising the following steps:

[0118] mixing the main raw material and other raw materials to obtain a mixture; the main raw material comprises one or more of a bio-inert ceramic material and a bioactive ceramic material;

[0119] kneading the mixture, the binder and the solvent to obtain a kneaded material;

[0120] aging the kneaded material and then pugging the kneaded material to obtain a pugged block;

[0121] The mud segment is subjected to extrusion forming to obtain a wet blank.

[0122] The wet blank is subjected to drying to obtain a dry blank.

[0123] The dry blank is subjected to sintering to obtain a ceramic framework.

[0124] The dry blank is subjected to sintering to obtain a ceramic framework.

[0125] The main raw material and other raw materials are mixed to obtain a mixture. In the present application, the composition of the main raw material is consistent with the foregoing description, which will not be repeated here. In the present application, the mixing is preferably carried out in a mixer. In the present application, the other raw materials preferably include a pore-forming agent and a solid binder. In the present application, the composition of the pore-forming agent is consistent with the foregoing description, which will not be repeated here. In the present application, the mass ratio of the pore-forming agent to the main raw material is preferably 1-50:100-120, more preferably 1:10. In the present application, the solid binder preferably includes hydroxypropyl methyl cellulose; the mass of the solid binder is preferably 1-6% of the mass of the main raw material, more preferably 3.3-5%.

[0126] After obtaining the mixture, the mixture, a liquid binder and a solvent are kneaded to obtain a kneaded material. In the present application, a dispersing agent is preferably added during the kneading process. In the present application, the composition of the solvent and the dispersing agent is consistent with the foregoing description, which will not be repeated here. In the present application, the liquid binder is preferably a PVA aqueous solution; the concentration of the PVA aqueous solution is preferably 3wt%; the mass of the PVA aqueous solution is preferably 1-6% of the mass of the main raw material, more preferably 1-5.5%. The present application uses a liquid binder and a solid binder, which has a better effect. In the present application, the dispersing agent is preferably glycerol; the mass of the glycerol is preferably 0.3-3% of the mass of the main raw material, more preferably 0.3-2.9%. In the present application, the mass ratio of the solvent to the main raw material is preferably 20-30:100-120, more preferably 26.5:100. In the present application, the kneading is preferably carried out in a kneader. In the present application, the number of revolutions of the kneading is preferably 12-30 revolutions per minute.

[0127] After obtaining the kneaded material, the kneaded material is aged and then subjected to mud refining to obtain a mud block. In the present application, the temperature of the aging is preferably 10-30°C, more preferably 10-28°C; the time of the aging is preferably 12-48h, more preferably 12-36h. In the present application, the mud refining is preferably carried out in a mud refiner. In the present application, the extrusion speed of the mud refiner is preferably 30-80cm / min.

[0128] After obtaining the kneaded clay block, the kneaded clay block is subjected to a clay segmenting step to obtain a clay segment. In the present application, the clay segmenting step is preferably performed in a clay segmenting machine. In the present application, the extrusion speed of the clay segmenting machine is preferably 20-60 cm / min.

[0129] After obtaining the clay segment, the clay segment is subjected to an extrusion molding step to obtain a wet green body. In the present application, the extrusion molding step is preferably performed in an extrusion molding machine. In the present application, the extrusion speed of the extrusion molding machine is preferably 30-100 cm / min.

[0130] After obtaining the wet green body, the wet green body is subjected to a drying step to obtain a dry green body. In the present application, the drying step is preferably microwave drying. In the present application, the microwave power of the microwave drying is preferably 1-5 kW, and the time of the microwave drying is preferably 50-120 s.

[0131] After obtaining the dry green body, the dry green body is subjected to a sintering step to obtain a ceramic framework. In the present application, the sintering process is consistent with the foregoing description, and will not be repeated here.

[0132] In specific embodiments of the present application, the method for preparing the ceramic framework further comprises a gel casting method, an organic template method, a foaming method, a particle packing method, or an additive manufacturing method.

[0133] The present application provides an application of the ceramic framework described in the above technical solution or the ceramic framework prepared by the preparation method described in the above technical solution in the preparation of a biomedical material. In the present application, the biomedical material preferably includes a denture, an artificial eye, or a bionic bone.

[0134] The present application provides a resin-ceramic composite material, comprising a ceramic framework and a resin filled in the porous structure of the ceramic framework; the ceramic framework is the ceramic framework described in the above technical solution or the ceramic framework prepared by the preparation method described in the above technical solution.

[0135] In the present application, the raw materials for preparing the resin preferably include one or more of monofunctional acrylate and multifunctional acrylate. In the present application, the multifunctional acrylate preferably includes one or more of difunctional acrylate and trifunctional acrylate. In the present application, the monofunctional acrylate preferably includes hydroxyethyl methacrylate, hydroxypropyl methacrylate, and methyl methacrylate; the difunctional acrylate preferably includes bisphenol A-glycidyl dimethacrylate, urethane dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethoxy bisphenol A-dimethacrylate, tetraethoxy bisphenol A-dimethacrylate, and decaethoxy bisphenol A-dimethacrylate; and the trifunctional acrylate preferably includes pentaerythritol triacrylate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate.

[0136] In specific embodiments of the present application, the raw materials for preparing the resin preferably include one or more of bisphenol A-glycidyl dimethacrylate (Bis-GMA, molecular weight 512.59), urethane dimethacrylate (UDMA, molecular weight 470.56), and triethylene glycol dimethacrylate (TEGDMA, molecular weight 286.321), and more preferably Bis-GMA, UDMA, and TEGDMA. In the present application, the mass ratio of Bis-GMA, UDMA, and TEGDMA is preferably (2-3.5):(3-5):(2-3.5), and more preferably (2.5-3.5):(3-5):(2.5-3.5). In the present application, the raw materials for preparing the resin preferably further include an initiator; the initiator preferably includes benzoyl peroxide (BPO); and the mass fraction of the initiator in the raw materials for preparing the resin is preferably 0.1-1.0%, and more preferably 0.55-1.0%. In the present application, the raw materials for preparing the resin preferably further include a PVA aqueous solution; the concentration of the PVA aqueous solution is preferably 3-15 wt%, and more preferably 5-15 wt%; and the molecular weight of PVA in the PVA aqueous solution is preferably 155000-182000, and more preferably 155000-180000. In the present application, the volume content of the PVA aqueous solution in the raw materials for preparing the resin is preferably 60-95%, and more preferably 65-91%.

[0137] The present application provides a preparation method of the resin-ceramic composite material described in the above technical solutions, which comprises the following steps:

[0138] The ceramic framework is immersed in a resin precursor solution, and cured to obtain a resin-ceramic composite material.

[0139] In the present application, the raw materials for preparing the resin precursor solution preferably include one or more of Bis-GMA, UDMA and TEGDMA, more preferably Bis-GMA, UDMA and TEGDMA. In the present application, the mass ratio of Bis-GMA, UDMA and TEGDMA is preferably (2-3.5):(3-5):(2-3.5), more preferably (2.5-3.5):(3-5):(2.5-3.5). In the present application, the raw materials for preparing the resin precursor solution preferably further include an initiator; the initiator preferably includes BPO; the mass fraction of the initiator in the raw materials for preparing the resin is preferably 0.1-1.0%, more preferably 0.55-1.0%. In the present application, the raw materials for preparing the resin precursor solution preferably further include a PVA aqueous solution; the concentration of the PVA aqueous solution is preferably 3-15 wt%, more preferably 5-15 wt%; the molecular weight of PVA in the PVA aqueous solution is preferably 155000-182000, more preferably 155000-180000. In the present application, the volume content of the PVA aqueous solution in the resin precursor solution is preferably 60-95%, more preferably 65-91%.

