CN114767940B - Ceramic polymer composite material and preparation method thereof - Google Patents
Ceramic polymer composite material and preparation method thereof Download PDFInfo
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- CN114767940B CN114767940B CN202210467016.8A CN202210467016A CN114767940B CN 114767940 B CN114767940 B CN 114767940B CN 202210467016 A CN202210467016 A CN 202210467016A CN 114767940 B CN114767940 B CN 114767940B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/427—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of other specific inorganic materials not covered by A61L27/422 or A61L27/425
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/007—Producing shaped prefabricated articles from the material by freezing the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B11/00—Apparatus or processes for treating or working the shaped or preshaped articles
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
Abstract
The invention relates to a ceramic polymer composite material and a preparation method thereof, wherein the composite material comprises 18-85% by volume of ceramic skeleton and 15-82% by volume of polymer material; the ceramic skeleton comprises a layered structure, wherein every two adjacent sheets in the layered structure form a bridging structure, and the high polymer material is filled in pores of the ceramic skeleton; the composite material is prepared by mixing raw materials of a ceramic skeleton to obtain slurry, preparing the slurry into a green body with a stacked layered structure by adopting bidirectional freezing casting, placing the green body in a compression mold for volume compression, sequentially performing degumming treatment and sintering treatment to obtain the ceramic skeleton, and impregnating the ceramic skeleton in liquid resin. The ceramic polymer composite material prepared by the technical scheme of the invention has better mechanical property and better transmittance, and is more suitable for denture materials.
Description
Technical Field
The invention relates to the technical field of dental materials and preparation methods thereof, in particular to a ceramic polymer composite material and a preparation method thereof.
Background
False teeth play an important role in oral cavity prevention and health care, tooth deformity correction and other medical treatments. Dentures are required to have superior mechanical properties, good biocompatibility, ease of processing, modeling and fabrication, stable physicochemical properties, and a high degree of aesthetic similarity as dental materials to be implanted into the oral cavity. The false teeth used at present comprise metal alloy teeth, porcelain teeth, all-porcelain teeth and false teeth manufactured by adopting ceramic matrix composite materials. The metal alloy and the porcelain tooth are easy to mislead diagnosis of medical images because of the existence of metal; all-ceramic dental materials have problems of excessively high hardness and brittle fracture. Therefore, dentures manufactured using ceramic matrix composite materials are favored by users because they are free of metal elements, have certain mechanical properties, and have an aesthetic appearance that more closely matches that of the original teeth.
However, the ceramic matrix composite materials in the domestic market generally have high processing difficulty, and the mechanical properties can not reach the application range of the original teeth, so that the application of the ceramic matrix composite materials in the repair of modern medical chairs is severely limited. How to obtain a ceramic matrix composite material which can lead the mechanical property of the manufactured false tooth to approach the original teeth infinitely and has aesthetic appearance comparable to the original teeth, and the ceramic matrix composite material becomes a core pain point and a difficulty recognized by the dental material industry.
Disclosure of Invention
The invention aims to solve the problems and provide a ceramic polymer composite material with higher mechanical property and better aesthetic appearance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the ceramic polymer composite material comprises 18-85% by volume of ceramic skeleton and 15-82% by volume of polymer material; the ceramic skeleton is integrally of a layered structure, each two adjacent sheets in the layered structure form a bridging structure, and the high polymer material is filled in the pores of the ceramic skeleton.
Preferably, the raw material components of the ceramic skeleton comprise 10-40wt% of ceramic powder, 0.4-1wt% of dispersing agent, 1-6wt% of binder and 0.5-3wt% of plasticizer.
The addition of the binder and the plasticizer ensures that the slurry has enough fluidity, and simultaneously ensures that the frozen ice crystals formed during the bidirectional freezing casting of the obtained slurry can grow in a controllable and directional manner, thereby ensuring that the obtained green embryo has enough strength and toughness and ensuring the structural integrity of the green embryo in the compression process; when the dosage of the adhesive and the plasticizer is too high, excessive connecting bridges are formed in the green body, and the operation difficulty of medium volume compression is increased; when the dosage of the adhesive and the plasticizer is too low, the strength and toughness of the layered structure of the green body are insufficient, so that the green body is broken in the compression process.
