CN114767940A - Ceramic polymer composite material and preparation method thereof - Google Patents
Ceramic polymer composite material and preparation method thereof Download PDFInfo
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- CN114767940A CN114767940A CN202210467016.8A CN202210467016A CN114767940A CN 114767940 A CN114767940 A CN 114767940A CN 202210467016 A CN202210467016 A CN 202210467016A CN 114767940 A CN114767940 A CN 114767940A
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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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- 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
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Abstract
The invention relates to a ceramic polymer composite material and a preparation method thereof, wherein the composite material comprises 18-85% of a ceramic framework by volume percentage and 15-82% of a polymer material by volume percentage; the ceramic framework comprises a layered structure, every two adjacent layers in the layered structure form a bridging structure, and the high polymer material is filled in pores of the ceramic framework; the composite material is prepared by mixing raw materials of a ceramic framework to obtain slurry, preparing the slurry into a green body with a stacked layered structure by adopting two-way freezing casting, placing the green body in a compression mould for volume compression, sequentially carrying out degumming treatment and sintering treatment to obtain the ceramic framework, and impregnating the ceramic framework in liquid resin. The ceramic polymer composite material prepared by the technical scheme of the invention has better mechanical property and 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
The false tooth plays an important role in multiple medical treatments such as oral cavity prevention and health care, tooth deformity correction and the like. The denture as a dental material to be implanted into the oral cavity needs to have excellent mechanical properties, good biocompatibility, easy processing, modeling and manufacturing, stable physicochemical properties and high aesthetic similarity. Dentures used at the present stage include metallic alloy teeth, porcelain teeth, all-ceramic teeth, and dentures made of ceramic matrix composites. Wherein, the metal alloy and the porcelain teeth are easy to mislead the diagnosis of the medical image because of the existence of metal; the all-ceramic tooth material has problems of excessive hardness and brittle fracture. Therefore, the denture made of the ceramic matrix composite material is favored by users because the denture does not contain metal elements, has certain mechanical properties and has an aesthetic appearance closer to that of the original teeth.
However, the existing ceramic matrix composite materials in the domestic market generally have high processing difficulty and mechanical properties which can not reach the application range of primary teeth, and the application of the ceramic matrix composite materials in the modern medical chair side repair is severely limited. How to obtain a ceramic matrix composite material which can lead the mechanical property of the manufactured false tooth to be infinitely close to the original tooth and has the aesthetic appearance comparable to the original tooth becomes a core pain point and difficulty accepted by the dental material industry.
Disclosure of Invention
The invention aims to solve the problems and provides a ceramic polymer composite material with high mechanical property and good aesthetic appearance.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a ceramic polymer composite material comprises a ceramic skeleton with the volume percentage of 18-85% and a polymer material with the volume percentage of 15-82%; the ceramic framework is integrally of a layered structure, every two adjacent sheet layers in the layered structure form a bridging structure, and the high polymer material is filled in the pores of the ceramic framework.
Preferably, the raw material components of the ceramic skeleton comprise 10-40 wt% of ceramic powder, 0.4-1 wt% of dispersant, 1-6 wt% of binder and 0.5-3 wt% of plasticizer.
The addition of the binder and the plasticizer ensures that the slurry has enough fluidity, and simultaneously, when the obtained slurry is subjected to bidirectional freezing casting, the formed frozen ice crystals can be subjected to controllable directional growth, so that the obtained green bodies have enough strength and toughness, and the structural integrity of the green bodies in the compression process is ensured; 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 the toughness of the layered structure of the green body are insufficient, and the green body is broken in the volume compression process.
Preferably, the ceramic powder comprises one or more of alumina ceramic powder, zirconia ceramic powder or titania ceramic powder; the dispersant comprises one or more of polyacrylic acid, polyethyleneimine, Dolapix series dispersant, Solo920, sodium dodecyl benzene sulfonate or sodium dodecyl sulfate; the binder comprises one or more of polyvinyl alcohol, polypropylene alcohol 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: dispersing ceramic powder, a dispersing agent, a binder and a plasticizer in a solvent to obtain slurry.