[0140] In the present application, the method for preparing the PVA aqueous solution preferably includes mixing PVA and water to obtain a PVA aqueous solution. In the present application, the temperature of the mixing is preferably 85-95°C, more preferably 90°C; the time of the mixing is preferably 3-12 h, more preferably 4-10 h.

[0141] In the present application, the ceramic framework preferably further includes a modification before being impregnated; the modification liquid used in the modification is a silane modification liquid; the silane modification liquid includes anhydrous ethanol, distilled water, acetic acid and γ-methacryloxypropyltrimethoxysilane (KH570); the mass ratio of the anhydrous ethanol, distilled water, acetic acid and KH570 is preferably (0.8-1.2):(0.7-1.2):(0.001-0.015):(0.002-0.01). In the present application, the impregnation is preferably vacuum infiltration. In the present application, the volume ratio of the ceramic framework and the resin precursor solution is preferably (6-8):(2-4), more preferably (6.5-7.5):(2.5-3.5). In the present application, the temperature of the impregnation is preferably 10-37°C, more preferably 20-30°C; the time of the impregnation is preferably 24-240 h, more preferably 36-200 h; the pressure of the impregnation is preferably 1-10000 Pa, more preferably 100-5000 Pa.

[0142] In the present application, the solidification is preferably performed in a warm isostatic press; the pressure of the solidification is preferably 0.1-500 MPa, more preferably 50-300 MPa; the temperature of the solidification is preferably 10-180℃, more preferably 60-120℃, further preferably 80-100℃; and the holding time of the solidification is preferably 1 min-48 h, more preferably 6-36 h.

[0143] In the present application, when the raw material of the resin precursor solution comprises a PVA aqueous solution, the solidification preferably comprises gelation, drying, atmospheric pressure solidification and water absorption treatment performed in sequence. In the present application, the gelation preferably comprises freezing and thawing performed in sequence; the temperature of the freezing is preferably -20℃ to -150℃, more preferably -20℃ to -120℃; the time of the freezing is preferably 0.5-48 h, more preferably 1-12 h; and the thawing is preferably performed at room temperature. In the present application, the freezing and thawing are preferably performed 2-3 times. The present application crosslinks the PVA through the gelation to obtain a PVA hydrogel with certain strength, high elasticity and lubricity. In the present application, the drying is preferably vacuum freeze-drying; the pressure of the drying is preferably 20-5000 Pa, more preferably 20-1000 Pa; the temperature of the drying is preferably -20-50℃, more preferably -20-35℃; and the time of the drying is preferably 0.5-48 h, more preferably 1-36 h. In the present application, the temperature of the atmospheric pressure solidification is preferably 30-80℃, more preferably 50-60℃; and the time of the atmospheric pressure solidification is preferably 2-72 h, more preferably 6-24 h. In the present application, the water absorption treatment is preferably soaking in deionized water. In the present application, the temperature of the water absorption treatment is preferably room temperature; and the time of the water absorption treatment is preferably 0.5-48 h, more preferably 2-36 h. The present application makes the PVA absorb water through the water absorption treatment, which can be released when under pressure, and can be absorbed again to keep the original state when the pressure decreases, thereby increasing the elasticity and lubricity of the PVA hydrogel.

[0144] In the present application, the hydrogel has a good porous structure similar to the structure of the cartilage tissue in the human body, and has good compression performance, water absorption performance, good biocompatibility and weak antigenicity, can be well combined with the original cartilage tissue in the human or animal body, and improves the cell adhesion of the PVA hydrogel. The addition of PVA can improve the biocompatibility of the resin ceramic composite material, and at the same time improve the toughness, so that a composite material with balanced hardness and toughness is obtained.

[0145] The application provides application of the resin ceramic composite material in preparation of biomedical materials. In the application, the biomedical materials preferably include dentures, artificial eyes or bionic bones. In the application, the application method preferably comprises processing the resin ceramic composite material to obtain the biomedical materials. In the application, the processing method preferably comprises turning.

[0146] The technical solutions in the application will be described clearly and completely in combination with the embodiments in the application. Apparently, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all the other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application.

[0147] In the embodiments of the application, the PMMA has a molecular weight of 100000-120000.

[0148] Example 1: Preparation of a ceramic framework

[0149] 1 μm sodium feldspar is used as a main raw material, a PVA aqueous solution (the average molecular weight of the PVA is 155000) with a mass concentration of 5% is used as a binder, PEG (the molecular weight of the PEG is 400) is used as a plasticizer, ammonium citrate is used as a dispersant, PMMA is used as a pore-forming agent, and deionized water is used as a medium, wherein the mass ratio of the sodium feldspar, the PVA aqueous solution, the PEG, the ammonium citrate and the deionized water is 100:12:0.4:0.7:86.9; three different casting slurries are prepared according to different contents and different particle sizes of the PMMA, wherein the mass ratio of the sodium feldspar to the PMMA in the first casting slurry is 90:5, and the particle size of the PMMA in the first casting slurry is 2 μm; the mass ratio of the sodium feldspar to the PMMA in the second casting slurry is 90:7, and the particle size of the PMMA in the second casting slurry is 3 μm; the mass ratio of the sodium feldspar to the PMMA in the third casting slurry is 90:9, and the particle size of the PMMA in the third casting slurry is 4 μm;

[0150] According to the above raw material ratio, the sodium feldspar, the PMMA, the deionized water and the ammonium citrate are ball milled (the rotation speed of the ball milling is 20 r / min) for 12 h, and then the PVA aqueous solution and the PEG are added and secondarily ball milled (the rotation speed of the ball milling is 20 r / min) for 8 h; the ball-milled slurry is stirred under vacuum for 1 h, and after the air bubbles in the slurry are removed, the first casting slurry, the second casting slurry and the third casting slurry are obtained respectively; the casting slurry without the PMMA is prepared by using the same method.

[0151] The above each casting slurry was respectively casted, the doctor blade height was adjusted to 0.3 mm, the casting speed was 0.5 m / min, and a casting sheet with a thickness of 0.12 mm was obtained;

[0152] Each casting sheet was cut into a square sheet with a size of 210 mm x 210 mm by an automatic cutting machine, and then was stacked by an automatic stacking machine. The stacking was from top to bottom in turn as follows: a casting sheet layer without PMMA with a thickness of 6 mm, a casting sheet layer formed by the first casting slurry with a thickness of 6 mm, a casting sheet layer formed by the second casting slurry with a thickness of 6 mm, and a casting sheet layer formed by the third casting slurry with a thickness of 6 mm, wherein the casting sheet layer without PMMA was obtained by stacking a plurality of casting sheets without PMMA, the casting sheet layer formed by the first casting slurry was obtained by stacking a plurality of casting sheets formed by the first casting slurry, the casting sheet layer formed by the second casting slurry was obtained by stacking a plurality of casting sheets formed by the second casting slurry, and the casting sheet layer formed by the third casting slurry was obtained by stacking a plurality of casting sheets formed by the third casting slurry. The sample after stacking was preliminarily pressed into a sample block with a thickness of 20 mm, and then was hot-pressed under the condition of warm isostatic pressing 90 MPa and temperature 40℃, the pressure maintaining time was 5 min, and the periphery was cut off by a cutting machine to obtain a stacked sheet with a size of 200 mm x 200 mm;

[0153] The stacked sheet was cut into small blocks with a size of 16 mm x 16 mm x 20 mm, and was put into a high-temperature furnace, and was heated from room temperature to 290℃ for 240 min, was kept at 290℃ for 60 min, was heated to 410℃ for 120 min, was kept at 410℃ for 1 h, was heated to 1000℃ for 240 min, and was kept at 1000℃ for 5.0 h, to obtain a ceramic framework with a connected pore structure as shown in FIG. 11, and the pore diameter gradually increased from top to bottom.