Preferably, the ceramic powder comprises one or more of alumina ceramic powder, zirconia ceramic powder or titania ceramic powder; the dispersing agent comprises one or more of polyacrylic acid, polyethyleneimine, dolapix series dispersing agent, solo920, sodium dodecyl benzene sulfonate or sodium dodecyl sulfate; the binder comprises one or more of polyvinyl alcohol, polyacrylate or gelatin; the plasticizer comprises one or two of allyl alcohol or ethylene glycol.
The invention also aims to provide a preparation method of the ceramic polymer composite material.
A preparation method of a ceramic polymer composite material comprises the following steps:
s1: and dispersing the ceramic powder, the dispersing agent, the binder and the plasticizer in a solvent to obtain slurry.
S2: the slurry in the step S1 is defoamed, then bidirectional freezing casting is carried out, and then low-pressure freezing drying treatment is carried out, so that a green body with a layered structure parallel to each other is obtained;
the slurry obtained in the step S1 is directionally arranged through the bidirectional freezing casting treatment to form a slurry freezing body with a layered structure which is arranged in parallel, and at the moment, the solvent is frozen in the slurry freezing body at the same time; the solvent sublimates during low-pressure freeze drying, so that a pore structure is formed in the slurry frozen body, a green body with mutually parallel lamellar structures is obtained, and the green body has a pore structure.
In addition, the layered structures of the resulting green bodies are connected by connecting bridges. The connection bridge is formed according to the following principle: in the bidirectional freezing casting process, the direction of the cold source is not completely consistent with the growth direction of frozen ice crystals, so that bulges are formed on the surface of the layered structure, and when the volume compression is carried out in the compression mould, the adjacent layered structures are connected together through the bulges to form a connecting bridge due to the mutual approaching of the layered structures, and the laminated ceramic framework connected through the bridging structure is formed after sintering. The volume compression amount of the green embryo after paraffin impregnation is controlled by controlling the volume fraction of the green embryo, so that the number of connecting bridges between adjacent lamellar structures is controlled, and finally, the mechanical property of the ceramic skeleton is controlled.
S3: and (2) preheating the green embryo in the step (S2) to 80-85 ℃ and then placing the green embryo in liquid paraffin with the same temperature for infiltration, placing the paraffin-infiltrated green embryo in a compression mold, and applying compression force in the direction perpendicular to the layered structure to compress the green embryo, wherein the compression force is 0.1-10MPa, and the volume shrinkage rate of the green embryo after paraffin infiltration after compression is 2-38%.
The purpose of compression is to reduce the interlayer distance of the layered structure, providing a basis for the later obtained ceramic skeleton to have better mechanical properties. The green embryo impregnated with paraffin is compressed under low pressure, so that the damage of larger compression pressure to the layered structure is avoided, and the continuity of the layered structure is ensured.
According to the invention, the compression mould is adopted to carry out volume compression on the paraffin-impregnated green embryo at low pressure, and under the condition of ensuring that the microstructure of the green embryo is not damaged, the volume fraction of the paraffin-impregnated green embryo is improved from 10% -30% to 32% -48%, so that the volume shrinkage rate of the paraffin-impregnated green embryo after compression is 2-38%. The compression is carried out at the same temperature as the preheating temperature, and the dispersing agent has better flexibility, so that the flexibility of the green embryo in the compression process is further ensured, the layered structure of the green embryo is prevented from being broken by compression, and meanwhile, the low-pressure compression is carried out under the assistance of the dispersing agent, so that the layered structure of the green embryo is not easy to be broken by compression, the continuity of the layered structure is ensured, the continuity of the layered structure in the ceramic skeleton is ensured, and the finally obtained ceramic high-polymer composite material has better mechanical property.
S4: and (3) sequentially performing degumming treatment and sintering treatment on the green blanks compressed in the step (S3) to obtain the laminated ceramic frameworks connected through the bridging structure.
Wherein the thickness of the single-layer flaky ceramic layer in the obtained ceramic skeleton is 5-25 mu m, and the interlayer spacing between the flaky ceramic layers is 1-10 mu m. During degumming treatment, the dispersing agent volatilizes to form a pore structure on the surface of the ceramic skeleton, wherein the closed pore porosity of the ceramic skeleton is about 1%, and the open pore porosity is 20-60vol%.
S5, impregnating the ceramic framework into liquid resin so that the liquid resin is filled in the pore structure of the ceramic framework, adding an initiator and the liquid resin to perform in-situ polymerization to generate a high polymer material, and performing annealing treatment to obtain the ceramic high polymer composite material.
