CN112206355B - Profiling artificial bone and preparation method thereof - Google Patents

Profiling artificial bone and preparation method thereof Download PDF

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CN112206355B
CN112206355B CN202011036723.9A CN202011036723A CN112206355B CN 112206355 B CN112206355 B CN 112206355B CN 202011036723 A CN202011036723 A CN 202011036723A CN 112206355 B CN112206355 B CN 112206355B
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artificial bone
tubular structure
carbon fiber
carbon
profiling
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CN112206355A (en
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谭周建
张翔
王斌
刘波
蔡志霞
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Hunan Carbon Kang Biotechnology Co ltd
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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
    • 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
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L27/54—Biologically active materials, e.g. therapeutic substances
    • 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
    • A61L27/56—Porous materials, e.g. foams or sponges
    • 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
    • A61L27/58—Materials at least partially resorbable by the body
    • 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
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses a profiling artificial bone and a preparation method thereof. The profiling artificial bone has an arc-shaped tubular structure, and bioactive materials are filled in the tubular structure. The preparation method of the profiling artificial bone comprises the steps of weaving or knitting carbon fibers into a tubular structure, filling thermoplastic polymer material particles into the tubular structure, utilizing a mold to assist in warm compaction molding, taking out the thermoplastic polymer material, densifying a carbon matrix, and finally filling a bioactive material into the tubular structure. The bionic low-density cancellous bone inside the copying artificial bone has good biocompatibility, the communicated gaps inside the bionic low-density cancellous bone are convenient for blood supply, the bionic cortical layer with the tubular structure shows excellent mechanical property, and a large number of gaps exist in the tube wall, so that the bionic cortical bone is favorable for autologous tissue adhesion and is particularly suitable for rib and phalanx repair.

Description

Profiling artificial bone and preparation method thereof
Technical Field
The invention relates to a profiling artificial bone, in particular to a profiling artificial bone with bionic shape and function and a preparation method thereof, belonging to the technical field of biological materials.
Background
Clinically, artificial bone implantation is an effective means for anatomically reconstructing clinical treatment due to bone defects caused by trauma, tumors, infection, and dysplasia. At present, the artificial bone implant materials mainly comprise metal, ceramic and high polymer materials, and the following problems mainly exist: the metal has the defects of easy abrasion, easy fatigue, easy corrosion, bone absorption, artifact of medical images and the like; the polymer material has the defects of poor aging and creep resistance, toxic reaction, thrombosis and the like, and the ceramic material has the defects of no plasticity, brittle quality, easy fracture and the like.
In recent years, the composite material with excellent mechanical property is rapidly developed, and a favorable opportunity is provided for the inorganic non-metallization of the artificial bone material. The carbon-based material has good biocompatibility, such as no medical image artifact, no toxic substance release, fiber reinforcement and the like, and shows the biomechanical property matched with the autogenous bone of a human body. For example, chinese patent (CN 110237298A) discloses a biological function modification method of a carbon/carbon composite material, and Chinese patent (CN 108546156A) discloses a carbon/carbon composite material modified by silicon carbide and hydroxyapatite gradient coating and a preparation method thereof, which are both prone to the modification of the material surface.
In fact, the outer layer of the human raw bone is a compact cortical layer, the center is low-density cancellous bone, the artificial bone not only needs to have a bionic shape, but also needs to achieve bionic functions on a macroscopic structure, the outer layer provides a mechanical structure, and the inner layer provides a tissue function. Human bones not only need to maintain the mechanical requirements needed by the self-supporting structure, but also face the influence of external dynamic factors, such as external force impact. Research shows that the impact toughness of the autogenous bone is about 8J/cm 2 Therefore, the design of the non-metal bionic artificial bone must meet the requirements of the autologous bone.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a profiling artificial bone which realizes bionics on both shape and function, a bioactive material bionic low-density cancellous bone with higher porosity and low density is arranged in a tubular structure, the tubular structure has better biocompatibility, the communicated gaps in the tubular structure are convenient for blood supply, the tubular structure is a carbon fiber/carbon composite bionic cortical layer with excellent mechanical property and higher porosity, the excellent mechanical property is shown, and a large number of gaps exist in the tube wall, so that the bionic cortical bone is favorable for autologous tissue adhesion and is particularly suitable for rib and phalanx repair.