[0154] Example 2 Preparation of ceramic framework

[0155] The main raw material is 0.1 μm sodium aluminosilicate, the binder is 5% PVA aqueous solution (the average molecular weight of PVA is 155000), the plasticizer is PEG (the molecular weight of PEG is 400), the dispersant is triammonium citrate, and the medium is deionized water, wherein the mass ratio of sodium aluminosilicate, PVA aqueous solution, PEG, triammonium citrate and deionized water is 100:8:0.3:0.6:91.1; three different casting slurries are prepared according to different contents and different particle sizes of PMMA, wherein the mass ratio of sodium aluminosilicate to PMMA in the first casting slurry is 90:10, and the particle size of PMMA in the first casting slurry is 30 μm; the mass ratio of sodium aluminosilicate to PMMA in the second casting slurry is 90:12, and the particle size of PMMA in the second casting slurry is 40 μm; the mass ratio of sodium aluminosilicate to PMMA in the third casting slurry is 90:14, and the particle size of PMMA in the third casting slurry is 50 μm;

[0156] According to the above raw material ratio, the sodium aluminosilicate, PMMA, deionized water and triammonium citrate are ball milled (the rotation speed of ball milling is 30 r / min) for 12 h, and then the PVA aqueous solution and PEG are added for secondary ball milling (the rotation speed of ball milling is 30 r / min) for 8 h; the well-milled slurry is vacuum-stirred for 1 h to remove the air bubbles inside, and then the first casting slurry, the second casting slurry and the third casting slurry are obtained respectively;

[0157] The above casting slurries are respectively subjected to casting forming, the doctor blade height is adjusted to 0.35 mm, and the casting speed is 0.3 m / min, so that the casting sheets with a thickness of 0.15 mm are obtained;

[0158] The casting sheets are cut into square sheets with a size of 210 mm×210 mm by an automatic cutting machine, and then are stacked by an automatic stacking machine, wherein the first casting slurry layer with a thickness of 8.1 mm, the third casting slurry layer with a thickness of 8.1 mm and the second casting slurry layer with a thickness of 8.1 mm are stacked from top to bottom; the first casting slurry layer is obtained by stacking a plurality of first casting sheets, the third casting slurry layer is obtained by stacking a plurality of third casting sheets, and the second casting slurry layer is obtained by stacking a plurality of second casting sheets; the stacked sample is preliminarily pressed into a sample block with a thickness of 20 mm, and then is hot-pressed under the condition of 90 MPa and 40℃, the pressure holding time is 5 min, and the surrounding part is cut off by a cutting machine to obtain a stacked sheet with a size of 200 mm×200 mm;

[0159] The laminated sheet is cut into small pieces of 16 mm x 16 mm x 20 mm, and is put into a high-temperature furnace, and is heated from room temperature to 290°C for 240 min, is kept at 290°C for 60 min, is heated to 410°C for 120 min, is kept at 410°C for 1 h, is heated to 820°C for 200 min, and is kept at 820°C for 2.0 h, to obtain a ceramic skeleton with a connected pore structure as shown in Fig. 15, in which the pore size first increases and then decreases.

[0160] Example 3 Preparation of a ceramic skeleton

[0161] 4 μm sodium feldspar is used as a main raw material, a PVA aqueous solution (the average molecular weight of PVA is 155000) with a mass concentration of 5% is used as a binder, PEG (the molecular weight of PEG is 400) is used as a plasticizer, triammonium citrate is used as a dispersant, PMMA is used as a pore-forming agent, and deionized water is used as a medium, wherein the mass ratio of sodium feldspar, the PVA aqueous solution, PEG, triammonium citrate and deionized water is 100:9:0.35:0.65:90; three different casting slurries are prepared according to different contents and different particle sizes of PMMA, wherein the mass ratio of sodium feldspar to PMMA in the first casting slurry is 90:15, and the particle size of PMMA in the first casting slurry is 5 μm; the mass ratio of sodium feldspar to PMMA in the second casting slurry is 90:18, and the particle size of PMMA in the second casting slurry is 25 μm; the mass ratio of sodium feldspar to PMMA in the third casting slurry is 90:21, and the particle size of PMMA in the third casting slurry is 50 μm;

[0162] According to the above raw material ratio, sodium feldspar, PMMA, deionized water and triammonium citrate are ball milled (the rotation speed of ball milling is 20 r / min) for 12 h, and then the PVA aqueous solution and PEG are added and secondarily ball milled (the rotation speed of ball milling is 20 r / min) for 8 h; the well ball milled slurry is stirred under vacuum for 1 h to remove the bubbles inside, and the first casting slurry, the second casting slurry and the third casting slurry are obtained respectively;

[0163] The above casting slurries are respectively subjected to casting forming, and the doctor blade height is adjusted to 0.35 mm, and the casting speed is 0.3 m / min, to obtain casting sheets with a thickness of 0.15 mm;

[0164] The cast sheets were cut into 210 mm x 210 mm square sheets by an automatic cutting machine, and then were stacked by an automatic stacking machine, and the stacking was from top to bottom in order of the cast sheet layer formed by the second cast slurry with a thickness of 6 mm, the cast sheet layer formed by the first cast slurry with a thickness of 8 mm, and the cast sheet layer formed by the third cast slurry with a thickness of 10 mm, wherein the cast sheet layer formed by the second cast slurry was obtained by stacking a plurality of cast sheets formed by the second cast slurry, the cast sheet layer formed by the first cast slurry was obtained by stacking a plurality of cast sheets formed by the first cast slurry, and the cast sheet layer formed by the third cast slurry was obtained by stacking a plurality of cast sheets formed by the third cast slurry; the stacked sample was preliminarily pressed into a sample block with a thickness of 20 mm, and then was hot-pressed under the conditions of warm isostatic pressing 90 MPa and temperature 40℃, the pressure maintaining time was 5 min, and the sample block was cut by a cutting machine to obtain a 200 mm x 200 mm stacked sheet;

[0165] The stacked sheet was cut into 16 mm x 16 mm x 20 mm small blocks, and was put into a high-temperature furnace, and was heated from room temperature to 290℃ at a rate of 240 min, was kept at 290℃ for 60 min, was heated to 410℃ at a rate of 120 min, was kept at 410℃ for 1 h, was heated to 1120℃ at a rate of 270 min, and was kept at 1120℃ for 1.5 h, to obtain a ceramic skeleton with a connected pore structure in which the pore size first decreases and then increases, as shown in FIG. 10.