S2: defoaming the slurry obtained in the step S1, then performing two-way freeze casting, and then performing low-pressure freeze drying to obtain a green body with a mutually parallel layered structure;
the bidirectional freeze casting process makes the slurry obtained in step S1 oriented to form a slurry frozen body with a parallel layered structure, and the solvent is frozen in the slurry frozen body at the same time; and sublimating the solvent during low-pressure freeze drying to form a pore structure in the slurry frozen body to obtain a green body with a mutually parallel layered structure, wherein the green body is internally provided with the pore structure.
In addition, the layered structures of the obtained green bodies are connected by connecting bridges. The forming principle of the connecting bridge is as follows: in the two-way freezing casting process, because the cold source direction is not completely consistent with the growth direction of freezing ice crystals, bulges can be formed on the surfaces of the layered structures, and when the volume is compressed in a compression mould, because the layered structures are close to each other, the adjacent layered structures are connected together through the bulges to form a connecting bridge, and a laminated ceramic skeleton connected through the bridging structure is formed after sintering. The volume compression amount of the blank after paraffin infiltration is controlled by controlling the volume fraction of the blank, so that the number of connecting bridges between adjacent layered structures is controlled, and finally, the mechanical performance of the ceramic skeleton is controlled.
S3: preheating the green blank obtained in the step S2 to 80-85 ℃, then placing the green blank into liquid paraffin with the same temperature for infiltration, then placing the paraffin-infiltrated green blank into a compression mold, and applying a compression force along the direction vertical to the laminated structure to compress the green blank, wherein the magnitude of the compression force is 0.1-10MPa, and the volume shrinkage of the paraffin-infiltrated green blank after compression is 2-38%.
The compression is carried out for the purpose of reducing the interlayer distance of the laminated structure and providing a basis for the ceramic skeleton obtained later to have better mechanical properties. The raw blank impregnated by the paraffin is compressed under low pressure, so that the damage of a laminated structure caused by large compression pressure is avoided, and the continuity of the laminated structure is ensured.
The method adopts a compression mould to compress the volume of the paraffin-impregnated green body by adopting low pressure, and improves the volume fraction of the paraffin-impregnated green body from 10-30% to 32-48% under the condition of ensuring that the microstructure of the green body is not damaged, so that the volume shrinkage of the paraffin-impregnated green body after compression is 2-38%. The compression is carried out at the same temperature as the preheating temperature, the dispersing agent has good flexibility, the flexibility of the green body in the compression process is further guaranteed, the layered structure of the green body is prevented from being broken by pressing, meanwhile, the low-pressure compression is carried out with the aid of the dispersing agent, the layered structure of the green body is not prone to being broken by pressing, the continuity of the layered structure is guaranteed, the continuity of the layered structure in the ceramic skeleton is guaranteed, and the finally obtained ceramic polymer composite material has better mechanical properties.
S4: and (4) sequentially carrying out degumming treatment and sintering treatment on the green body compressed in the step S3 to obtain the laminated ceramic skeleton connected through the bridging structure.
Wherein the thickness of the single-layer flaky ceramic layer in the obtained ceramic framework is 5-25 μm, and the interlayer spacing between the flaky ceramic layers is 1-10 μm. During degumming treatment, the dispersing agent is volatilized on the surface of the ceramic skeleton to form a pore structure, the closed porosity of the ceramic skeleton is about 1%, and the open porosity is 20-60 vol%.
S5, impregnating the ceramic skeleton into liquid resin to enable the liquid resin to be filled in the pore structure of the ceramic skeleton, adding an initiator to carry out in-situ polymerization with the liquid resin to generate a high polymer material, and then annealing to obtain the ceramic high polymer composite material.
In the liquid resin impregnation process, excessive liquid resin is adopted to impregnate 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 the 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 enables the excessive liquid resin to volatilize, thereby avoiding the residual liquid resin entering the 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, dimethyl acrylic acid carbamate (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 a 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 the step of impregnating the ceramic skeleton with the liquid resin, the method further includes: and carrying out surface modification on the ceramic framework by adopting a surface modifier. The method is used for improving the wettability of the ceramic framework and liquid resin, so that the liquid resin can be filled in the ceramic framework more easily, and meanwhile, the use of the surface modifier increases the interface bonding strength of the ceramic framework and a high polymer material generated by in-situ polymerization, and increases the mechanical strength and toughness of the finally obtained ceramic high polymer composite material.
