CN116253562A - Resin-infiltrated ceramic composite material and preparation method thereof - Google Patents

Resin-infiltrated ceramic composite material and preparation method thereof Download PDF

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CN116253562A
CN116253562A CN202310182063.2A CN202310182063A CN116253562A CN 116253562 A CN116253562 A CN 116253562A CN 202310182063 A CN202310182063 A CN 202310182063A CN 116253562 A CN116253562 A CN 116253562A
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resin
ceramic
composite material
preparation
infiltrated
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王惠宁
陈媛媛
崔本仓
麻健丰
孙诚
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SCHOOL & HOSPITAL OF STOMATOLOGY WENZHOU MEDICAL UNIVERSITY
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/833—Glass-ceramic composites
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
    • A61K6/838—Phosphorus compounds, e.g. apatite
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    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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Abstract

The invention belongs to the technical field of composite materials, and discloses a resin-infiltrated ceramic composite material and a preparation method thereof. The preparation method comprises the following steps: sintering, ball milling and forming the ceramic material to prepare a ceramic blank; sintering the ceramic blank to obtain a ceramic block; penetrating mixed resin containing an initiator into the ceramic block to obtain a resin-penetrated ceramic block; and carrying out temperature isostatic pressing curing treatment on the resin-penetrated ceramic block to obtain the resin-penetrated ceramic composite material. The invention also provides the resin-infiltrated ceramic composite material prepared according to the preparation method. The invention has the advantages of low cost and easy acquisition of raw materials, low cost, simplified process, easy control of parameters and convenient mass production by adopting an isostatic pressing preparation process. The composite material prepared by the method has higher mechanical property and aesthetic property.

Description

Resin-infiltrated ceramic composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a resin-infiltrated ceramic composite material and a preparation method thereof.
Background
Prevention and repair of oral diseases is a matter of urgent concern. The market scale of oral services in China is also increasing, and more dental restoration crown products are put into research and production and application.
With the development of computer aided design/computer aided manufacturing (CAD/CAM) technology, indirect repair composites that can be used for chair side repair are receiving increasing attention. Commercial CAD/CAM blocks have proven to be machinable, high strength and high cutting efficiency.
The currently predominant CAD/CAM machinable materials are: zirconia, alumina, polymethyl methacrylate, and the like. Wherein the hardness of the zirconia ceramic Lava TMY-TZP (3M ESPE) is about 13GPa; the Alumina ceramic (VITAIn-Ceram Alumina, vita Zahn fabrik) has an elastic modulus of 410GPa and a hardness of about 19.8GPa; polymethyl methacrylate (poliden PMMA) has an elastic modulus of 2.77GPa and a hardness of about 0.25GPa; VITACAD-Temp (Vita Zahn fabrik, a crosslinked acrylate polymer with microfiller) has a flexural strength of 80MPa and an elastic modulus of 2.8GPa. However, in natural teeth, the bending strength of enamel is 60-90 MPa, the elastic modulus is 48-115 GPa, and the hardness is 2.7-6.4 GPa; the bending strength of dentin is 213-280 MPa, the elastic modulus is 8.7-25 GPa, and the hardness is 2.7-6.4 GPa. In terms of mechanical properties, flexural strength is significant for restoring the masticatory function of defects and deletions of teeth, and hardness affects the wear resistance of dental materials. If zirconia with too high hardness is used, excessive wear to teeth and adjacent teeth can result. Which in turn causes the teeth to lack contact, interfering with chewing efficiency. The stress concentration of the zirconia and alumina with high elastic modulus on the structure and the surface of the repaired gravure is high. If the material with too low hardness such as polymethyl methacrylate is selected, the wear resistance and scratch resistance are poor, and the material can only be used as a temporary repair material.
In recent years, with the increasing medical ideas, the enhancement of natural tooth consciousness, and the high-tech trend of prosthesis preparation, many researches have focused on developing new materials to achieve mechanical compatibility with natural teeth. The mode of 'co-participation' of the relationship between the oral doctor and the patient also enables the patient to fully communicate with the doctor, so that more knowledge is provided for the selection of the repairing material and higher requirements are put forward. Thus, achieving mechanical properties that match those of natural teeth, with good aesthetic properties, is a major challenge for dental composites.