In the liquid resin infiltration process, excessive liquid resin is adopted to infiltrate the ceramic framework, so that the liquid resin can be fully filled between layered ceramic layers and in a pore structure of the ceramic framework, an interlocking structure is formed between a polymer generated after in-situ polymerization and the ceramic framework, and the strength and toughness of the composite material are improved. The annealing treatment releases the residual stress in the material, and simultaneously enables the resin which is not fully reacted in the in-situ polymerization to completely react or volatilize excessive liquid resin, so that the residual liquid resin is prevented from entering blood circulation after the ceramic polymer composite material is used as the denture material.
Preferably, the liquid resin comprises one or more of methyl methacrylate resin, acrylic resin, urethane Dimethacrylate (UDMA), triethylene glycol dimethacrylate (TEGEMA) or bisphenol a glycidyl methacrylate (BIS-GMA); the initiator comprises one or two of azodiisobutyronitrile or dibenzoyl peroxide.
Further preferably, the liquid resin solution is selected from methyl methacrylate resin or a mixed solution of 95% methyl methacrylate resin and 5% acrylic resin or a mixed solution of 50% udma and 50% tegema.
Preferably, in step S5, before impregnating the ceramic skeleton with the liquid resin, the method further comprises: and adopting a surface modifier to carry out surface modification on the ceramic framework. The preparation method is used for improving the wettability of the ceramic skeleton and the liquid resin, so that the liquid resin can be filled in the ceramic skeleton more easily, and meanwhile, the use of the surface modifier increases the interface bonding strength of the ceramic skeleton and the polymer material generated by in-situ polymerization, and increases the mechanical strength and toughness of the finally obtained ceramic polymer composite material.
Preferably, after step S4 and before step S5, the method further comprises: and (3) soaking the ceramic skeleton obtained in the step (S4) in a dyeing liquid, and sequentially carrying out drying treatment and sintering treatment on the dyed ceramic skeleton after the soaking is finished. Wherein the staining solution component comprises one or more metal inorganic salt compounds; the metal inorganic salt compound comprises acetic acid, oxalic acid, citric acid, acetylacetone or nitrate of metal iron, metal manganese, metal cobalt, metal erbium or metal praseodymium. The drying treatment temperature is 60-80 ℃ and the drying time is 2-2.5h; the sintering treatment temperature is 1350-1450 ℃ and the sintering time is 2-2.5h.
Preferably, the compression mold comprises a mold cavity assembly for enclosing a compression mold cavity of a compressed paraffin-impregnated green body, and a power assembly for applying a compression power to the mold cavity assembly.
The beneficial effects of the invention at least comprise:
the ceramic polymer composite material comprises a ceramic skeleton and a polymer material filled in the ceramic skeleton; the ceramic polymer composite material is prepared by mixing raw materials of a ceramic skeleton to obtain slurry, preparing the slurry into blanks with mutually parallel lamellar structures by adopting bidirectional freezing casting, placing the obtained blanks into a compression mould to perform volume compression under low pressure, sequentially performing degumming treatment and sintering treatment to obtain the ceramic skeleton, and impregnating the ceramic skeleton into liquid resin to polymerize the liquid resin into a pore structure of the ceramic skeleton to obtain the polymer material. The ceramic polymer composite material has higher hardness, strength and fracture toughness, simultaneously obtains transmittance, color and luster which are more similar to those of human teeth in an attractive manner, and has better application prospect as a denture material.
The invention fills the ceramic skeleton in the mode of in-situ polymerization to generate the polymer material, thereby increasing the fracture toughness and the mechanical property of the obtained ceramic composite material.
In the preparation process of the ceramic polymer composite material, the compression mold is adopted to compress the obtained green embryo at low pressure, so that the distance between the layered structures in the green embryo is increased, the volume fraction of the green embryo is increased, the mechanical strength of the green embryo is increased, the damage to the microstructure of the layered structure of the green embryo is avoided, the integrity of the layered structure is ensured, the continuity of the layered structure in the obtained ceramic skeleton is further ensured, the internal structure of the finally prepared ceramic polymer composite material is further ensured to have better continuity, the interface is less, and the light transmittance of the ceramic polymer composite material is improved.
Drawings
FIG. 1 is a scanning electron microscope test chart of the ceramic polymer composite material obtained by the invention;
FIG. 2 is a schematic view of a compression mold of the present invention;
fig. 3 is a schematic view of the state of the compression mold during the compression operation.