The second purpose of the invention is to provide a preparation method of the profiling artificial bone, which has simple operation and low cost and is beneficial to large-scale production.
In order to achieve the above technical objects, the present invention provides a contoured artificial bone having an arc-shaped tubular structure, the tubular structure being filled with a bioactive material; the tubular structure is constructed of a carbon fiber/carbon composite.
The shape of the profiling artificial bone is similar to that of a native bone, the profiling artificial bone is structurally a tubular structure filled with active substances, the interior of the tubular structure is a bioactive material bionic low-density cancellous bone with high porosity and low density, the tubular structure has good biocompatibility, communicated gaps inside the tubular structure are convenient for blood supply, the tubular structure is a carbon fiber/carbon composite material bionic cortical layer with excellent mechanical property and high porosity, the excellent mechanical property is shown, and a large number of pores exist in the wall of the tubular structure, so that autologous tissue adhesion is facilitated.
As a preferred aspect, the bioactive material includes a bioceramic powder and a biodegradable polymer powder. The bionic cancellous bone is formed by mixing the biological ceramic powder and the biodegradable polymer, and the biodegradable polymer is slowly degraded in a physiological environment, so that the biological ceramic powder is loosely accumulated to form the bionic cancellous bone with high porosity and low density.
In a more preferred embodiment, the bioceramic powder is at least one of hydroxyapatite, β -tricalcium phosphate, calcium silicate, and bioglass. The particle size of the biological ceramic powder is 20-100 μm.
As a preferred embodiment, the biodegradable polymer powder is at least one of polycaprolactone, polyurethane, polyglycolic acid, and polylactic acid. The biodegradable polymer powder has a particle size of 10 to 80 μm
As a preferable scheme, the mass ratio of the biological ceramic powder to the biodegradable polymer is 1. The proportion of the ceramic powder is too low, the biological ceramic powder is discontinuous after the polymer is degraded, the proportion of the ceramic powder is too high, and the bioactive material is densely filled.
As a preferable mode, the carbon fiber/carbon composite material is composed of a carbon fiber fabric having a tubular structure and a carbon matrix inside the fabric (the carbon matrix is distributed on the surface of the carbon fibers and filled between the carbon fibers). The main body of the tubular structure is woven or knitted by carbon fiber, has better mechanical property, has a large number of pores for the adhesion and growth of biological tissues and is beneficial to the contact with the tissues.
As a preferable scheme, the carbon fiber/carbon composite material consists of 60-80% of carbon fiber fabric and 20-40% of carbon matrix by mass percent. The porosity of the carbon fiber/carbon composite material accounts for 40-60% of the volume ratio. The proportion of the carbon matrix is too low, the proportion of the through holes is high, bioactive substances in the cavity can seep out through the pipe wall, the effective load transmission is not facilitated, the deformation resistance is weak, the proportion of the carbon matrix is too high, the aperture ratio is reduced, and the tissue ingrowth is not facilitated.
The invention also provides a preparation method of the profiling artificial bone, which is to weave or knit the carbon fiber into a tubular structure; filling thermoplastic polymer material particles in the tubular structure tube cavity, and performing warm-pressing molding by using a mold to obtain a profiling artificial bone blank; taking out the thermoplastic polymer material filled in the cavity of the copying artificial bone blank body, densifying a carbon matrix on the copying artificial bone blank body by a chemical vapor deposition method, and filling a bioactive material in the cavity of the copying artificial bone blank body.
Preferably, the thermoplastic polymer material is at least one of polyethylene, polypropylene, polyvinyl chloride and polystyrene. The particle size of the thermoplastic polymer material particles is 0.5 mm-5 mm. By utilizing the hot melting characteristics of the high polymer materials, the carbon fiber can be woven or knitted into a tubular structure for shaping, and is convenient to take out.
