CN110606746B - Skull repairing patch and preparation method thereof - Google Patents
Skull repairing patch and preparation method thereof Download PDFInfo
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- CN110606746B CN110606746B CN201910924729.0A CN201910924729A CN110606746B CN 110606746 B CN110606746 B CN 110606746B CN 201910924729 A CN201910924729 A CN 201910924729A CN 110606746 B CN110606746 B CN 110606746B
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- skull
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims description 46
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a skull repairing sheet and a preparation method thereof, wherein the skull repairing sheet is formed by overlapping a layer of carbon fiber knitted fabric and one or two layers of carbon fiber cloth; the carbon fiber cloth is formed by overlapping carbon fiber woven cloth and carbon fiber non-woven cloth; matrix carbon and/or silicon carbide are filled between the carbon fiber knitted fabric and the carbon fibers of the carbon fiber cloth. The skull repairing patch has the characteristics of light weight, good biocompatibility, good chemical stability, mechanical property similar to human bones, good fatigue, strong designability, no artifact and the like, and is particularly suitable for repairing the skull.
Description
Technical Field
The invention relates to a skull repairing sheet, in particular to a carbon fiber composite skull repairing sheet and a preparation method thereof, and belongs to the technical field of biomedical materials.
Background
Clinical symptoms may occur due to craniocerebral defects of greater than 3cm in diameter caused by trauma, infection, tumor, surgery, and the like. In order to keep the cranial cavity closed, repair the appearance of the patient, avoid physiological abnormality and the like, skull repair surgery is required.
The materials for skull repair mainly comprise autogenous bones, and materials such as artificial macromolecules, metals and the like are common materials for skull repair. In contrast, titanium alloys are ideal in terms of rigidity, strength, plasticity and biocompatibility, but have certain drawbacks: (1) poor mechanical compatibility, uneven stress distribution, implant loosening or dislocation, local osteoporosis, bone resorption, fracture, delayed bone healing and the like. (2) The edges are usually sharp and easily damage the skin, resulting in exposure of the implant; (3) the heat conductivity coefficient is high, which can cause the patient to feel uncomfortable under the condition of large temperature difference. (4) The strength and the hardness are lower than those of skull tissues, and the plastic deformation is easy to generate when the skull tissue is impact-resistant. (5) The medical examination has artifacts, which can affect the later diagnosis and rehabilitation treatment. The carbon material has good biocompatibility and can be applied to various aspects of biomedicine, but related reports of successful design and preparation of the skull repairing patch by adopting the carbon material are not found in the prior art.
Disclosure of Invention
Aiming at the defects of the skull repairing piece in the prior art, the invention aims to provide the carbon fiber composite skull repairing piece combining carbon fiber weaving and profiling, which has the characteristics of light weight, good biocompatibility, good chemical stability, mechanical property close to human bones, good fatigue property, strong designability, no artifacts and the like, and is particularly suitable for skull repairing.
Another purpose of the invention is to provide a method for preparing the skull repairing patch, which has simple steps and easily obtained raw materials.
In order to realize the technical purpose, the invention provides a skull repairing sheet which is formed by overlapping a layer of carbon fiber knitted fabric and one or two layers of carbon fiber cloth; the carbon fiber cloth is formed by overlapping carbon fiber woven cloth and carbon fiber non-woven cloth; matrix carbon and/or silicon carbide are filled between the carbon fiber knitted fabric and the carbon fibers of the carbon fiber cloth.
The carbon fiber woven fabric and the carbon fiber knitted fabric in the skull repairing patch are both formed by long carbon fibers, wherein the carbon fiber content of the carbon fiber woven fabric is high, and the carbon fiber woven fabric mainly provides strength support, and the carbon fiber knitted fabric has high porosity and can provide a favorable space for subsequent new tissues; the carbon fiber non-woven fabric is formed by short fibers, can be arranged on the top layer, can provide a large number of effective surfaces for the attachment of hydroxyapatite by utilizing the characteristic of high porosity of the carbon fiber non-woven fabric when arranged on the top layer, simultaneously utilizes the short fibers to penetrate into the inner layer of the carbon fiber cloth to play a riveting role, and is beneficial to the hydroxyapatite to penetrate into the carbon fiber cloth, thereby effectively utilizing the hydroxyapatite in the pore and on the surface of the skull repairing piece to guide the tissue growth so as to improve the binding capacity of the skull repairing piece and the tissue. Carbon fiber non-woven fabric also can set up between carbon fiber looped fabric and carbon fiber woven cloth, play the filling effect, and utilize the impaling effect of short fiber to play the riveting between the layer, and make the surperficial production hole of weaving of top layer carbon fiber woven cloth, be favorable to providing effective surface for the adhesion of hydroxyapatite, and be favorable to inside the hydroxyapatite infiltration carbon fiber woven cloth, thereby inside guide tissue growth to skull repair piece, be favorable to improving the combining ability of skull repair piece and tissue.