Wherein a is a layered structure, b is a bridging structure, c is a polymer material, 11 is a connecting plate, 111 is a chute, 12 is a frame, 121 is a first side plate, 122 is a second side plate, 123 is a third side plate, 13 is a fixed baffle, 21 is a connecting rod, 22 is a supporting plate, 23 is a guide rod, 24 is a sliding plate, 25 is a push rod, 26 is a pressing plate, 27 is a rotating wheel, and 3 is a bottom plate.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The ceramic polymer composite material is prepared by mixing raw materials of a ceramic skeleton to obtain slurry, preparing the slurry into a green body with a stacked layered structure by adopting bidirectional freezing casting, placing the green body into a compression mold for volume compression, sequentially performing degumming treatment and sintering treatment to obtain the ceramic skeleton, and impregnating the ceramic skeleton into liquid resin. Fig. 1 is a scanning electron microscope test chart of a ceramic polymer composite material obtained by the invention, as shown in fig. 1, the ceramic skeleton of the ceramic polymer composite material comprises a layered structure a, each two adjacent sheets in the layered structure a form a bridging structure b, the polymer material c is filled in pores of the ceramic skeleton, and the layered structures a are stacked in parallel.
Example 1
In the embodiment, zirconia ceramic powder is selected, 61 parts of zirconia powder, 0.305 part of Solo920,1.22 parts of polyvinyl alcohol and 1.22 parts of polyacrylic acid are subjected to ball milling for 24 hours, and zirconia is uniformly dispersed in 90 parts of deionized water to obtain slurry with the volume fraction of 10%.
Pouring the slurry into a bidirectional freezing casting mould with a freezing angle of 10 degrees for bidirectional freezing casting, and performing low-pressure freezing and drying treatment after the slurry is completely solidified so as to fully sublimate frozen ice crystals, thereby obtaining a zirconia laminar green body with the volume fraction of about 9%; wherein the pressure during the low-pressure freeze drying treatment is set to be 1Pa, the treatment is carried out for 24 hours at the temperature of minus 55 ℃, and the temperature of the sample heating plate is 40 ℃.
Preheating the embryo blank to 80 ℃, placing the embryo blank in liquid paraffin with the same temperature, standing for 30 minutes until the paraffin permeates the ceramic embryo blank, placing the paraffin-permeated embryo blank in a special compression mould while the embryo blank is hot, namely placing the paraffin and the embryo blank in the compression mould at the same time, enabling the compression direction to be perpendicular to the direction of the layered structure, and providing a pressure of about 0.1Mpa to reduce the thickness of the embryo blank to 28.5% of the original size. After the embryo is cooled, placing the embryo in a muffle furnace for degumming and sintering treatment to obtain a ceramic skeleton with a bionic bridge layer structure; the degumming treatment temperature is 550 ℃, and the treatment time is 2 hours; the sintering treatment temperature is 1150 ℃ and the treatment time is 2 hours.
And (3) impregnating the ceramic skeleton with liquid resin. The impregnation process sequentially comprises the following steps:
1. ceramic surface modification: placing the ceramic skeleton into a solution of 50 parts of gamma-methacryloxypropyl trimethoxy silane (KH 570) and 50 parts of ethanol as a silane coupling agent, and preserving for 12 hours at normal temperature; 2. impregnating with liquid resin: 99.5 parts of MMA and 0.5 part of BPO are mixed by stirring for 5 minutes and then poured into the ceramic skeleton; 3. activation initiator/pre-polymerization: placing the ceramic skeleton immersed with the liquid resin in a water bath at 70 ℃ for 20 minutes, wherein the liquid resin presents a viscosity similar to that of glycerol; 4. in-situ polymerization: the temperature of the water bath is reduced to 45 ℃, and the liquid resin is completely solidified after 24 hours of maintenance; 5. annealing: the ceramic and resin were placed in an oven at 120 ℃ for 2h to remove residual stress. And (3) impregnating the ceramic skeleton with a polymer to obtain the ceramic polymer bionic composite material with a bionic bridge layer structure.