As a preferred scheme, twisting at least two carbon fiber bundles into a carbon fiber rope, and then weaving or knitting the carbon fiber rope into a carbon fiber tubular structure; the carbon fiber bundle contains at least 1k carbon fibers, wherein k represents one thousand. The carbon fiber bundle is processed into the carbon fiber rope, and then the carbon fiber rope is further woven or knitted into a tubular structure, so that the impact toughness can be improved to a certain extent.
As a preferable mode, the warm compaction conditions are as follows: the temperature is 200-240 ℃, and the time is 3-10 h.
As a preferred embodiment, the chemical vapor deposition method has the following conditions: the temperature is 850-1300 ℃, the time is 10-200 h, aliphatic hydrocarbon is used as a carbon gas source, and nitrogen or hydrogen is used as diluent gas.
The preparation method of the profiling artificial bone comprises the following specific steps:
1) Twisting a plurality of carbon fiber bundles (1 k (k represents one thousand), 3k, 6k, 12k, \8230;) into a carbon fiber rope, and weaving the carbon fiber rope into a carbon fiber tubular structure by adopting a conventional weaving or knitting process;
2) Thermoplastic polymer material particles are filled in the inner cavity of the tubular structure, warm-pressing molding is carried out by means of a mold (the mold is a conventional mold and has a rib-shaped inner cavity), and the warm-pressing molding conditions are as follows: the temperature is 200-240 ℃, the time is 3-10 h, and an arc-shaped tubular structure, namely the copying artificial bone blank body, is manufactured;
3) Cooling, removing the mold, heating to 80-180 ℃ again, and taking out the softened thermoplastic polymer material in the inner cavity of the profiling artificial bone blank;
4) The shaped compact carbon matrix of the profiling artificial bone blank body adopts a chemical vapor deposition process, and the specific process comprises the following steps: placing the carbon fiber preform into a deposition furnace, and depositing for 50-200 h at the temperature of 850-1300 ℃ by introducing a carbon-containing gas source (natural gas, methane or propylene, and the like, nitrogen or hydrogen is used as a diluent gas, and the flow ratio of the carbon source gas to the diluent gas is 1-0);
5) Processing, including cutting the end or processing a fixing hole and the like; the aperture size of the fixing hole is generally 0.5 mm-2 mm (wherein, the fixing hole can also be reserved in the carbon fiber weaving or knitting process, which can effectively avoid the reduction of mechanical property caused by the damage of the artificial bone of the carbon fiber composite material in the later processing);
6) Placing the machined copying artificial bone blank into a high-temperature furnace, heating under the condition of vacuum or protective atmosphere to remove impurities, wherein the treatment temperature is 1500-2300 ℃, and the heat preservation time is 1-10 h (the step can be adopted or not adopted according to the requirement);
7) Filling a bioactive mixture into the copying artificial bone blank to obtain a copying artificial bone; the bioactive material consists of bioceramic powder and biodegradable polymer powder according to a mass ratio of 1; the biological ceramic powder is at least one of hydroxyapatite, beta-tricalcium phosphate, calcium silicate and biological glass; the biodegradable polymer powder is at least one of polycaprolactone, polyurethane, polyglycolic acid and polylactic acid.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
the technical scheme of the invention provides a profiling artificial bone which mainly solves the problem of insufficient overall biological activity in the existing artificial bone, an arc-shaped tubular structure is designed, a composite biological active substance is filled in the inner cavity of the tubular structure, the overall bionics of the inner part and the outer wall is realized, the inner part of the tubular structure is a bioactive material bionic low-density cancellous bone with higher porosity and low density, the tubular structure has better biocompatibility, the communicated inner part is convenient for blood supply, and the tubular structure is made of a material with excellent mechanical property (the modulus is 10 GPa-20 GPa, and the impact toughness is more than 10J/cm) 2 ) The carbon fiber-carbon composite material bionic cortical layer with high porosity shows excellent mechanical property, a large number of gaps exist in the tube wall, autologous tissue attachment is facilitated, the outer surface is smooth, tissue damage is reduced, and the carbon fiber-carbon composite material bionic cortical layer is suitable for rib and phalanx repair.