In a preferred embodiment, the matrix carbon includes at least one of pyrolytic carbon, resin carbon, and pitch carbon.
The preferable scheme is that carbon fibers are adopted to rivet between the carbon fiber knitted fabric and the carbon fiber cloth and between the carbon fiber woven fabric and the carbon fiber non-woven fabric in a layer-by-layer needling mode or a puncturing mode, and the surface density of riveting points is 5 points/cm225 dots/cm2. The bonding strength between the carbon fiber knitted fabric and the carbon fiber cloth and between the carbon fiber woven fabric and the carbon fiber non-woven fabric can be improved by adopting proper riveting point surface density.
In a preferred scheme, the center of the skull patch is provided with fixing-drainage holes, the hole distance is 1 cm-3 cm, and the hole diameter is 0.1 cm-0.3 mm. The skull patch can also be further provided with fixing holes at the periphery, wherein the hole spacing is 0.5 cm-1 cm, and the hole diameter is 0.1 cm-0.3 mm.
In a preferable scheme, hydroxyapatite is adhered to the pores and the surface layer of the skull repairing piece. In a more preferable scheme, the mass of the hydroxyapatite coating accounts for 5% -15% of the mass of the skull repairing piece. The hydroxyapatite adhered in the pores and on the surface layer can improve biocompatibility, form an effective transition layer, facilitate the guiding of the growth of biological tissues, improve the binding capacity of the skull repairing sheet and the tissues, and simultaneously can reduce the falling and transfer of matrix particles.
In a preferred embodiment, when the skull patch comprises two layers of carbon fiber cloth, the carbon fiber knitted cloth is arranged between the two layers of carbon fiber cloth. The carbon fiber knitted fabric is arranged on the middle layer, so that the middle layer has certain porosity, and a favorable space can be provided for subsequent new tissues.
Preferably, the carbon fiber woven cloth comprises an areal density of 120g/m2～1000g/m2In plain weaveCloth, twill or satin. More preferably 200g/m2～600g/m2。
Preferably, the carbon fiber knitted fabric comprises an areal density of 200g/m2～800g/m2Warp knitted fabric or weft knitted fabric. The carbon fiber knitted fabric is formed by twisting carbon fiber bundles and weft knitting; the twist of the carbon fiber bundle is 10-500 twists/m, and the single carbon fiber bundle comprises 1k, 3k, 6k, 12k or 24k carbon fibers (1k represents 1 thousand carbon fibers). The carbon fiber bundles are twisted and then weft-knitted, so that the rigidity can be greatly improved, and the flexural modulus can be improved.
Preferably, the surface density of the carbon fiber non-woven fabric is 10g/m2～60g/m2. More preferably 20g/m2～40g/m2。
The carbon fiber preform forming die adopts common die materials in the prior art, such as aluminum alloy, carbon materials and the like.
The invention also provides a preparation method of the skull repairing patch, which comprises the following steps:
1) laminating a layer of carbon fiber woven fabric and a layer of carbon fiber non-woven fabric (riveting in the thickness direction to improve the interlayer bonding strength) to obtain carbon fiber cloth, then laminating a carbon fiber knitted fabric and one or two layers of carbon fiber cloth (riveting in the thickness direction to improve the interlayer bonding strength), and forming a carbon fiber preform through mold auxiliary forming;
2) densifying matrix carbon and/or silicon carbide on the carbon fiber preform by adopting a chemical vapor infiltration method and/or a dipping-cracking method and/or a reaction infiltration method to obtain a blank, and performing shape processing and punching on the blank to obtain the carbon fiber preform; or further generating hydroxyapatite on the surface of the blank, and then carrying out shape processing and punching to obtain the composite material.
The process for generating the matrix carbon by chemical vapor infiltration comprises the following steps: and (2) putting the carbon fiber preform into a vacuum furnace, cracking 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: 0-2) at the temperature of 850-1300 ℃, then permeating a chemical vapor into the carbon fiber blank, and preparing the carbon fiber composite blank after 10-100 hours.