At present, some novel composite materials are developed, namely, the resin-infiltrated ceramic composite materials are generally obtained by mixing, pressing and sintering the ceramic materials such as zirconia, alumina and the like according to single components or a plurality of ceramic materials to form a porous ceramic blank body and then performing resin infiltration and heat curing. However, they have a certain gap from the mechanical properties of natural teeth. This is because there are still some problems in the preparation method, such as the ceramic is relatively dense, and it is difficult to mix the infiltration resin uniformly; in the preparation process, the resin polymer can be burst, so that a certain potential safety hazard exists, and the resin permeable composite material can be cracked; and for example, the double bond conversion rate of the resin is not high, so that the strength and the compression resistance of the resin penetrating the ceramic composite material are limited.
Therefore, it is highly desirable to provide a preparation method which is safe and can prepare a resin-infiltrated ceramic composite material having excellent mechanical properties and good aesthetic properties for dental restoration.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a preparation method of the resin-infiltrated ceramic composite material, which adopts isostatic compaction for preparation, has lower cost, is suitable for mass production, and simplifies the preparation process; and the temperature isostatic pressing curing treatment can lead fewer smaller pores to exist in the composite material, so that the uniformity is higher, and the mechanical property of the composite material is higher.
The invention also provides the resin-infiltrated ceramic composite material prepared according to the preparation method.
According to one aspect of the present invention, there is provided a method for preparing a resin-infiltrated ceramic composite material, comprising the steps of:
s1: sintering, ball milling and forming the ceramic material to prepare a ceramic blank;
s2: sintering the ceramic blank to obtain a ceramic block;
s3: penetrating mixed resin containing an initiator into the ceramic block to obtain a resin-penetrated ceramic block;
s4: and carrying out temperature isostatic pressing curing treatment on the resin-penetrated ceramic block to obtain the resin-penetrated ceramic composite material.
In some embodiments of the invention, the ceramic material comprises Hydroxyapatite (HA) and bioactive glass (BAG).
In some embodiments of the invention, the bioactive glass comprises SiO 2 CaO and P 2 O 5 。
In some preferred embodiments of the invention, the bioactive glass comprises 59mol% SiO 2 36mol% CaO and 5mol% P 2 O 5 。
In some embodiments of the invention, the sintering temperature in step S1 is 700 to 750 ℃ for 3 to 3.2 hours.
Specifically, step S1 sinters the hydroxyapatite and the bioactive glass, respectively.
Specifically, after the ceramic material is sintered in step S1, the activity of the ceramic material may be reduced, so as to facilitate the penetration of the subsequent resin.
In some embodiments of the present invention, the method of ball milling in step S1 comprises: and adding a binder and a dispersing agent into the solvent, uniformly mixing, and then adding the sintered ceramic material for ball milling.
In some embodiments of the present invention, the mass ratio of the binder to the dispersant is (1-2): (1-2).
In some preferred embodiments of the present invention, the mass ratio of the binder to the dispersant is 1:1.
in some preferred embodiments of the present invention, the mass ratio of the solvent, the binder, and the dispersant is 1:0.875:0.875.
in some embodiments of the invention, the binder is sodium carboxymethyl cellulose.
In some embodiments of the invention, the dispersant comprises at least one of polyethylene glycol, N-methylpyrrolidone, acetamide, or N, N-dimethylformamide.
In some preferred embodiments of the present invention, step S1 adds a binder and a dispersant to a solvent, mixes them well, and then adds hydroxyapatite and bioactive glass to ball mill.
Specifically, the mass ratio of the hydroxyapatite to the bioactive glass is (3-9): 1.
in some embodiments of the invention, the solvent is water.
In some embodiments of the invention, the ball milling is performed at a rotational speed of 200 to 250rpm for a period of 3.5 to 4 hours.
In some preferred embodiments of the invention, the ball milling is carried out at 200rpm for 3.5 hours.
In some embodiments of the present invention, step S1 further comprises drying the ball-milled mixed slurry and grinding the dried mixed slurry into powder.
Specifically, the temperature of the drying is 60-65 ℃ and the time is 11.5-12 h.