Preferably, after step S4 and before step S5, the method further comprises: and (5) soaking the ceramic framework obtained in the step (S4) in a dyeing solution, and after soaking, sequentially drying and sintering the dyed ceramic framework. Wherein the dyeing liquor 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 temperature is 60-80 ℃, and the drying time is 2-2.5 h; the sintering treatment temperature is 1350-.
Preferably, the compression mould comprises a mould cavity assembly and a power assembly, wherein the mould cavity assembly is used for enclosing a compression mould cavity of the compression paraffin impregnated green blank, and the power assembly is used for applying compression power to the mould cavity assembly.
The beneficial effects of the invention at least comprise:
the ceramic polymer composite material comprises a ceramic framework and a polymer material filled in the ceramic framework; 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 mutually parallel layered structure by adopting two-way freezing casting, placing the obtained green body in a compression mould, carrying out volume compression under low pressure, sequentially carrying out degumming treatment and sintering treatment to obtain the ceramic skeleton, and impregnating the ceramic skeleton in liquid resin to ensure that the liquid resin is polymerized in a pore structure of the ceramic skeleton to generate a polymer material. The ceramic polymer composite material has higher hardness, strength and fracture toughness, and obtains more close to the transmittance, color and luster of human teeth in appearance, and has better application prospect as a denture material.
According to the invention, the ceramic framework is filled in a mode of generating the high polymer material by in-situ polymerization, so that the fracture toughness of the obtained ceramic composite material is increased, and the mechanical property of the ceramic composite material is improved.
In the preparation process of the ceramic polymer composite material, the obtained green body is compressed at low pressure by adopting the compression mold, so that the distance between the layered structures in the green body is increased, the volume fraction of the green body is improved, the mechanical strength of the green body is increased, meanwhile, the damage to the microstructure of the layered structure of the green body 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 ensured to have better continuity, the interfaces are fewer, 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 present 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 in the compression operation.
Wherein, a is a laminated structure, b is a bridging structure, c is a polymer material, 11 is a connecting plate, 111 is a chute, 12 is an Contraband-shaped 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
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying 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 in the description of the invention herein 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 the raw materials of a ceramic skeleton to obtain slurry, preparing the slurry into a green body with a stacked layered structure by adopting two-way freezing casting, placing the green body in a compression mould for volume compression, sequentially carrying out degumming treatment and sintering treatment to obtain the ceramic skeleton, and impregnating the ceramic skeleton in liquid resin. Fig. 1 is a scanning electron microscope test chart of the ceramic polymer composite material obtained in the present invention, as shown in fig. 1, the ceramic skeleton of the ceramic polymer composite material includes a layered structure a, every two adjacent sheets in the layered structure a form a bridging structure b, the polymer material c is filled in the pores of the ceramic skeleton, and the layered structures a are stacked in parallel.
Example 1
In the embodiment, the ceramic powder is zirconia ceramic powder, and 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 to uniformly disperse zirconia in 90 parts of deionized water to obtain slurry with the volume fraction of 10%.
Pouring the slurry into a bidirectional freezing casting mold with a freezing angle of 10 degrees for bidirectional freezing casting, and after the slurry is completely solidified, performing low-pressure freezing and drying treatment to fully sublimate frozen ice crystals so as to obtain a zirconium oxide layered blank with the volume fraction of about 9%; wherein the pressure during the low-pressure freeze drying treatment is set to be 1Pa, the sample is treated at-55 ℃ for 24h, and the temperature of a heating plate of the sample is 40 ℃.