The invention relates to a process for generating matrix carbon by liquid phase impregnation-cracking densification, which comprises the following steps: the carbon fiber preform is subjected to densification processes such as resin (furan, phenolic aldehyde, furfuryl ketone and the like) or asphalt (graphite asphalt, coal asphalt) vacuum pressurization impregnation, curing treatment (resin), cracking (resin: 900-1050 ℃, normal pressure; asphalt: 750-850 ℃, 50-100 MPa) and the like. The dipping pressure is 1.0MPa to 5.0MPa, and the dipping time is 2 hours to 10 hours; the curing temperature is 160-230 ℃, and the curing time is 10-50 hours; the cracking time is 2-20 hours.
The invention relates to a process for generating a silicon carbide substrate by a chemical vapor infiltration method, which comprises the following steps: putting the carbon fiber preform into a vacuum furnace, introducing a gas source (trichloromethyl silane, hydrogen is a carrier gas and a diluent gas, the flow ratio of trichloromethyl silane to hydrogen is 1: 1-10) at the temperature of 900-1300 ℃, cracking, permeating chemical vapor into a carbon fiber blank, and preparing the carbon fiber composite blank after 10-100 hours.
The invention relates to a process for generating a silicon carbide-carbon matrix by a chemical vapor infiltration method, which comprises the following steps: the matrix carbon may be generated first and then silicon carbide, or both carbon and silicon carbide. The process for simultaneously generating the matrix carbon and the silicon carbide comprises the following steps: and simultaneously introducing a carbon matrix gas source and trichloromethylsilane, wherein other conditions are the same as the process conditions for generating the matrix carbon.
The invention relates to a process for generating a silicon carbide substrate by a dipping-cracking method, which comprises the following steps: the carbon fiber preform is subjected to densification processes such as vacuum pressurization impregnation, curing treatment, cracking and the like of a silicon-containing precursor (polycarbosilane PCS and polymethylsilane PMS). The dipping pressure is 1.0MPa to 5.0MPa, and the dipping time is 2 hours to 10 hours; the curing temperature is 160-230 ℃, and the curing time is 10-50 hours; the cracking temperature is 800-1150 ℃, and the time is 2-20 hours; the ceramic temperature is 1200-1600 deg.C, and the time is 2-10 hours.
The process for generating the silicon carbide-carbon matrix by the impregnation-pyrolysis method can compact the matrix carbon firstly and then compact the silicon carbide, or compact the matrix carbon and the silicon carbide simultaneously, or compact the silicon carbide firstly and then compact the matrix carbon. The process for simultaneously compacting the matrix carbon and the silicon carbide comprises the following steps: simultaneously impregnating the resin/pitch and the silicon-containing precursor under the same other conditions as the process conditions of the dense matrix carbon.
The conditions for generating the silicon carbide matrix by the reaction infiltration method are as follows: the granularity of the silicon powder is 1-50 μm; the infiltration temperature is 1450-1750 ℃, and the time is 1-6 hours. The carbon matrix is preferably formed before the reaction infiltration process is performed to form the silicon carbide, so as to reduce the reaction damage strength of the carbon fiber during the reaction infiltration process to form the silicon carbide.
The blank can also be subjected to high-temperature impurity removal and thermal refining treatment, and the treatment process conditions are as follows: the temperature is 1500-2300 ℃, and the holding time is 1-10 hours.
The process for generating the hydroxyapatite comprises the following steps:
(1) plasma spraying method:
1) the granularity of the hydroxyapatite powder is 20-150 mu m; 2) the plasma spraying power is 20 kW-40 kW; 3) the heat treatment temperature is 600-800 ℃, and the time is 1-5 hours.
(2) Electrochemical deposition:
1) the ratio of Ca ions to P ions in the phosphorus-containing and calcium-containing solution is 1.67; 2) the current density is 0.5mA/cm2～3mA/cm2(ii) a 3) The deposition time is 20min to 150 min; 4) the temperature of the electrolyte is 25-90 ℃; 5) the heat treatment temperature is 700-1000 ℃ and the time is 1-5 hours.
(3) Sol-gel method:
1) the sol is prepared by mixing and reacting a phosphorus-containing compound, ethanol and calcium salt, wherein the ratio of Ca ions to P ions is 1.67; 2) the gel temperature is 80-120 ℃, and the time is 3-20 hours; 3) the heat treatment temperature is 400-800 ℃, and the time is 1-5 hours.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the skull repairing sheet disclosed by the invention is made of a carbon fiber composite material, has the characteristics of light weight, good biocompatibility, good chemical stability, mechanical property close to that of human bones, good fatigue property, strong designability, no artifact and the like, and is particularly suitable for repairing the skull.