2) The preparation process of the profiling artificial bone is simple, the cost is low, and the industrial production is facilitated.
Drawings
Fig. 1 is a physical diagram of a copying artificial bone.
Detailed Description
The following examples are intended to illustrate the present disclosure in further detail, but not to limit the scope of the claims.
Example 1
1) Firstly twisting 2 bundles of 12k carbon fiber bundles into a fiber rope, and then weaving the fiber rope with the cross-sectional area of 20mm by using 20 carbon fiber ropes 2 The surface of the tubular structure is reserved with 2.0mm fixing holes;
2) Filling polyethylene particles in the inner cavity of the tubular structure, and carrying out warm-pressing molding by means of a mold (the mold is a conventional mold and has a human bone-shaped inner cavity), wherein the warm-pressing molding conditions are as follows: the temperature is 200 ℃, the time is 4 hours, and an arc-shaped tubular structure, namely the copying artificial bone blank body, is prepared;
3) Cooling, removing the mold, heating to 80 deg.C, and taking out the softened thermoplastic polymer material from the inner cavity of the artificial bone blank;
4) The shaped profiling artificial bone blank compact carbon matrix adopts a chemical vapor deposition process, and the specific process comprises the following steps: placing the carbon fiber preform into a deposition furnace, introducing a carbon-containing gas source (methane and hydrogen with the flow ratio of 1: 0.5) at the temperature of 1100 ℃, and depositing for 80 hours;
5) Performing machining including cutting the end portion and the like;
6) Filling a bioactive mixture into the copying artificial bone blank to obtain a copying artificial bone; the bioactive substance consists of hydroxyapatite and polycaprolactone according to a mass ratio of 1;
artificial bone performance: the mass percentage of the carbon fiber and the carbon matrix is 65 percent to 35 percent; the modulus is 20GPa; the impact toughness is 15J/cm 2 。
Example 2
1) Twisting 3 bundles of 3k carbon fiber bundles into fiber ropes, and weaving the fiber ropes with the cross-sectional area of 30mm by using 50 carbon fiber ropes 2 The surface of the tubular structure is reserved with 0.5mm fixing holes;
2) Filling polyethylene particles in the inner cavity of the tubular structure, and carrying out warm-pressing molding by means of a mold (the mold is a conventional mold and has a human bone-shaped inner cavity), wherein the warm-pressing molding conditions are as follows: preparing an arc-shaped tubular structure, namely a profiling artificial bone blank body, at the temperature of 220 ℃ for 6 hours;
3) Cooling, removing the mold, heating to 120 deg.C, and taking out the softened thermoplastic polymer material from the inner cavity of the artificial bone blank;
4) A compact carbon matrix of the shaped profiling artificial bone blank body; the densified carbon substrate adopts a chemical vapor deposition process, and the specific process comprises the following steps: putting the carbon fiber preform into a deposition furnace, introducing natural gas at 1200 ℃, and depositing for 60 hours;
5) Performing machining including cutting the end portion and the like;
6) Placing the machined copying artificial bone blank into a high-temperature furnace for high-temperature treatment, heating under the condition of argon protective atmosphere for impurity removal, wherein the treatment temperature is 1800 ℃, and the heat preservation time is 3 hours;
7) Filling a bioactive mixture into the copying artificial bone blank to obtain a copying artificial bone; the bioactive substance consists of bioglass and polyurethane according to a mass ratio of 1;
artificial bone performance: the mass percentage of the carbon fiber to the carbon matrix is 68 percent to 32 percent; the modulus is 15GPa; the impact toughness is 13J/cm 2 。
Example 3
1) Twisting 2 bundles of 12k carbon fiber bundles into fiber ropes, and weaving the fiber ropes with the cross-sectional area of 20mm by using 20 carbon fiber ropes 2 The carbon fiber tubular structure of (1);
2) Filling polystyrene particles in the inner cavity of the tubular structure, and carrying out warm-pressing molding by means of a mold (the mold is a conventional mold and has an inner cavity in the shape of a human bone), wherein the warm-pressing molding condition is as follows: preparing an arc-shaped tubular structure, namely a profiling artificial bone blank body, at the temperature of 220 ℃ for 6 hours;