[0166] Example 4 Preparation of a ceramic skeleton

[0167] The 1.5 μm sodium feldspar is used as a main raw material, the 5% PVA aqueous solution (the average molecular weight of PVA is 155000) is used as a binder, the PEG (the molecular weight of PEG is 400) is used as a plasticizer, the triammonium citrate is used as a dispersant, and the deionized water is used as a medium, wherein the mass ratio of the sodium feldspar, the PVA aqueous solution, the PEG, the triammonium citrate and the deionized water is 100:12:0.4:0.7:86.9; four different kinds of casting slurries are prepared according to different types, different contents and different particle sizes of the pore-forming agent, wherein the mass ratio of the sodium feldspar and the pore-forming agent in the casting slurry a is 90:20, the pore-forming agent is a mixture of PMMA and corn starch (the mass ratio of PMMA to corn starch is 1:1), the PMMA is obtained by mixing the PMMA with a particle size of 0.5 μm, the PMMA with a particle size of 1 μm and the PMMA with a particle size of 10 μm according to a mass ratio of 1:1:1; the mass ratio of the sodium feldspar and the pore-forming agent in the casting slurry b is 90:20, the pore-forming agent is PMMA, the PMMA is obtained by mixing the PMMA with a particle size of 5 μm, the PMMA with a particle size of 10 μm and the PMMA with a particle size of 25 μm according to a mass ratio of 1:1:1; the mass ratio of the sodium feldspar and the pore-forming agent in the casting slurry c is 90:10, the pore-forming agent is PMMA, the PMMA is obtained by mixing the PMMA with a particle size of 10 μm, the PMMA with a particle size of 20 μm and the PMMA with a particle size of 45 μm according to a mass ratio of 1:1:2; the mass ratio of the sodium feldspar and the pore-forming agent in the casting slurry d is 90:5, the pore-forming agent is PMMA, the PMMA is obtained by mixing the PMMA with a particle size of 20 μm, the PMMA with a particle size of 25 μm and the PMMA with a particle size of 50 μm according to a mass ratio of 1:1:3;

[0168] According to the above raw material ratio, the sodium feldspar, the pore-forming agent, the deionized water and the triammonium citrate are ball milled (the rotation speed of ball milling is 20 r / min) for 12 h, and then the PVA aqueous solution and the PEG are added and secondarily ball milled (the rotation speed of ball milling is 20 r / min) for 12 h; the well ball milled slurry is stirred under vacuum for 1 h, and then the casting slurry a, the casting slurry b, the casting slurry c and the casting slurry d are obtained respectively after removing the bubbles inside;

[0169] The above casting slurries are respectively subjected to casting forming, the doctor blade height is adjusted to 0.35 mm, and the casting speed is 0.3 m / min, so as to obtain the casting sheet with a thickness of 0.15 mm;

[0170] The cast sheets were cut into 210 mm x 210 mm square sheets by an automatic cutting machine, and then were stacked by an automatic stacking machine, and the stacking was performed in the order of a cast sheet layer formed of the cast slurry a having a thickness of 3 mm, a cast sheet layer formed of the cast slurry b having a thickness of 6 mm, a cast sheet layer formed of the cast slurry c having a thickness of 7 mm, and a cast sheet layer formed of the cast slurry d having a thickness of 8 mm from top to bottom, wherein the cast sheet layer formed of the cast slurry a was obtained by stacking a plurality of cast sheets formed of the cast slurry a, the cast sheet layer formed of the cast slurry b was obtained by stacking a plurality of cast sheets formed of the cast slurry b, the cast sheet layer formed of the cast slurry c was obtained by stacking a plurality of cast sheets formed of the cast slurry c, and the cast sheet layer formed of the cast slurry d was obtained by stacking a plurality of cast sheets formed of the cast slurry d. The stacked sample was preliminarily pressed to a thickness of 20 mm, and then was hot-pressed at 90 MPa and 40°C for 5 min by warm isostatic pressing, and was cut by a cutting machine to obtain a 200 mm x 200 mm stacked sheet.

[0171] The stacked sheet was cut into 16 mm x 16 mm x 20 mm pieces, and was put into a high-temperature furnace, and was heated from room temperature to 290°C over 240 min, was maintained at 290°C for 60 min, was heated to 410°C over 120 min, was maintained at 410°C for 1 h, was heated to 1030°C over 255 min, and was maintained at 1030°C for 2.0 h to obtain a ceramic skeleton having a through-hole structure in which the pore diameter gradually increases from one end to the other end as shown in FIG. 1.

[0172] Example 5 Preparation of a Ceramic Skeleton

[0173] The 1.5 μm sodium feldspar is used as a main raw material, 5% PVA aqueous solution (the average molecular weight of PVA is 155000) is used as a binder, PEG (the molecular weight of PEG is 400) is used as a plasticizer, triammonium citrate is used as a dispersant, PMMA is used as a pore forming agent, and deionized water is used as a medium, wherein the mass ratio of sodium feldspar, PVA aqueous solution, PEG, triammonium citrate and deionized water is 100:12:0.4:0.7:86.9; three different casting slurries are prepared according to different contents and different particle sizes of PMMA, wherein the mass ratio of sodium feldspar and PMMA in the casting slurry a is 90:15, the PMMA is obtained by mixing PMMA with a particle size of 0.5 μm, PMMA with a particle size of 1 μm and PMMA with a particle size of 10 μm according to a mass ratio of 1:1:1; the mass ratio of sodium feldspar and PMMA in the casting slurry b is 90:21, the PMMA is obtained by mixing PMMA with a particle size of 5 μm, PMMA with a particle size of 10 μm and PMMA with a particle size of 25 μm according to a mass ratio of 1:1:1; the mass ratio of sodium feldspar and PMMA in the casting slurry c is 90:18, the PMMA is obtained by mixing PMMA with a particle size of 10 μm, PMMA with a particle size of 20 μm and PMMA with a particle size of 45 μm according to a mass ratio of 1:1:2;

[0174] According to the above raw material ratio, the sodium feldspar, PMMA, deionized water and triammonium citrate are ball milled (the rotation speed of ball milling is 20 r / min) for 12 h, and then the PVA aqueous solution and PEG are added for secondary ball milling (the rotation speed of ball milling is 20 r / min) for 8 h; the well ball milled slurry is stirred under vacuum for 1 h to remove the air bubbles in it, and then the casting slurry a, the casting slurry b and the casting slurry c are obtained respectively;

[0175] The above casting slurries are respectively subjected to casting forming, the doctor blade height is adjusted to 0.35 mm, and the casting speed is 0.3 m / min, so that the casting sheets with a thickness of 0.15 mm are obtained;

[0176] The casting sheets are cut into square sheets with a size of 210 mm×210 mm by an automatic cutting machine, and then are stacked by an automatic stacking machine, wherein the casting sheet layers formed by the casting slurry a with a thickness of 8 mm, the casting sheet layers formed by the casting slurry c with a thickness of 8 mm and the casting sheet layers formed by the casting slurry b with a thickness of 8 mm are sequentially stacked from top to bottom, wherein the casting sheet layer formed by the casting slurry a is obtained by stacking a plurality of casting sheets formed by the casting slurry a, the casting sheet layer formed by the casting slurry c is obtained by stacking a plurality of casting sheets formed by the casting slurry c, and the casting sheet layer formed by the casting slurry b is obtained by stacking a plurality of casting sheets formed by the casting slurry b; the sample after stacking is preliminarily pressed into a sample block with a thickness of 20 mm, and then is subjected to hot pressing under the conditions of warm isostatic pressing 90 MPa and temperature 40℃, the pressure maintaining time is 5 min, and the sample block is cut by a cutting machine to obtain a stacked sheet with a size of 200 mm×200 mm;

[0177] The laminated sheet was cut into small pieces of 16 mm x 16 mm x 20 mm, and was put into a high-temperature furnace, and was heated from room temperature to 290°C for 240 min, was kept at 290°C for 60 min, was heated to 410°C for 120 min, was kept at 410°C for 1 h, was heated to 1050°C for 260 min, and was kept at 1050°C for 2.5 h, to obtain a ceramic skeleton having a through-hole structure as shown in Fig. 3, in which the pore size increases first and then decreases from one end to the other end.