The skull repairing sheet provided by the invention is of a laminated structure of carbon fiber knitted fabric, carbon fiber woven fabric and carbon fiber non-woven fabric, has good mechanical properties, has a certain porosity on the surface, is beneficial to the penetration of hydroxyapatite into the interior and the guidance of tissue cells to grow into the interior, and improves the binding capacity with tissues.
The invention has good mechanical properties, such as compression strength more than or equal to 150MPa, bending strength more than or equal to 100MPa and bending modulus more than or equal to 10 GPa.
The skull repairing piece is a product combining carbon fiber weaving technology and profiling, and the skull repairing piece in any shape can be designed and prepared according to actual needs, so that the operation needs are met.
The skull repairing sheet provided by the invention contains hydroxyapatite in pores and on the surface, so that the biocompatibility can be improved, an effective transition layer is formed, and the falling and transfer of carbon-based particles are reduced.
Drawings
FIG. 1 is a pictorial view of a skull patch; wherein, the holes uniformly distributed in the center of the skull repairing piece are fixing-drainage holes.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
1) A layer of 3k carbon fiber plain cloth (the surface density is 200 g/m)2) And a layer with an areal density of 20g/m2The carbon fiber non-woven fabric is laminated, needle punching, forming and riveting are carried out in the thickness direction to obtain the carbon fiber fabric, and the 6k twisted carbon fiber is knitted into the carbon fiber non-woven fabric with the surface density of 300g/m2The carbon fiber knitted fabric is laminated with a layer of carbon fiber cloth, needling is carried out in the thickness direction to form riveting, and the areal density of a riveting point is 10 points/cm2Forming a carbon fiber preform through mold auxiliary forming;
2) putting the carbon fiber preform into a vacuum furnace, introducing natural gas at the temperature of 1000 ℃, taking nitrogen as diluent gas, enabling the flow ratio of the natural gas to the nitrogen to be 1:0.5, cracking, enabling chemical vapor to permeate into a carbon fiber blank, and preparing a carbon fiber composite material blank after 40 hours.
3) Coating hydroxyapatite on the surface of the blank by adopting plasma spraying: the particle size of the hydroxyapatite powder is 75 μm; 2) the plasma spraying power is 30 kW; 3) the heat treatment temperature is 700 ℃, and the time is 3 hours; 4) the hydroxyapatite accounts for 8% of the mass, the appearance is processed, a fixing-drainage hole is drilled in the center, the hole interval is 2cm, the hole diameter is 0.2mm, and the surface is polished to obtain the hydroxyapatite.
The prepared skull repairing sheet has the compression strength of 170MPa, the bending strength of 140MPa, the bending modulus of 15GPa, the surface porosity of the skull repairing sheet is high, hydroxyapatite can permeate into pores, and the surface layer of the hydroxyapatite is uniformly adhered.
Example 2
1) A layer of 1k carbon fiber twill cloth (the surface density is 140 g/m)2) And a layer with an areal density of 30g/m2The carbon fiber non-woven fabric is laminated, needle punching, forming and riveting are carried out in the thickness direction to obtain the carbon fiber fabric, and the carbon fiber fabric is weft knitted by 1k twisted carbon fiber to have the surface density of 500g/m2The carbon fiber knitted fabric is laminated with a layer of carbon fiber cloth, needling is carried out in the thickness direction to form riveting, and the areal density of a riveting point is 20 points/cm2Forming a carbon fiber preform through mold auxiliary forming;
2) putting the carbon fiber preform into a vacuum furnace, introducing methane at 1200 ℃, taking nitrogen as diluent gas, enabling the flow ratio of methane to nitrogen to be 1:0.2, cracking, enabling chemical vapor to permeate into a carbon fiber blank, and preparing a carbon fiber composite material blank after 30 hours. And then carrying out densification processes such as furfuryl ketone resin vacuum pressure impregnation, curing treatment, cracking and the like on the carbon fiber preform. The dipping pressure is 3.0MPa, and the dipping time is 7 hours; the curing temperature is 220 ℃, and the curing time is 20 hours; the cracking temperature is 900 ℃ and the time is 8 hours.
3) Coating hydroxyapatite on the surface of the blank by adopting plasma spraying: the particle size of the hydroxyapatite powder is 45 mu m; 2) the plasma spraying power is 20 kW; 3) the heat treatment temperature is 800 ℃, and the time is 2 hours; 4) the mass of the hydroxyapatite accounts for 15 percent. Processing the shape, punching fixing-drainage holes in the center, wherein the hole spacing is 2cm, the hole diameter is 0.2mm, and polishing the surface to obtain the product.