3) Cooling, removing the mold, heating to 150 deg.C, and taking out the softened thermoplastic polymer material from the inner cavity of the artificial bone blank;
4) A compact carbon matrix of the shaped profiling artificial bone blank body; the densified carbon substrate adopts a chemical vapor deposition process, and the specific process comprises the following steps: placing the carbon fiber preform into a deposition furnace, introducing a carbon-containing gas source (1: propylene and nitrogen gas) at the temperature of 950 ℃, and depositing for 50 hours;
5) Processing, including cutting the end or processing a fixing hole and the like; the aperture size of the fixed hole is generally 1.0mm;
6) Filling a bioactive mixture into the copying artificial bone blank to obtain a copying artificial bone; the bioactive substance consists of calcium silicate and polylactic acid according to the mass ratio of 1;
the performance of the artificial bone is as follows: the mass percentage of the carbon fiber to the carbon matrix is 72 percent to 28 percent; the modulus is 15GPa; the impact toughness is 10J/cm 2 。
Example 4
1) Firstly twisting 4 bundles of 6k carbon fiber bundles into fiber ropes, and then weaving the fiber ropes with the cross-sectional area of 40mm by using 80 carbon fiber ropes 2 The surface of the tubular structure is reserved with a fixing hole of 1.0mm;
2) Filling polypropylene particles in the inner cavity of the tubular structure, and carrying out warm-pressing molding by means of a mold (the mold is a conventional mold and has a human bone-shaped inner cavity), wherein the warm-pressing molding conditions are as follows: the temperature is 240 ℃, the time is 6h, and an arc-shaped tubular structure, namely the copying artificial bone blank body, is prepared;
3) Cooling, removing the mold, heating to 160 ℃ again, and taking out the thermoplastic polymer material softened in the inner cavity of the copying artificial bone blank;
4) A compact carbon matrix of the shaped profiling artificial bone blank body; the densified carbon substrate adopts a chemical vapor deposition process, and the specific process comprises the following steps: putting the carbon fiber preform into a deposition furnace, introducing natural gas at 1200 ℃, and depositing for 80h;
5) Performing machining including cutting the end portion and the like;
6) Placing the machined copying artificial bone blank into a high-temperature furnace for high-temperature treatment, heating under a vacuum condition to remove impurities, wherein the treatment temperature is 1500 ℃, and the heat preservation time is 8 hours;
7) Filling a bioactive mixture into the copying artificial bone blank to obtain a copying artificial bone; the bioactive substance consists of beta-tricalcium phosphate and polyvinyl alcohol according to the mass ratio of 1;
artificial bone performance: the mass percentage of the carbon fiber to the carbon matrix is 74 percent to 26 percent; the modulus is 18GPa; the impact toughness is 18J/cm 2 。
Example 5
1) Firstly twisting 2 bundles of 1k carbon fiber bundles into fiber ropes, and then weaving the fiber ropes with the cross-sectional area of 10mm by using 40 carbon fiber ropes 2 Of tubular structure of carbon fiber, anda fixing hole of 0.5mm is reserved on the surface of the tubular structure;
2) Filling polypropylene particles in the inner cavity of the tubular structure, and carrying out warm-pressing molding by means of a mold (the mold is a conventional mold and has a human bone-shaped inner cavity), wherein the warm-pressing molding conditions are as follows: the temperature is 240 ℃ and the time is 6h, and an arc-shaped tubular structure, namely the copying artificial bone blank body, is prepared;
3) Cooling, removing the mold, heating to 160 ℃ again, and taking out the thermoplastic polymer material softened in the inner cavity of the copying artificial bone blank;
4) Compacting a carbon matrix of the shaped profiling artificial bone blank; the densified carbon matrix adopts a chemical vapor deposition process, and the specific process comprises the following steps: putting the carbon fiber preform into a deposition furnace, introducing natural gas at the temperature of 1150 ℃, and depositing for 100 hours;