[0178] Example 6 Preparation of a ceramic skeleton

[0179] Example 6 Preparation of a ceramic skeleton 1.8 μm sodium feldspar was used as the main raw material, a PVA aqueous solution (the average molecular weight of PVA was 155000) with a mass concentration of 5% was used as the binder, PEG (the molecular weight of PEG was 400) was used as the plasticizer, ammonium citrate was used as the dispersant, and deionized water was used as the medium, wherein the mass ratio of sodium feldspar, PVA aqueous solution, PEG, ammonium citrate and deionized water was 100:12:0.4:0.7:86.9; four different kinds of casting slurries were prepared according to the different types, different contents and different particle sizes of the pore-forming agent, wherein the mass ratio of sodium feldspar and pore-forming agent in the casting slurry a was 90:15, the pore-forming agent was a mixture of PMMA and corn starch (the mass ratio of PMMA to corn starch was 1:1), and the PMMA was obtained by mixing PMMA with a particle size of 0.5 μm, PMMA with a particle size of 1 μm and PMMA with a particle size of 10 μm according to a mass ratio of 1:1:1; the mass ratio of sodium feldspar and pore-forming agent in the casting slurry b was 90:15, the pore-forming agent was PMMA, and the PMMA was obtained by mixing PMMA with a particle size of 5 μm, PMMA with a particle size of 10 μm and PMMA with a particle size of 25 μm according to a mass ratio of 1:1:1; the mass ratio of sodium feldspar and pore-forming agent in the casting slurry c was 90:15, the pore-forming agent was PMMA, and the PMMA was obtained by mixing PMMA with a particle size of 10 μm, PMMA with a particle size of 20 μm and PMMA with a particle size of 45 μm according to a mass ratio of 1:1:2; the mass ratio of sodium feldspar and pore-forming agent in the casting slurry d was 90:15, the pore-forming agent was PMMA, and the PMMA was obtained by mixing PMMA with a particle size of 10 μm, PMMA with a particle size of 20 μm and PMMA with a particle size of 45 μm according to a mass ratio of 1:1:3; the mass ratio of sodium feldspar and pore-forming agent in the casting slurry e was 90:15, the pore-forming agent was PMMA, and the PMMA was obtained by mixing PMMA with a particle size of 10 μm, PMMA with a particle size of 25 μm and PMMA with a particle size of 50 μm according to a mass ratio of 1:1:2.

[0180] According to the above raw material ratio, the sodium feldspar, the pore-forming agent, the deionized water and the triammonium citrate were ball milled (the rotation speed of ball milling was 20 r / min) for 12 h, and then the PVA aqueous solution and the PEG were added for secondary ball milling (the rotation speed of ball milling was 20 r / min) for 8 h; the ball-milled slurry was stirred under vacuum for 1 h, and then the air bubbles were removed to obtain the casting slurry a, the casting slurry b, the casting slurry c, the casting slurry d and the casting slurry e, respectively;

[0181] Each of the casting slurries was subjected to casting forming, the height of the doctor blade was adjusted to 0.35 mm, and the casting speed was 0.3 m / min to obtain a casting sheet with a thickness of 0.15 mm;

[0182] Each of the casting sheets was cut into a square sheet with a size of 210 mm x 210 mm by an automatic cutting machine, and then was stacked by an automatic stacking machine, wherein the middle layer was a layer of the casting sheet formed by the casting slurry a, the upper and lower layers adjacent to the middle layer were layers of the casting sheet formed by the casting slurry b, the outer side of the layers of the casting sheet formed by the casting slurry b was a layer of the casting sheet formed by the casting slurry c, and then outward in turn were a layer of the casting sheet formed by the casting slurry d and a layer of the casting sheet formed by the casting slurry e, and the total number of layers was 9, the thickness of the middle layer was 4 mm, and the thickness of each of the remaining layers was 2.5 mm, wherein the layer of the casting sheet formed by the casting slurry a was obtained by stacking a plurality of the casting sheets formed by the casting slurry a, the layer of the casting sheet formed by the casting slurry b was obtained by stacking a plurality of the casting sheets formed by the casting slurry b, the layer of the casting sheet formed by the casting slurry c was obtained by stacking a plurality of the casting sheets formed by the casting slurry c, the layer of the casting sheet formed by the casting slurry d was obtained by stacking a plurality of the casting sheets formed by the casting slurry d, and the layer of the casting sheet formed by the casting slurry e was obtained by stacking a plurality of the casting sheets formed by the casting slurry e; the sample after stacking was preliminarily pressed into a sample block with a thickness of 20 mm, and then was hot-pressed under the condition of a temperature of 40℃ and a pressure of 90 MPa for 5 min, and the sample block was cut to remove the periphery to obtain a stacked sheet with a size of 200 mm x 200 mm;

[0183] The stacked sheet was cut into small blocks with a size of 16 mm x 16 mm x 20 mm, and was placed in a high-temperature furnace, and was heated from room temperature to 290℃ for 240 min, was kept at 290℃ for 60 min, was heated to 410℃ for 120 min, was kept at 410℃ for 1 h, and was heated to 1080℃ for 270 min, and was kept at 1080℃ for 3.5 h to obtain a ceramic skeleton with a through-hole structure as shown in FIG. 2, wherein the pore size first decreases and then increases.