Preheating a blank body of a blank to 80 ℃, placing the blank body in liquid paraffin at the same temperature, standing for 30 minutes until the paraffin penetrates through the ceramic blank body, placing the blank body impregnated with the paraffin into a special compression mold while the blank body is hot, namely simultaneously placing the paraffin and the blank body into the compression mold, enabling the compression direction to be vertical to the direction of the laminated structure, and providing pressure of about 0.1Mpa to reduce the thickness of the blank body to 28.5 percent of the original size. After the blank body is cooled, placing the blank body in a muffle furnace for degumming and sintering treatment to obtain a ceramic framework 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 h.
And (3) performing liquid resin impregnation on the ceramic framework. The infiltration process comprises the following steps in sequence:
1. modifying the surface of the ceramic: placing the ceramic skeleton into a solution of 50 parts of gamma-methacryloxypropyl trimethoxy silane (KH570) serving as a silane coupling agent and 50 parts of ethanol, and storing at normal temperature for 12 hours; 2. liquid resin impregnation: 99.5 parts of MMA and 0.5 part of BPO were mixed by stirring for 5 minutes and then poured over a ceramic skeleton; 3. activation initiator/prepolymerization: placing the ceramic skeleton soaked with the liquid resin in a water bath at 70 ℃ for 20 minutes, wherein the liquid resin has the viscosity similar to that of glycerol; 4. in-situ polymerization: reducing the temperature of the water bath to 45 ℃, and maintaining for 24 hours until the liquid resin is completely cured; 5. and (3) annealing treatment: and (3) placing the ceramic and the resin in an oven for heat preservation for 2 hours at 120 ℃, and removing residual stress. And (3) obtaining the ceramic polymer bionic composite material with the bionic bridge layer structure after the ceramic framework is subjected to polymer infiltration.
Example 2
Example 2 is different from example 1 in that it further comprises dyeing the ceramic skeleton. The dyeing process comprises the steps of: and (3) placing the ceramic framework in a pre-prepared dyeing solution, soaking for 30s, drying at 80 ℃ for 2h, and sintering at 1350 ℃ for 2h to obtain the dyed ceramic framework. 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 example 1, the present example is different in that alumina ceramic powder is used as the ceramic powder in the present example.
Comparative example 1
The volume of the green body impregnated in paraffin was compressed under high pressure using an existing common compression mold.
Respectively carrying out performance tests on the ceramic polymer composite materials prepared in the examples 1-3 and the comparative example 1, wherein the performance tests comprise a porosity test of a ceramic framework, and a Young modulus test, a fracture toughness test, a porosity test and a light transmittance performance test of the ceramic polymer composite material; the porosity test of the ceramic framework adopts a mercury intrusion method, the Young modulus test adopts a Young modulus tester to test, the fracture toughness test adopts the single-opening bending resistance test and the light transmission performance test in American society for materials standard E1820, and the test methods comprise translucency index (TP) and direct transparency (T).
The results of the performance tests are shown in the following table:
referring to a performance test result table, the open porosity of the ceramic skeleton prepared by the schemes of the embodiments 1 to 3 is respectively 72 vol%, 72 vol% and 20 to 82 vol%, which are respectively greater than the open porosity of the ceramic skeleton prepared by the scheme of the comparative example 1, and the larger open porosity enables more high polymer materials to be filled in the open structure, so that the contact area between the high polymer materials and the ceramic skeleton is increased, and further more interlocking structures are formed between the high polymer materials and the ceramic skeleton, so that the physical performance of the prepared ceramic high polymer materials is improved. Reference Young's modulus, fracture toughness KICFracture toughness KJCAnd bending strength test results, the strength and toughness of the ceramic polymer composite materials prepared by the embodiments 1-3 of the invention are superior to those of the composite material prepared by the scheme of the comparative example 1. Referring to the transmittance test results, the transmittance and the semi-transmittance values of the ceramic polymer composite materials prepared by the schemes of examples 1 to 3 of the invention are smaller than those of the composite material prepared by the scheme of comparative example 1, which shows that the inventionThe transmittance of the ceramic polymer composite material prepared by the embodiment is in a proper range, and the prepared denture is more moist and beautiful and is closer to the aesthetic appearance of the original teeth.
Example 4
The compression mold according to the present invention, fig. 2 is a schematic view of the compression mold according to the present invention, and as shown in fig. 2, 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 compressed paraffin-impregnated green body, and the power assembly is used for applying a compression power to the mold cavity assembly.