Example 2
Example 2 is different from example 1 in that it further includes dyeing treatment of the ceramic skeleton. The dyeing process comprises the steps of: placing the ceramic skeleton in a pre-prepared dyeing liquid, soaking for 30s, drying at 80 ℃ for 2h, and sintering at 1350 ℃ for 2h to obtain the dyed ceramic skeleton. The dyeing liquid comprises one or more of oxalic acid, acetic acid, ferric nitrate, neodymium nitrate, erbium nitrate or cerium acetate.
Example 3
Compared with the embodiment 1, the difference of the embodiment is that the ceramic powder in the embodiment is alumina ceramic powder.
Comparative example 1
The green embryos impregnated in paraffin were volume compressed at high pressure using an existing common compression mold.
The ceramic polymer composites prepared in examples 1 to 3 and comparative example 1 were subjected to performance tests, respectively, including a porosity test of a ceramic skeleton, and Young's modulus test, fracture toughness test, porosity test and light transmittance test of the ceramic polymer composites; the porosity test of the ceramic skeleton adopts mercury intrusion method, young modulus test adopts Young modulus tester to test, fracture toughness test adopts single opening bending resistance test and light transmittance test method described in American society for materials standard E1820, and is translucence index (TP) and direct transparency (T).
The results of the performance tests are shown in the following table:
referring to the performance test result table, the open pore porosities of the ceramic frameworks prepared by adopting the schemes of examples 1-3 are respectively 72vol%, 72vol% and 20-82vol% which are larger than those of the ceramic frameworks prepared by adopting the scheme of comparative example 1, and the larger open pore porosities enable more polymer materials to be filled in the open pore structure, so that the contact area between the polymer materials and the ceramic frameworks is increased, and further, more interlocking structures are formed between the polymer materials and the ceramic frameworks, so that the physical properties of the prepared ceramic polymer materials are improved. Reference Young's modulus, fracture toughness K IC Fracture toughness K JC And the flexural strength test results show that the strength and toughness of the ceramic polymer composite materials prepared by adopting the embodiments 1-3 are better than those of the composite materials prepared by adopting the scheme of the comparative example 1. According to the transmittance test result, the transmittance and the semi-transmittance value of the ceramic polymer composite material prepared by adopting the scheme of the embodiment 1-3 are smaller than those of the composite material prepared by adopting the scheme of the comparative example 1, so that the transmittance of the ceramic polymer composite material prepared by the embodiment of the invention is in a proper range, and the appearance of the prepared denture is more warm, moist and attractive and is more similar to the aesthetic appearance of the original teeth.
Example 4
Fig. 2 is a schematic diagram of a compression mold according to the present invention, and as shown in fig. 2, the compression mold includes a mold cavity assembly and a power assembly, the mold cavity assembly is used for enclosing a compression mold cavity of a green blank impregnated with compressed paraffin, and the power assembly is used for applying compression power to the mold cavity assembly.
The die cavity assembly comprises a connecting plate 11, a type frame 12 which is connected to the connecting plate 11 in a sliding manner, and a fixed baffle 13 which is arranged at the opening end of the type frame 12, wherein the fixed baffle 13 and the type frame 12 enclose a compression die cavity; the bottom of the fixed baffle 13 is fixedly arranged on the connecting plate 11.
The power assembly comprises a connecting rod 21, fixed support plates 22, a guide rod 23, a slide plate 24, a push rod 25 and a pressing plate 26, wherein the connecting rod 21 is arranged in parallel along the sliding direction of the type frame 12, the fixed support plates 22 are arranged at two ends of the connecting rod 21, the guide rod 23 is parallel to the connecting rod 21 and is rotationally connected with the support plates 22, the slide plate 24 is movably connected with the connecting rod 21 and the guide rod 23, the push rod 25 extends from the slide plate 24 to the type frame 12 and penetrates through and protrudes out of the support plates 22, and the pressing plate 26 is arranged at the protruding end of the push rod 25; the guide rod 23 is far away from one end of the die cavity assembly and protrudes out of the fixed support plate 22, the sliding plate 24 is in threaded connection with the guide rod 23, the sliding plate 24 is driven to reciprocate by the rotation of the guide rod 23, and the sliding plate 24 drives the push rod 25 and the pressing plate 26 to reciprocate together along the direction parallel to the guide rod 23.
The bottom support plate 22 is provided with a hole for the push rod 25 to pass through, the guide rod 23 is preferably a fine thread threaded rod or a screw rod, the slide plate 24 is provided with a threaded hole matched with the guide rod 23, and the slide plate 24 is also provided with a through hole for the connecting rod 21 to pass through.