[0184] Example 7 Preparation of a ceramic skeleton

[0185] Sodium feldspar with a particle size of 5.0 μm was used as a main raw material, PVA aqueous solution (the average molecular weight of PVA was 155000) with a mass concentration of 10% was used as a binder, PEG (the molecular weight of PEG was 400) was used as a plasticizer, ammonium citrate was used as a dispersant, PMMA was used as a pore-forming agent, and deionized water was used as a medium; three different casting slurries were prepared according to different contents of components, wherein the mass ratio of sodium feldspar, PVA aqueous solution, PEG, ammonium citrate, deionized water and PMMA in the ceramic slurry a was 100:12:0.4:0.7:50:5, the PMMA was obtained by mixing PMMA with a particle size of 50 μm, PMMA with a particle size of 80 μm and PMMA with a particle size of 100 μm according to a mass ratio of 1:1:1; the mass ratio of sodium feldspar, PVA aqueous solution, PEG, ammonium citrate, deionized water and PMMA in the ceramic slurry b was 100:12:0.4:0.7:55:10, the PMMA was obtained by mixing PMMA with a particle size of 100 μm, PMMA with a particle size of 300 μm and PMMA with a particle size of 500 μm according to a mass ratio of 1:1:1; the mass ratio of sodium feldspar, PVA aqueous solution, PEG, ammonium citrate, deionized water and PMMA in the ceramic slurry c was 100:12:0.4:0.7:60:15, the PMMA was obtained by mixing PMMA with a particle size of 500 μm, PMMA with a particle size of 700 μm and PMMA with a particle size of 1000 μm according to a mass ratio of 1:1:1;

[0186] According to the above raw material ratio, sodium feldspar, PMMA, deionized water and ammonium citrate were ball milled (the rotation speed of ball milling was 20 r / min) for 12 h, and then PVA aqueous solution and PEG were added for secondary ball milling (the rotation speed of ball milling was 20 r / min) for 8 h; the well ball milled slurry was stirred under vacuum for 1 h, and the ceramic slurry a, the ceramic slurry b and the ceramic slurry c were obtained after removing the air bubbles in the slurry, respectively;

[0187] The ceramic slurry a was introduced into the mold 1 and frozen in the-20 ℃ freezing device for 1 h, and the first frozen block was obtained after the freezing was completed; the first frozen block was placed in the mold 2, the mold 2 had three ejector pins at the bottom, the first frozen block was suspended in the mold 2, then the ceramic slurry b was poured into the mold 2 and covered the first frozen block, and the mold 2 was placed in the-20 ℃ freezing device for freezing again for 1 h, and the second frozen block was obtained;

[0188] The second frozen block was placed in the mold 3, the mold 3 had three ejector pins at the bottom, the second frozen block was suspended in the mold 3, then the ceramic slurry c was poured into the mold 3 and covered the second frozen block, and the mold 3 was placed in the-80 ℃ freezing device for freezing again for 1 h, and the third frozen block was obtained;

[0189] The third frozen block was placed in a vacuum freeze-drying box and dried at 50 Pa and 5°C for 6 h to obtain a dried sample block; the dried sample block was placed in a high-temperature furnace, and the temperature was raised from room temperature to 290°C over 240 min, maintained at 290°C for 60 min, raised to 410°C over 120 min, maintained at 410°C for 1 h, raised to 1200°C over 300 min, and maintained at 1200°C for 1.0 h to obtain a ceramic framework with a three-dimensional through-hole structure with a pore size gradually increasing from the inside to the outside, as shown in FIG. 13.

[0190] Example 8 Preparation of a ceramic framework

[0191] Albite with a particle size of 3.0 μm was used as the main raw material, a PVA aqueous solution with a mass concentration of 12% (the average molecular weight of the PVA was 155000) was used as the binder, PEG (the molecular weight of the PEG was 400) was used as the plasticizer, ammonium citrate was used as the dispersant, PMMA was used as the pore-forming agent, and deionized water was used as the medium; three different casting slurries were prepared according to different contents of the components, wherein the mass ratio of the albite, the PVA aqueous solution, the PEG, the ammonium citrate, the deionized water, and the PMMA in the ceramic slurry a was 100:12:0.4:0.7:50:5, the PMMA was obtained by mixing PMMA with a particle size of 50 μm, PMMA with a particle size of 80 μm, and PMMA with a particle size of 100 μm according to a mass ratio of 1:2:1; the mass ratio of the albite, the PVA aqueous solution, the PEG, the ammonium citrate, the deionized water, and the PMMA in the ceramic slurry b was 100:12:0.4:0.7:55:10, the PMMA was obtained by mixing PMMA with a particle size of 70 μm, PMMA with a particle size of 100 μm, and PMMA with a particle size of 150 μm according to a mass ratio of 1:2:1; the mass ratio of the albite, the PVA aqueous solution, the PEG, the ammonium citrate, the deionized water, and the PMMA in the ceramic slurry c was 100:12:0.4:0.7:60:15, the PMMA was obtained by mixing PMMA with a particle size of 100 μm, PMMA with a particle size of 150 μm, and PMMA with a particle size of 200 μm according to a mass ratio of 1:2:1.

[0192] According to the above raw material ratio, the albite, the PMMA, the deionized water, and the ammonium citrate were ball milled (the rotation speed of the ball milling was 20 r / min) for 12 h, and then the PVA aqueous solution and the PEG were added and secondarily ball milled (the rotation speed of the ball milling was 20 r / min) for 8 h; the well ball milled slurry was stirred under vacuum for 1 h to remove the air bubbles inside, and then the ceramic slurry a, the ceramic slurry b, and the ceramic slurry c were obtained, respectively.

[0193] The ceramic slurry a is introduced into the mold 1 and frozen in a -30℃ freezing device for 1h, and a first frozen block is obtained after the freezing is completed; the first frozen block is placed into the mold 2b, then the ceramic slurry b is poured into the mold 2b and covers the first frozen block, and the mold 2b is placed into the -30℃ freezing device again for freezing for 1h, and a second frozen block is obtained;

[0194] The second frozen block is placed into the mold 3c, then the ceramic slurry c is poured into the mold 3c and covers the second frozen block, and the mold 3c is placed into the -30℃ freezing device again for freezing for 1h, and a third frozen block is obtained;

[0195] The third frozen block is placed into a 5℃ vacuum freeze-drying box and dried at 50Pa for 4h, and a dried sample block is obtained; the dried sample block is placed into a high-temperature furnace, and the temperature is raised from room temperature to 290℃ in 240min, kept at 290℃ for 60min, raised to 410℃ in 120min, kept at 410℃ for 1h, raised to 1100℃ in 280min, and kept at 1100℃ for 4.5h, and a ceramic framework with a divergent through-hole structure with a gradually increasing pore size from the starting position as shown in FIG. 14 is obtained.

[0196] Example 9 Preparation of a ceramic framework

[0197] 5μm sodium feldspar and 100nm sodium aluminum silicate are used as main raw materials, and the mass ratio is 6:4; a 3% mass concentration PVA aqueous solution is used as a binder, and the mass ratio of the binder to the main raw materials is 1:10; anhydrous ethanol is used as a solvent, and the mass ratio of the solvent to the main raw materials is 3:2;

[0198] The main raw materials, the binder, and the solvent are wet ball milled, the rotation speed is 26r / min, and the ball milling time is 3h, and a ball milled material is obtained;

[0199] The ball milled material is dried at 55℃ for 12h, and a dry powder is obtained;

[0200] The dry powder is passed through a 100 mesh sieve, and then the obtained undersize is dry pressed under a pressure of 10MPa for 50s to obtain a dry pressed block;

[0201] The dry pressed block is isostatic pressed under a pressure of 230MPa for 3min to obtain a green body;

[0202] The green body is placed into a high-temperature furnace, and the temperature is raised from room temperature to 290℃ in 240min, kept at 290℃ for 60min, raised to 410℃ in 120min, kept at 410℃ for 1h, raised to 890℃ in 180min, and kept at 890℃ for 4h to obtain a ceramic framework, and the pore structure distribution of the ceramic framework is relatively uniform, and the pore size is relatively close, and there is no obvious change trend.