More specifically, the temperature of the drying is 60 ℃ and the time is 12 hours.
In some embodiments of the invention, the shaping of step S1 comprises compression molding and cold isostatic pressing.
In some embodiments of the invention, the compression molding is performed at a pressure of 2 to 2.2MPa.
In some preferred embodiments of the invention, the compression molding pressure is 2MPa.
In some embodiments of the invention, the cold isostatic pressing pressure is 200-250 MPa.
Specifically, the ground powder is subjected to compression molding and cold isostatic pressing in sequence to prepare the ceramic blank.
In some embodiments of the invention, the sintering method of step S2 comprises: raising the temperature to 1000-1100 ℃ at a heating rate of 2-2.5 ℃/min, and preserving the temperature for 2.8-3.2 h.
Specifically, the sintering temperature and the heating rate in the step S2 affect the porosity and the shrinkage of the ceramic body, so as to affect the mechanical properties of the resin-infiltrated ceramic composite material. The sintering temperature is controlled at 1000-1100 ℃, the heating rate is controlled at 2-2.5 ℃/min, and the finally formed resin-infiltrated ceramic composite material can have proper porosity so as to absorb proper resin, thereby endowing the resin-infiltrated ceramic composite material with higher flexural modulus and hardness.
In some preferred embodiments of the present invention, the sintering method of step S2 comprises: raising the temperature to 1000-1100 ℃ at a heating rate of 2 ℃/min, and preserving the temperature for 3 hours.
Specifically, the ceramic block prepared in step S2 is a porous ceramic block.
In some embodiments of the invention, the initiator of step S3 is selected from peroxides and/or azo-based compounds.
In some preferred embodiments of the invention, the initiator of step S3 is selected from the peroxides.
In some more preferred embodiments of the present invention, the initiator of step S3 is selected from benzoyl peroxide.
In some embodiments of the invention, the hybrid resin of step S3 includes triethylene glycol dimethacrylate and bisphenol a diglycidyl dimethacrylate.
In some embodiments of the present invention, the initiator and the mixed resin are mixed in step S3 to prepare the initiator-containing mixed resin.
In some preferred embodiments of the present invention, the triethylene glycol dimethacrylate and the initiator are mixed to obtain a mixed solution in step S3, and then the bisphenol a glycidyl dimethacrylate is mixed with the mixed solution to obtain the initiator-containing mixed resin.
In some preferred embodiments of the invention, the mass ratio of the triethylene glycol dimethacrylate to the initiator is 50:1, wherein the mass ratio of the bisphenol A dimethacrylate to the triethylene glycol dimethacrylate is 1:1.
in some embodiments of the present invention, step S3 immerses the ceramic block in the mixed resin containing the initiator, and infiltrates in a vacuum drying oven to obtain the resin infiltrated ceramic block.
In some embodiments of the invention, the pressure of the permeation in step S3 is (-0.09) to (-0.1) MPa for a period of 72 to 120 hours.
In some embodiments of the present invention, the temperature of the temperature isostatic curing treatment in step S4 is 80-100 ℃ for 3-6 hours.
In some preferred embodiments of the present invention, the warm isostatic curing process described in step S4 is performed in two steps at different temperatures: the resin-infiltrated ceramic mass is first conducted at a low temperature of 50 to 80 ℃ (inclusive of the case of 80 ℃) and then at a high temperature of 80 to 100 ℃ (exclusive of the case of 80 ℃). The total time of the two steps of curing treatment is 1-6 hours.
According to a second aspect of the present invention, a resin-infiltrated ceramic composite material prepared according to the preparation method is provided.
According to a preferred embodiment of the invention, there is at least the following advantageous effect:
the raw materials are cheap and easy to obtain, the isostatic pressing preparation process is adopted, the cost is low, the process is simplified, the parameters are easy to control, and the mass production is convenient; and the isostatic pressing preparation process ensures that the ceramic green body is uniformly stressed in all directions and has higher density than the green body obtained by compression molding. The adoption of the temperature isostatic pressing curing treatment can lead fewer smaller pores to exist in the composite material, so that the uniformity is higher, the mechanical property of the composite material is higher, and the potential safety hazard existing in the prior art of drying and curing (the drying and curing are easy to generate explosion and crack, so that the composite material has poor mechanical property) is overcome. Therefore, the resin-infiltrated ceramic composite material prepared by the preparation method of the invention effectively combines the advantages of ceramic and resin, and has higher mechanical property and aesthetic property; the composite material takes hydroxyapatite as a main body and has good biocompatibility (because teeth mainly consist of apatite crystals).