Alternatively, in order to ensure the smoothness of the running of the sliding plate 24, the connecting rod 21 and the guide rod 23 are distributed in an isosceles triangle shape. Specifically, the connecting rod 21 is disposed near the bottom of the slide plate 24, and the guide rod 23 is disposed near the top of the slide plate 24. It should be noted that, in the embodiment of the present invention, the top refers to a direction away from the base plate 3, and the bottom refers to a direction close to the base plate 3. The push rods 25 are symmetrically arranged on two sides of the pressing plate 26, and the connecting plane of the push rods 25 is positioned between the guide rod 23 and the connecting rod 21.
Alternatively, the support plate 22 is Fang Xingban; further preferably, the support plate 22 further includes a base disposed at the bottom of the square plate, the Fang Xingban is connected to the bottom plate 3 through the base, and a section formed by the base and the square plate is T-shaped or L-shaped.
The frame 12 includes a first side plate 121 disposed parallel to the fixed baffle 13, and a second side plate 122 and a third side plate 123 disposed perpendicularly on two sides of the first side plate 121, where bottoms of the second side plate 122 and the third side plate 123 are respectively slidably connected with the connecting plate 11.
The central axis of the pressing plate 26 corresponds to the central axis of the first side plate 121. Preferably, the ratio of the surface area of the pressing plate 26 to the surface area of the first side plate 121 is 2/3-1; the surface area of the first side plate 121 is equal to the surface area of the fixed baffle 13.
The connecting plate 11 is provided with a chute 111 at a position corresponding to the second side plate 122 and the third side plate 123, and bottom ends of the second side plate 122 and the third side plate 123 are embedded into the chute 111. Alternatively, a sliding member is provided at the bottom end of the type frame 12, which is cooperatively connected with the chute 111.
The guide rod 23 is provided with a scale for measuring the sliding distance of the sliding plate 24, so as to accurately control the compression amount and the compression force.
The guide rod 23 is provided with a rotating wheel 27 penetrating the end of the support plate 22 at the other end. Alternatively, in order to control the rotation of the rotating wheel 27 more conveniently, a handle is provided on the rotating wheel 27.
The compression mold further comprises a bottom plate 3 used for setting the mold cavity assembly and the power assembly, wherein the mold cavity assembly is connected with the bottom plate 3 through a connecting plate 11, the power assembly is connected with the bottom plate 3 through a supporting plate 22, and the supporting plate 22 is perpendicular to the plane of the bottom plate 3.
Fig. 3 is a schematic view of the state of the compression mold during the compression operation, and as shown in fig. 3, the principle of using the compression mold according to the present invention is as follows:
when the device is used, the rotating wheel 27 is rotated to enable the guide rod 23 to rotate, the sliding plate 24 connected to the guide rod 23 moves towards the type frame 12, the push rod 25 connected to the sliding plate 24 is driven to move towards the type frame 12, the pressing plate 26 connected to the protruding end of the push rod 25 is driven to move towards the type frame 12, the pressing plate 26 is further enabled to be in contact with the first side plate 121 of the type frame 12 and push the type frame 12 to move close to the fixed baffle 13, the volume of a compression mold cavity enclosed by the type frame 12 and the fixed baffle 13 is reduced, and therefore the volume compression of a sample to be compressed in the compression mold cavity is achieved; stopping rotating the rotating wheel 27 during compression, so that the compression mould continuously performs isobaric compression on a sample to be compressed; after compression, the rotating wheel 27 is reversely rotated to drive the pressing plate 26 to be far away from the type frame 12.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples only represent preferred embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. The ceramic polymer composite material is characterized by comprising 18-85% by volume of ceramic skeleton and 15-82% by volume of polymer material; the ceramic skeleton comprises a layered structure, wherein every two adjacent sheets in the layered structure form a bridging structure, and the high polymer material is filled in pores of the ceramic skeleton; the polymer material is formed by filling liquid resin into a pore structure of the ceramic skeleton, adding an initiator and the liquid resin for in-situ polymerization;
the raw material components of the ceramic skeleton comprise 10-40wt% of ceramic powder, 0.4-1wt% of dispersing agent, 1-6wt% of binder and 0.5-3wt% of plasticizer;
the preparation method of the ceramic skeleton comprises the following steps:
s1: dispersing ceramic powder, a dispersing agent, a binder and a plasticizer in a solvent, and performing ball milling treatment to obtain slurry; the ceramic powder comprises one or more of alumina ceramic powder, zirconia ceramic powder or titanium oxide ceramic powder;
s2: the slurry in the step S1 is defoamed, then bidirectional freezing casting is carried out, and then low-pressure freezing drying treatment is carried out, so that a green body with a layered structure parallel to each other is obtained; forming a bulge on the surface of the layered structure;
s3: preheating the green embryo in the step S2 to 80-85 ℃ and then placing the green embryo in liquid paraffin with the same temperature for infiltration, placing the paraffin-infiltrated green embryo in a compression mold, applying compression force in the direction perpendicular to the layered structure to compress the green embryo, wherein the layered structures are close to each other during compression so that adjacent layered structures are connected together through the protrusions to form a connecting bridge, the compression force is 0.1-10MPa, and the volume shrinkage rate of the paraffin-infiltrated green embryo after compression is 2-38%;
s4: sequentially degumming and sintering the green blanks compressed in the step S3 to obtain laminated ceramic frameworks connected through a bridging structure;
the compression mold comprises a mold cavity assembly and a power assembly, wherein the mold cavity assembly is used for enclosing a compression mold cavity of a green blank impregnated with compressed paraffin, and the power assembly is used for applying compression power to the mold cavity assembly.