[0203] Example 10 Preparation of ceramic framework

[0204] The main raw material is 3.5 μm sodium feldspar, 2 μm PMMA and potato powder are used as the pore-forming agent, and hydroxypropyl methyl cellulose is used as the binder; the mass ratio of the pore-forming agent to the main raw material is 1:10; the potato powder is the undersize obtained by passing through a 180-mesh sieve, and the mass ratio of PMMA to potato powder is 1:1; the mass ratio of hydroxypropyl methyl cellulose to the main raw material is 1:20;

[0205] The sodium feldspar, PMMA, potato powder and hydroxypropyl methyl cellulose are dry-mixed according to the proportions by using a mixer to obtain a mixture;

[0206] The mixture, glycerol, water and 3% mass concentration PVA aqueous solution are added together into a kneader to obtain a kneaded material; the mass ratio of glycerol to the main raw material is 1.5:100; the mass ratio of water to the main raw material is 26.5:100; the mass ratio of the PVA aqueous solution to the main raw material is 1:100; the number of revolutions of the kneader is 15 revolutions / min;

[0207] The kneaded material is aged for 12 h and then is milled by using a pug mill to obtain a mud block; the extrusion speed of the pug mill is 80 cm / min;

[0208] The mud block is opened into mud segments by using a mud segment machine; the extrusion speed of the mud segment machine is 30 cm / min;

[0209] The mud segments are extruded and cut by using an extrusion molding machine to obtain a wet blank; the extrusion speed of the extrusion molding machine is 50 cm / min;

[0210] The wet blank is subjected to microwave drying to obtain a dry blank; the microwave power of the microwave drying is 3 kW, and the time of the microwave drying is 65 s;

[0211] The dry blank is placed into a high-temperature furnace, and the temperature is raised from room temperature to 290°C over 240 min, is kept at 290°C for 60 min, is raised to 410°C over 120 min, is kept at 410°C for 1 h, is raised to 1100°C over 280 min, and is kept at 1100°C for 3 h to obtain a ceramic framework with a three-dimensional through-hole structure as shown in FIG. 8.

[0212] Examples 11-20 Preparation of resin-ceramic composite material

[0213] Preparation of resin precursor solution:

[0214] Bis-GMA, UDMA, TEGDMA and BPO were mixed in the proportions shown in Table 1 to obtain a resin precursor solution. The mass fraction of BPO in the resin precursor solution was 0.1% in Example 19, and the mass fraction of BPO in the resin precursor solution was 0.55% in the other examples.

[0215] Ceramic framework modification:

[0216] The ceramic framework prepared in the above examples was soaked in the silane modification solution shown in Table 1, and modified at room temperature for 24 h, and then modified at 60°C for 1.5 h to obtain a modified ceramic framework.

[0217] Preparation of resin-ceramic composite material:

[0218] The modified ceramic framework was immersed in the resin precursor solution, vacuum impregnated at room temperature, the vacuum impregnation time was 36 h, and the vacuum impregnation pressure was 500 Pa. After impregnation, resin curing was performed in a warm isostatic press (the curing pressure, temperature and time are shown in Table 1) to obtain a resin-ceramic composite material.

[0219] Table 1 Conditions for preparing resin-ceramic composite material

[0220] Example 21 Preparation of resin-ceramic composite material

[0221] Preparation of PVA aqueous solution:

[0222] 85 g of deionized water was weighed in a beaker, and 15 g of PVA (average molecular weight 175000) was added to the beaker while stirring. The mixture was heated and stirred at 90°C for 4 h to obtain a viscous PVA aqueous solution.

[0223] Preparation of resin precursor solution:

[0224] Bis-GMA, UDMA, TEGDMA and BPO were mixed to obtain a mixed solution. The mass ratio of Bis-GMA, UDMA and TEGDMA was 1:1:2, and the mass fraction of BPO in the mixed solution was 0.55%. The mixed solution and the PVA aqueous solution were thoroughly stirred and mixed in a volume ratio of 1:10 to obtain a resin precursor solution.

[0225] Ceramic framework modification:

[0226] The ceramic framework prepared in Example 8 was soaked in a silane modification solution (the mass ratio of anhydrous ethanol, distilled water, acetic acid and KH570 was 1:1:0.009:0.01), and modified at room temperature for 24 h, and then modified at 60°C for 1.5 h to obtain a modified ceramic framework.

[0227] Preparation of resin ceramic composite material

[0228] The modified ceramic framework is immersed in the prepared resin precursor liquid, vacuum impregnation is carried out at room temperature, the pressure of vacuum impregnation is 1000 Pa, the time of vacuum impregnation is 24 h, and the impregnated ceramic framework is obtained;

[0229] The impregnated ceramic framework is frozen at-20℃ for 12 h, then thawed at room temperature, the freezing and thawing are repeated twice, then vacuum drying is carried out at a pressure of 50 Pa and a temperature of 5℃ for 2 h, resin curing is carried out at 50℃ for 6 h, the cured sample is placed in deionized water, and soaking is carried out at room temperature and normal pressure for 2 h, and the resin ceramic composite material is obtained.

[0230] The resin ceramic composite material prepared in the embodiment has high hardness and strength, the resin is distributed in the PVA hydrogel, and the three are firmly combined.

[0231] Comparative example 1

[0232] The preparation method is basically the same as that of example 12, except that PMMA is not added, and the prepared ceramic framework has a relatively uniform pore size distribution, and only a single pore structure.

[0233] Test example

[0234] The properties of the resin ceramic composite materials prepared in examples 11-20 and comparative example 1 are shown in Table 2. In Table 2, the detection standard of hardness is GB / T 4340.1-2009, the detection standard of fracture toughness is GB 30367-2013, and the detection standard of bending strength is GB 30367-2013. The properties of the resin ceramic composite material prepared in example 21 are shown in Table 3, the detection standard of tensile strength is GB / T 10654-2001, the detection standard of compressive modulus is GB / T 1041-2008, and the detection standard of cytotoxicity grade is GB / T 16886.5-2017.

[0235] Table 2 Properties of resin ceramic composite materials prepared in examples 11-20 and comparative example 1

[0236] Table 3 Comparison of properties of resin ceramic composite material prepared in example 21 and human cartilage

[0237] As can be seen from Table 2, the density, strength and toughness of the resin-ceramic composite material are related to the content of the pore-forming agent. The higher the content of the pore-forming agent, the higher the porosity, and more resin can be penetrated, so the comprehensive density will be reduced, the toughness will be enhanced, and the strength will be increased first and then reduced. In addition, with the same porosity, the smaller the pore size, the less conducive to resin penetration, so the strength and toughness will be reduced. Therefore, by adjusting the different pore sizes and porosities, resin-ceramic composite materials with different mechanical properties can be obtained, which can be used in different scenarios to meet different needs.

[0238] As can be seen from Table 3, the PVA hydrogel resin-ceramic composite material in Example 21 is close to human cartilage in performance, has similar stretchability, compressibility, good elasticity and lubricity, and passes the cytotoxicity test, so it can be used as a substitute material for human cartilage. In addition, by selecting raw materials with good biocompatibility and different particle sizes, adjusting the particle size and content of the pore-forming agent, and adjusting the water absorption of the PVA hydrogel, a porous structure and mechanical properties close to human bone can be obtained. The material with good biocompatibility and porous structure is conducive to cell adhesion and tissue repair, and can be used as a human bionic bone material.