In addition, the resin-infiltrated ceramic composite material prepared by the preparation method can be successfully prepared into an all-ceramic crown restoration body after CAD/CAM cutting, and has smooth surface and good edge adhesion. The bending strength is close to that of natural enamel, and the whole porcelain crown prosthesis is not easy to break when a patient chews. The flexural modulus is close to the elastic modulus of natural dentin, and compared with the restoration materials with high elastic modulus such as zirconia, the composite material with low elastic modulus can reduce stress concentration of the abutment and the crown. Hardness is between enamel and dentin, and the natural teeth are protected preferentially, so that abrasion and abrasion are reduced.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a schematic diagram of the macrostructure of a resin infiltrated HA/BAG ceramic composite material of examples 1, 3, 5, and 7 of the present invention;
FIG. 2 is a schematic diagram of a sample strip according to embodiment 1 of the present invention;
FIG. 3 is a view showing a structure of a scanning electron microscope of a porous ceramic block according to embodiment 5 of the present invention;
FIG. 4 is a diagram showing the structure of a scanning electron microscope of the resin-infiltrated HA/BAG ceramic composite material 5 of example 5 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is exemplary, and is provided merely to illustrate the invention and should not be construed as limiting the invention.
In the description of the present invention, unless explicitly defined otherwise, terms such as sintering, grinding, etc. should be construed broadly and the specific meaning of the terms in the present invention can be reasonably determined by a person skilled in the art in combination with the specific contents of the technical solutions.
In the description of the present invention, reference to the term "one embodiment," "some embodiments," etc., means that a particular feature, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment. Furthermore, the particular features, materials, or characteristics may be combined in any suitable manner in any one or more embodiments.
The test methods used in the examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
Example 1
The resin-infiltrated ceramic composite material 1 is prepared in the embodiment, and the specific process is as follows:
and sintering the ceramic material hydroxyapatite HA and bioactive glass BAG powder for 3 hours at 700 ℃. 0.0063g of sodium carboxymethylcellulose and 0.0063g of polyethylene glycol are weighed, 7mL of deionized water is added, stirring is uniform, the sintered ceramic material is added, namely 22.5g of HA and 2.5g of BAG are added, and ball milling is carried out for 3.5 hours at a rotating speed of 200rpm, so as to obtain mixed slurry. And (3) drying the mixed slurry at 60 ℃ for 12 hours, and grinding to obtain powder. The powder is compression molded under the pressure of 2MPa, and the ceramic blank is obtained by cold isostatic pressing under the pressure of 250MPa. Raising the temperature to 1000 ℃ at the heating rate of 2 ℃/min, sintering the ceramic body at the temperature, and preserving the heat for 3 hours to obtain the porous ceramic block.
Quickly and uniformly mixing triethylene glycol dimethacrylate and benzoyl peroxide by an ultrasonic cleaner to obtain a mixed solution, adding bisphenol A dimethacrylate into the mixed solution, and stirring to obtain a mixed resin containing an initiator, wherein the mass ratio of the triethylene glycol dimethacrylate to the bisphenol A dimethacrylate is 1:1, benzoyl peroxide was 1wt.% of the total mass of the two resins and stirred for a total of 12h.
The mixed resin containing the initiator is injected into a container, and the porous ceramic block is placed in the mixed resin containing the initiator, and the mixed resin cannot overflow the porous ceramic block. Then placing the porous ceramic block into a vacuum drying oven with the pressure of minus 0.1MPa for 72 hours, and penetrating the resin by utilizing vacuum capillary action until the porous ceramic block is fully penetrated. And (3) carrying out thermal isostatic pressing curing treatment on the porous ceramic blocks with sufficient resin permeation, wherein the curing temperature is 90 ℃, and the curing time is 3 hours, so as to obtain the resin permeation ceramic composite material 1.