The die cavity assembly comprises a connecting plate 11, an Contraband type frame 12 connected to the connecting plate 11 in a sliding manner, and a fixed baffle 13 arranged at the opening end of the Contraband type frame 12, wherein the fixed baffle 13 and the Contraband 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 arranged in parallel along the sliding direction of the Contraband type frame 12, fixed supporting plates 22 arranged at two ends of the connecting rod 21, a guide rod 23 parallel to the connecting rod 21 and rotatably connected with the supporting plates 22, a sliding plate 24 movably connected to the connecting rod 21 and the guide rod 23, a push rod 25 extending from the sliding plate 24 to the Contraband type frame 12 and penetrating and protruding out of the supporting plates 22, and a pressing plate 26 arranged at the protruding end of the push rod 25; one end of the guide rod 23, which is far away from the die cavity assembly, protrudes out of the fixed support plate 22, the sliding plate 24 is in threaded connection with the guide rod 23, the guide rod 23 rotates to drive the sliding plate 24 to reciprocate on the guide rod, and the sliding plate 24 drives the push rod 25 and the pressure plate 26 to reciprocate together along the direction parallel to the guide rod 23.
The bottom end support plate 22 is provided with a hole for the push rod 25 to pass through, the guide rod 23 is preferably a fine threaded rod or a screw rod, the sliding plate 24 is provided with a threaded hole matched with the guide rod 23, and the sliding plate 24 is further provided with a through hole for the connecting rod 21 to pass through.
Alternatively, in order to ensure the smooth operation of the slide plate 24, the connecting rod 21 and the guide bar 23 are distributed in an isosceles triangle. Specifically, the connecting rod 21 is disposed near the bottom of the slide plate 24, and the guide bar 23 is disposed near the top of the slide plate 24. It should be noted that the top in the embodiment of the present invention refers to a direction away from the bottom plate 3, and the bottom refers to a direction close to the bottom plate 3. The push rods 25 are symmetrically arranged on two sides of the pressing plate 26, and the connection plane of the push rods 25 is located between the guide rod 23 and the connecting rod 21.
Optionally, the support plate 22 is a square plate; further preferably, the supporting plate 22 further comprises a base arranged at the bottom of the square plate, the square plate is connected with the bottom plate 3 through the base, and the cross section formed by the base and the square plate is T-shaped or L-shaped.
The Contraband-shaped frame 12 comprises a first side plate 121 parallel to the fixed baffle 13, and a second side plate 122 and a third side plate 123 vertically arranged at two sides of the first side plate 121, wherein the bottoms of the second side plate 122 and the third side plate 123 are respectively connected with the connecting plate 11 in a sliding manner.
The central axis of the pressing plate 26 is arranged corresponding to the central axis of the first side plate 121. Preferably, the ratio of the surface area of the pressure 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.
A sliding groove 111 is formed in the connecting plate 11 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 in the sliding groove 111. Optionally, the bottom end of the Contraband-shaped frame 12 is provided with a sliding member in fit connection with the sliding groove 111.
Scales for measuring the sliding distance of the sliding plate 24 are arranged on the guide rod 23, so that the compression amount and the compression force can be accurately controlled.
The guide rod 23 penetrates through the end part of the support plate 22 at the other end, and a rotating wheel 27 is arranged at the end part. Alternatively, in order to control the rotation of the wheel 27 more conveniently, a handle is provided on the wheel 27.
The compression mold further comprises a bottom plate 3 used for arranging the mold cavity assembly and the power assembly, 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 a state of the compression mold during compression operation, and as shown in fig. 3, the compression mold according to the present invention has the following usage principle:
when the device is used, the rotating wheel 27 is rotated to enable the guide rod 23 to rotate, so that the sliding plate 24 connected to the guide rod 23 moves towards the Contraband-shaped frame 12, the push rod 25 connected to the sliding plate 24 is driven to move towards the Contraband-shaped frame 12, the pressure plate 26 connected to the protruding end of the push rod 25 is driven to move towards the Contraband-shaped frame 12, the pressure plate 26 is further made to be in contact with the first side plate 121 of the Contraband-shaped frame 12 and push the Contraband-shaped frame 12 to move close to the fixed baffle 13, the volume of a compression cavity defined by the Contraband-shaped frame 12 and the fixed baffle 13 is reduced, and therefore volume compression is performed on a sample to be compressed in the compression cavity; when in compression, the rotating wheel 27 stops rotating, so that the compression mold continuously compresses the sample to be compressed in an isobaric manner; after compression is completed, the runner 27 is rotated in the reverse direction to move the pressing plate 26 away from the Contraband-shaped frame 12.