5) Performing machining including cutting the end portion and the like;
6) Placing the machined copying artificial bone blank into a high-temperature furnace for high-temperature treatment, heating under the Ar protective atmosphere condition for impurity removal, wherein the treatment temperature is 2000 ℃, and the heat preservation time is 1h;
7) Filling a bioactive mixture into the copying artificial bone blank to obtain a copying artificial bone; the bioactive substance consists of beta-tricalcium phosphate and polyvinyl alcohol according to the mass ratio of 1;
the performance of the artificial bone is as follows: the mass percentage of the carbon fiber to the carbon matrix is 78 percent to 22 percent; the modulus is 10GPa; the impact toughness is 12J/cm 2 。
Comparative example 1
Step 1) firstly weaving 40 bundles of 12k carbon fiber bundles with the cross section area of 20mm 2 The surface of the tubular structure is reserved with 2.0mm fixing holes;
steps 2) to 6) are the same as in example 1;
artificial bone performance: the mass percentage of the carbon fiber and the carbon matrix is 65 percent to 35 percent; the modulus is 12GPa; the impact toughness is 5J/cm 2 。
Comparative example 2
Steps 1) to 3) are the same as in example 2;
step 4), carrying out compact carbon matrix on the shaped profiling artificial bone blank; the densified carbon substrate adopts a chemical vapor deposition process, and the specific process comprises the following steps: putting the carbon fiber preform into a deposition furnace, introducing natural gas at 1200 ℃, and depositing for 30h;
steps 5) to 7) are the same as in example 2; the performance of the artificial bone is as follows: the mass percentage of the carbon fiber to the carbon matrix is 80 percent to 20 percent; the modulus is 10GPa; the impact toughness is 6J/cm 2 。

Claims (3)

1. A preparation method of a copying artificial bone is characterized by comprising the following steps:
the profiling artificial bone is provided with an arc-shaped tubular structure, and bioactive materials are filled in the tubular structure; the tubular structure is composed of a carbon fiber/carbon composite material;
the bioactive material comprises a bioceramic powder and a biodegradable polymer powder;
the biological ceramic powder is at least one of hydroxyapatite, beta-tricalcium phosphate, calcium silicate and biological glass;
the biodegradable polymer powder is at least one of polycaprolactone, polyurethane, polyglycolic acid and polylactic acid;
the mass ratio of the biological ceramic powder to the biodegradable polymer powder is 1 to 4;
the carbon fiber/carbon composite material consists of 60-80 mass percent of carbon fiber fabric and 20-40 mass percent of carbon matrix;
the profiling artificial bone is prepared by the following method:
twisting at least two carbon fiber bundles into a carbon fiber rope, and weaving the carbon fiber rope into a tubular structure; the carbon fiber bundle comprises at least 1k carbon fibers, wherein k represents one thousand; thermoplastic polymer material particles are filled in the tubular structure tube cavity, and a mould is utilized to assist warm-pressing forming to obtain a copying artificial bone blank body, wherein the warm-pressing forming conditions are as follows: the temperature is 200-240 ℃, and the time is 3-10 h; taking out the thermoplastic polymer material filled in the cavity of the copying artificial bone blank body, densifying a carbon matrix on the copying artificial bone blank body by a chemical vapor deposition method, and filling a bioactive material in the cavity of the copying artificial bone blank body.
2. The method for preparing a conformable artificial bone according to claim 1, wherein: the thermoplastic polymer material is at least one of polyethylene, polypropylene, polyvinyl chloride and polystyrene.
3. The method for preparing a contoured artificial bone according to claim 1, characterized in that: the conditions of the chemical vapor deposition method are as follows: the temperature is 850-1300 ℃, the time is 50-200 h, aliphatic hydrocarbon is used as a carbon gas source, and nitrogen or hydrogen is used as diluent gas.
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