The resin-rich layer on the surface of the resin-infiltrated ceramic composite material 1 is polished by a grinder to obtain the resin-infiltrated HA/BAG ceramic composite material 1 for dental restoration crowns, the macroscopic structure of which is shown in figure 1, and the color of which is seen to be in milky white color close to that of the original teeth. The composite material was cut by a dicing cutter and then sanded and polished with 500 mesh, 2000 mesh and 4000 mesh sandpaper to obtain the test bars, as shown in fig. 2.
Example 2
In this example, a resin-infiltrated ceramic composite material 2 was prepared by the same method as in example 1, except that the ceramic body of this example was sintered at 1100 ℃.
Example 3
This example prepared a resin-infiltrated ceramic composite 3, the method of preparation being the same as example 1, except that 21.25g of hydroxyapatite and 3.75g of bioactive glass were weighed.
Example 4
The resin-infiltrated ceramic composite material 4 was prepared in this example, except that 21.25g of hydroxyapatite and 3.75g of bioactive glass were weighed in this example, as in example 1; and the ceramic body is sintered at a temperature of 1100 ℃.
Example 5
In this example, a resin-infiltrated ceramic composite material 5 was prepared in the same manner as in example 1, except that 20g of hydroxyapatite and 5g of bioactive glass were weighed.
The structure of the scanning electron microscope of the porous ceramic block prepared in the embodiment is shown in fig. 3, and the structure of the scanning electron microscope of the resin-infiltrated HA/BAG ceramic composite material 5 is shown in fig. 4. As can be seen from the figure, the resin phase and the ceramic phase in the composite material form a good bond.
Example 6
The resin-infiltrated ceramic composite material 6 was prepared in this example, and the preparation method was the same as in example 1, except that 20g of hydroxyapatite and 5g of bioactive glass were weighed in this example; and the ceramic body is sintered at a temperature of 1100 ℃.
Example 7
This example prepared a resin-infiltrated ceramic composite 7, the method of preparation being the same as example 1, except that 18.75g of hydroxyapatite and 6.25g of bioactive glass were weighed.
Example 8
The resin-infiltrated ceramic composite material 8 was prepared in this example, except that 18.75g of hydroxyapatite and 6.25g of bioactive glass were weighed in this example, as in example 1; and the ceramic body is sintered at a temperature of 1100 ℃.
Comparative example 1
The comparative example prepared a warm-isostatic cured pure resin material a, and the preparation method and warm-isostatic curing treatment method of the mixed resin containing the initiator were the same as in example 1; the difference from example 1 is that the ceramic component is not contained.
Comparative example 2
In this example, ceramic material b was prepared, and the porous ceramic block was prepared in the same manner as in example 1; the difference from example 1 is that no resin permeation was performed.
The porous ceramic block prepared by the comparative example has large brittleness and low hardness, is easy to break during cutting, and cannot be used for preparing a spline, so that the mechanical property cannot be measured.
Comparative example 3
The present example produced a resin-infiltrated ceramic composite material c, differing from example 1 in that HA and BAG powders were not subjected to sintering treatment at 700 c, respectively.
The porous ceramic block prepared in the comparative example was cracked after high temperature sintering, and mechanical properties could not be measured.
Comparative example 4
The present example produced a resin-infiltrated ceramic composite material d, differing from example 1 in that the porous ceramic block having sufficient resin infiltration was not subjected to the warm isostatic curing treatment, but was subjected to the normal pressure 90 ℃ curing treatment in a drying oven.
The composite material prepared in this comparative example was unable to measure mechanical properties due to cracks generated in the resin.
Test examples
The present test example tests the flexural strength, flexural modulus and vickers hardness of the ceramic composites prepared in the examples and comparative examples. Wherein:
flexural strength and flexural modulus were tested using a universal tester (AGS, shimadzu, japan). The three-point bending test was used, the loading rate was 1mm/min, and the width X height X length of the sample was (2.+ -. 0.1) mm X (25.+ -. 2) mm. The span was 20mm.
Hardness was measured using a Vickers hardness tester (VH 1150, wilson, USA) with a sample width X height X length of (6.+ -. 0.1) mm X (3.+ -. 0.1) mm X (25.+ -. 2) mm.