All possible combinations of the technical features in the above embodiments may not be described for the sake of brevity, but should be considered as being within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above examples only express preferred embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The ceramic polymer composite material is characterized by comprising 18-85% by volume of a ceramic skeleton and 15-82% by volume of a polymer material; the ceramic framework comprises a layered structure, every two adjacent layers in the layered structure form a bridging structure, and the high polymer material is filled in pores of the ceramic framework.
2. The ceramic polymer composite material according to claim 1, wherein the raw material components of the ceramic skeleton comprise 10-40 wt% of ceramic powder, 0.4-1 wt% of dispersant, 1-6 wt% of binder and 0.5-3 wt% of plasticizer.
3. The ceramic polymer composite material according to claim 2, wherein the ceramic powder comprises one or more of alumina ceramic powder, zirconia ceramic powder or titania ceramic powder; 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, polypropylene alcohol or gelatin; the plasticizer comprises one or two of allyl alcohol or ethylene glycol.
4. The preparation method of the ceramic polymer composite material is characterized by comprising the following steps:
s1: dispersing ceramic powder, a dispersing agent, a binder and a plasticizer in a solvent, and then performing ball milling treatment to obtain slurry;
s2: defoaming the slurry obtained in the step S1, then performing two-way freezing casting, and then performing low-pressure freezing drying treatment to obtain green blanks with mutually parallel layered structures;
s3: preheating the blank in the step S2 to 80-85 ℃, then placing the blank in liquid paraffin at the same temperature for impregnation, then placing the paraffin-impregnated blank in a compression mould, and applying a compression force along the direction vertical to the laminated structure to compress the blank, wherein the magnitude of the compression force is 0.1-10MPa, and the volume shrinkage rate of the paraffin-impregnated blank after compression is 2-38%;
s4: sequentially degumming and sintering the green blank compressed in the step S3 to obtain a laminated ceramic skeleton connected through a bridging structure;
s5, impregnating the ceramic skeleton into liquid resin to enable the liquid resin to be filled in the pore structure of the ceramic skeleton, adding an initiator to carry out in-situ polymerization with the liquid resin to generate a high polymer material, and then annealing to obtain the ceramic high polymer composite material.
5. The method for preparing the ceramic polymer composite material according to claim 4, wherein the liquid resin comprises one or more of methyl methacrylate resin, acrylic resin, dimethyl acrylic acid carbamate, triethylene glycol dimethacrylate and bisphenol A glycidyl methacrylate; the initiator comprises one or two of azodiisobutyronitrile or dibenzoyl peroxide.
6. The method of claim 5, wherein the liquid resin solution is selected from the group consisting of a methyl methacrylate resin, a mixture of 95% methyl methacrylate resin and 5% acrylic resin, and a mixture of 50% UDMA and 50% TEGEMA.
7. The method of claim 4, wherein before the step S5 of impregnating the ceramic skeleton with a liquid resin, the method further comprises: and carrying out surface modification on the ceramic framework by adopting a surface modifier.
8. The method of claim 4, further comprising, after the step S4 and before the step S5: and (5) soaking the ceramic framework obtained in the step (S4) in a dyeing solution, and after soaking, sequentially drying and sintering the dyed ceramic framework.
9. The method of claim 4, wherein the compression mold comprises a mold cavity assembly and a power assembly, the mold cavity assembly is used for enclosing a compression mold cavity of a raw blank impregnated with compressed paraffin, and the power assembly is used for applying compression power to the mold cavity assembly.
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