[0239] The above only describes the preferred embodiments of the present application, and it should be pointed out that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the protection scope of the present application.

Claims

1. A ceramic skeleton, characterized by, The ceramic framework has a porous structure. The porous structure comprises one or more of a communicating pore structure and a through-pore structure. The communicating pore structure is formed by a plurality of communicating pores. The through-pore structure comprises one or more of a unidirectional through-pore structure and a divergent through-pore structure.

2. The ceramic skeleton according to claim 1, characterized in that, The pores in the communicating pore structure are regular and / or irregular pores.

3. The ceramic skeleton according to claim 1, wherein The pore size of the pores in the communicating pore structure increases from one end to the other end, or the pore size of the pores first increases and then decreases from one end to the other end, or the pore size of the pores first decreases and then increases from one end to the other end.

4. The ceramic skeleton according to claim 1 or 3, characterized in that, The pore size of the pores in the communicating pore structure is independently less than or equal to 1000 μm.

5. The ceramic skeleton according to claim 1, wherein The unidirectional through-pore structure is formed by a plurality of through-pores from one end to the other end.

6. The ceramic skeleton according to claim 1, wherein The divergent through-pore structure comprises a plurality of through-pores diverging from a starting position in the interior of the ceramic framework to the surrounding.

7. The ceramic skeleton according to claim 1, wherein The divergent through-pore structure comprises a three-dimensional through-pore structure. The three-dimensional through-pore structure is formed by a plurality of three-dimensional through-pores penetrating up, down, left, right, front and back.

8. The ceramic skeleton according to claim 1, wherein The pore size of each through-pore in the unidirectional through-pore structure independently increases from one end to the other end, or the pore size of each through-pore independently first increases and then decreases from one end to the other end, or the pore size of each through-pore independently first decreases and then increases from one end to the other end.

9. The ceramic skeleton according to claim 1 or 8, characterized in that, The pore size of each through-pore in the unidirectional through-pore structure is independently less than or equal to 1000 μm.

10. The ceramic skeleton of claim 1, wherein, The pore size of each through-pore in the divergent through-pore structure independently gradually increases from the starting position to the surrounding to form a horn shape, or the pore size of each through-pore independently gradually decreases from the starting position to the surrounding, or the pore size of each through-pore independently first increases and then decreases from the starting position to the surrounding, or the pore size of each through-pore independently first decreases and then increases from the starting position to the surrounding.

11. The ceramic skeleton according to claim 1 or 10, characterized in that, The pore size of each through-pore in the divergent through-pore structure is independently less than or equal to 1000 μm.

12. The ceramic skeleton according to claim 7, wherein The pore size of each three-dimensional through-pore in the three-dimensional through-pore structure independently gradually increases from the middle to the surrounding to form a horn shape, or the pore size of each three-dimensional through-pore independently gradually decreases from the middle to the surrounding, or the pore size of each three-dimensional through-pore independently first increases and then decreases from the middle to the surrounding, or the pore size of each three-dimensional through-pore independently first decreases and then increases from the middle to the surrounding.

13. The ceramic skeleton according to claim 7 or 12, characterized in that, The pore size of each three-dimensional through-pore in the three-dimensional through-pore structure is independently less than or equal to 1000 μm.

14. A method for preparing the ceramic framework according to any one of claims 1 to 13, comprising the following steps: mixing a main raw material, a binder and a solvent to obtain a slurry; the main raw material comprises one or more of a biologically inert ceramic material and a biologically active ceramic material; flow casting the slurry to obtain a flow cast sheet; stacking the flow cast sheet to obtain a stacked sheet; sintering the stacked sheet to obtain the ceramic framework.

15. The method of claim 14, wherein, The biologically inert ceramic material comprises one or more of zirconia, alumina, quartz, lithium disilicate, glass powder, magnesium aluminum spinel, sodium aluminum silicate, feldspar, silicon carbide, carbon nanostructure and nitride. The bioactive ceramic material includes one or more of hydroxyapatite, fluorapatite, bioglass ceramic, A-W glass ceramic, calcium phosphate, calcium carbonate and calcium sulfate.

16. The method of claim 14, wherein, The slurry further includes one or more of dispersant, plasticizer and pore-forming agent.

17. The method of claim 16, wherein, The pore-forming agent includes one or more of polymethyl methacrylate, corn starch and potato powder.

18. A method for preparing the ceramic framework according to any one of claims 1-13, comprising the following steps: mixing the main raw material and solvent to obtain a ceramic slurry; the main raw material includes one or more of bioinert ceramic material and bioactive ceramic material; freezing the ceramic slurry to obtain frozen blocks; drying the frozen blocks to obtain dried blocks; sintering the dried blocks to obtain the ceramic framework.

19. A method for preparing the ceramic framework according to any one of claims 1-13, comprising the following steps: mixing the main raw material and other raw materials to prepare a ceramic powder; the main raw material includes one or more of bioinert ceramic material and bioactive ceramic material; dry pressing and / or isostatic pressing the ceramic powder to obtain a green body; sintering the green body to obtain the ceramic framework.

20. A method for preparing the ceramic framework according to any one of claims 1-13, comprising the following steps: mixing the main raw material and other raw materials to obtain a mixture; the main raw material includes one or more of bioinert ceramic material and bioactive ceramic material; kneading the mixture, binder and solvent to obtain a kneaded mixture; aging the kneaded mixture and then pugging to obtain pugged blocks; opening the pugged blocks to obtain mud segments; extruding the mud segments to obtain wet bodies; drying the wet bodies to obtain dry bodies; sintering the dry bodies to obtain the ceramic framework.

21. Use of the ceramic framework according to any one of claims 1-13 or prepared by the method according to any one of claims 14-20 in preparing a biomedical material.

22. The use according to claim 21, characterized in that, The biomedical material includes a denture, an artificial eye or a bionic bone.

23. A biomaterial for medical use, characterized in that, The biomedical material contains the ceramic framework according to any one of claims 1-13 or prepared by the method according to any one of claims 14-20.

24. A resin ceramic composite material, characterized by, The resin preparation raw material includes one or more of monofunctional acrylate and multifunctional acrylate.

25. The resin ceramic composite of claim 24, wherein, 26. A method for preparing the resin-ceramic composite material according to any one of claims 24-25, comprising the following steps: immersing the ceramic framework in a resin precursor solution and curing to obtain the resin-ceramic composite material. The resin precursor solution preparation raw material includes one or more of bisphenol A-glycidyl dimethacrylate, diurethane dimethacrylate and triethylene glycol dimethacrylate.

27. The method of claim 26, wherein, The resin precursor solution preparation raw material further includes polyvinyl alcohol aqueous solution.

28. The method of manufacturing according to claim 26 or 27, wherein, ​ 29. The preparation method according to claim 26, characterized in that, The curing pressure is 0.1-500 MPa; the curing temperature is 10-180℃; and the curing pressure-keeping and temperature-keeping time is 1 min-48 h.

30. Use of the resin ceramic composite material according to any one of claims 24-25 or prepared by the method according to any one of claims 26-29 in the preparation of a biomedical material.

31. The use according to claim 30, wherein The biomedical material comprises a denture, an artificial eye or a bionic bone.

32. A biomedical material, characterized in that, The resin ceramic composite material according to any one of claims 24-25 or prepared by the method according to any one of claims 26-29 is contained.

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