The test results are shown in Table 1.
TABLE 1
Figure SMS_1
As can be seen from examples 1 to 8, the invention adopts the isostatic pressing method to prepare the porous ceramic block, then the resin is permeated into the porous ceramic block, and the resin permeated ceramic composite material obtained by the warm isostatic pressing curing treatment has better mechanical property. The mass ratio and sintering temperature of HA and BAG have a certain influence on the mechanical properties of the composite material. As can be seen from comparative examples 1 to 2, the porous ceramic block has high brittleness, low fracture toughness, and no bright color. The composite material subjected to the warm isostatic pressing curing treatment has low flexural modulus, low Vickers hardness and high flexural strength. The resin-infiltrated ceramic composites of examples 1-8 combine the features of both, and have improved aesthetic properties, and significantly improved flexural modulus and vickers hardness. As can be seen from comparative example 3, the ceramic material powder not sintered in advance has higher activity, and the ceramic block is easy to crack after high-temperature sintering. As can be seen from comparative example 4, the resin cured by the warm isostatic pressing does not burst and a solid block with uniform density can be obtained, compared with the normal pressure.
The resin-infiltrated ceramic composite materials of examples 1-8 of the present invention are applied to dental restoration crowns, wherein example 5 has the best performance, the flexural strength of which is close to the flexural strength of natural enamel (60-90 MPa), the flexural modulus of which is close to the elastic modulus of natural dentin (8.7-25 GPa), and the hardness of which is between enamel (2.7-6.4 GPa) and dentin (0.12-0.67 GPa). Therefore, the resin-infiltrated HA/BAG ceramic composite material prepared by the invention is expected to become a novel CAD/CAM dental crown material.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.

Claims (10)

1. The preparation method of the resin-infiltrated ceramic composite material is characterized by comprising the following steps of:
s1: sintering, ball milling and forming the ceramic material to prepare a ceramic blank;
s2: sintering the ceramic blank to obtain a ceramic block;
s3: penetrating mixed resin containing an initiator into the ceramic block to obtain a resin-penetrated ceramic block;
s4: and carrying out temperature isostatic pressing curing treatment on the resin-penetrated ceramic block to obtain the resin-penetrated ceramic composite material.
2. The method according to claim 1, wherein the temperature of the warm isostatic curing treatment in step S4 is 80 to 100 ℃ for 3 to 6 hours.
3. The method according to claim 1, wherein the sintering temperature in step S1 is 700 to 750 ℃ for 3 to 3.2 hours.
4. The method of manufacturing according to claim 1, wherein the ceramic material comprises hydroxyapatite and bioactive glass;
preferably, step S1 sinters the hydroxyapatite and the bioactive glass separately.
5. The method according to claim 4, wherein the ball milling method of step S1 comprises: adding a binder and a dispersing agent into a solvent, and then adding a sintered ceramic material for ball milling;
preferably, step S1 adds the binder and the dispersant to the solvent, and then adds the hydroxyapatite and the bioactive glass for ball milling;
preferably, the mass ratio of the hydroxyapatite to the bioactive glass is (3-9): 1.
6. the method of claim 1, wherein the shaping in step S1 comprises compression molding and cold isostatic pressing; the pressure of compression molding is 2-2.2 MPa, and the pressure of cold isostatic pressing is 200-250 MPa.
7. The method according to claim 1, wherein the sintering temperature in step S2 is 1000-1100 ℃ for 2.8-3.2 h.
8. The preparation method according to claim 1, wherein the initiator in step S3 is selected from peroxides and/or azo compounds;
preferably, the mixed resin of step S3 comprises triethylene glycol dimethacrylate and bisphenol a dimethacrylate;
preferably, the initiator and the mixed resin are mixed in step S3 to prepare the initiator-containing mixed resin.
9. The preparation method according to claim 1, wherein step S3 is to immerse the ceramic block in the mixed resin containing the initiator, infiltrate in a vacuum drying oven, and obtain the resin infiltrated ceramic block; the pressure of permeation is (-0.09) to (-0.1) MPa, and the time is 72-120 h.
10. A resin-infiltrated ceramic composite material prepared according to the method of any one of claims 1 to 9.
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