2. The ceramic polymer composite material according to claim 1, wherein the dispersant comprises one or more of polyacrylic acid, polyethyleneimine, dolapix series dispersant, zhongjing grease SELOSOL920, sodium dodecyl benzene sulfonate or sodium dodecyl sulfate; the binder comprises one or more of polyvinyl alcohol, polyacrylate or gelatin; the plasticizer comprises one or two of allyl alcohol or ethylene glycol.
3. A method for producing the ceramic polymer composite according to claim 1 or 2, comprising the steps of:
s1: dispersing ceramic powder, a dispersing agent, a binder and a plasticizer in a solvent, and performing ball milling treatment to obtain slurry;
s2: the slurry in the step S1 is defoamed, then bidirectional freezing casting is carried out, and then low-pressure freezing drying treatment is carried out, so that a green body with a layered structure parallel to each other is obtained;
s3: preheating the green embryo in the step S2 to 80-85 ℃ and then placing the green embryo in liquid paraffin with the same temperature for infiltration, placing the paraffin-infiltrated green embryo in a compression mold, and applying compression force in the direction perpendicular to the layered structure to compress the green embryo, wherein the compression force is 0.1-10MPa, and the volume shrinkage rate of the green embryo after paraffin infiltration after compression is 2-38%;
s4: sequentially degumming and sintering the green blanks compressed in the step S3 to obtain laminated ceramic frameworks connected through a bridging structure;
s5, impregnating the ceramic framework into liquid resin so that the liquid resin is filled in the pore structure of the ceramic framework, adding an initiator and the liquid resin to perform in-situ polymerization to generate a high polymer material, and performing annealing treatment to obtain the ceramic high polymer composite material.
4. The method for preparing a ceramic polymer composite material according to claim 3, wherein the liquid resin comprises one or more of methyl methacrylate resin, acrylic resin, urethane dimethacrylate, triethylene glycol dimethacrylate and bisphenol a glycidyl methacrylate; the initiator comprises one or two of azodiisobutyronitrile or dibenzoyl peroxide.
5. The method for producing a ceramic polymer composite material according to claim 4, wherein the liquid resin solution is selected from the group consisting of a mixed solution of methyl methacrylate resin, 95% methyl methacrylate resin and 5% acrylic resin, and a mixed solution of 50% udma and 50% tegema.
6. The method for producing a ceramic polymer composite according to claim 3, further comprising, before impregnating the ceramic skeleton with the liquid resin in step S5: and adopting a surface modifier to carry out surface modification on the ceramic framework.
7. The method for preparing a ceramic polymer composite according to claim 3, further comprising, after step S4 and before step S5: and (3) soaking the ceramic skeleton obtained in the step (S4) in a dyeing liquid, and sequentially carrying out drying treatment and sintering treatment on the dyed ceramic skeleton after the soaking is finished.
8. A method of preparing a ceramic polymeric composite material as claimed in claim 3 wherein the compression mould comprises a mould cavity assembly for enclosing a compression mould cavity of a compressed paraffin impregnated green body and a power assembly for applying a compression power to the mould cavity assembly.
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