The prepared skull repairing patch has the compression strength of 165MPa, the bending strength of 135MPa and the bending modulus of 12 GPa. The skull repairing piece has high surface porosity, hydroxyapatite can permeate into the pores, and the surface layer of the hydroxyapatite is uniformly adhered.
Example 3
1) A layer of 6k carbon fiber satin cloth (surface density 280 g/m)2) With a layer of areal density of 20g/m2The carbon fiber non-woven fabric is laminated, needle punching, forming and riveting are carried out in the thickness direction to obtain the carbon fiber fabric, and the carbon fiber fabric is weft knitted by 3k twisted carbon fiber to have the surface density of 400g/m2The carbon fiber knitted fabric is laminated with a layer of carbon fiber cloth, needling is carried out in the thickness direction to form riveting, and the areal density of a riveting point is 15 points/cm2Forming a carbon fiber preform through mold auxiliary forming;
2) and (3) carrying out densification processes such as phenolic resin vacuum pressure impregnation, curing treatment, cracking and the like on the carbon fiber preform. The dipping pressure is 3.0MPa, and the dipping time is 7 hours; the curing temperature is 220 ℃, and the curing time is 20 hours; the cracking temperature is 800 ℃, the pressure is 100MPa, and the time is 6 hours.
3) Coating hydroxyapatite on the surface of the blank by adopting plasma spraying: the particle size of the hydroxyapatite powder is 150 mu m; 2) the plasma spraying power is 25 kW; 3) the heat treatment temperature is 650 ℃, and the time is 4 hours; 4) the mass of the hydroxyapatite accounts for 10 percent. Processing the shape, punching fixing-drainage holes at the center with hole spacing of 2cm and hole diameter of 0.2mm, punching fixing holes at the periphery with hole spacing of 0.6cm and hole diameter of 0.2mm, and polishing the surface to obtain the final product.
The prepared skull repairing patch has the compression strength of 180MPa, the bending strength of 160MPa and the bending modulus of 17 GPa. The skull repairing piece has high surface porosity, hydroxyapatite can permeate into the pores, and the surface layer of the hydroxyapatite is uniformly adhered.
Example 4
1) A layer of 12k carbon fiber satin cloth (with the surface density of 480 g/m)2) And a layer with an areal density of 30g/m2The carbon fiber non-woven fabric is laminated, needle punching, forming and riveting are carried out in the thickness direction to obtain the carbon fiber fabric, and the carbon fiber fabric is weft knitted by 3k twisted carbon fiber to have the surface density of 400g/m2The carbon fiber knitted fabric is laminated with a layer of carbon fiber cloth, and is needled in the thickness direction to form riveting, wherein the density of riveting points is 12 points/cm2Forming a carbon fiber preform through mold auxiliary forming;
2) and (3) carrying out densification processes such as vacuum pressure impregnation, curing treatment, cracking and the like on the carbon fiber preform by using a silicon-containing precursor PCS. The dipping pressure is 4.0MPa, and the dipping time is 6 hours; the curing temperature is 180 ℃, and the curing time is 30 hours; the cracking temperature is 1100 ℃, and the time is 4 hours; the ceramization temperature was 1400 ℃ and the time was 4 hours. A green body is obtained.
3) Adopting a chemical deposition method to generate hydroxyapatite on the surface of the blank: the ratio of Ca ions to P ions in the phosphorus-containing and calcium-containing solution is 1.67; 2) the current density is 1mA/cm2(ii) a 3) The deposition time is 60 min; 4) the temperature of the electrolyte is 30 ℃; 5) the heat treatment temperature is 800 ℃, and the time is 2 hours; 6) the mass of the hydroxyapatite accounts for 10 percent. Processing the shape, punching fixing-drainage holes at the center with hole spacing of 2cm and hole diameter of 0.2mm, punching fixing holes at the periphery with hole spacing of 0.6cm and hole diameter of 0.2mm, and polishing the surface to obtain the final product.
The prepared skull repairing patch has the compression strength of 190MPa, the bending strength of 165MPa and the bending modulus of 19 GPa. The skull repairing piece has high surface porosity, hydroxyapatite can permeate into the pores, and the surface layer of the hydroxyapatite is uniformly adhered.
Example 5
1) A layer of 6k carbon fiber satin cloth (the surface density is 320 g/m)2) And a layer with an areal density of 30g/m2The carbon fiber non-woven fabric is laminated, needle punching, forming and riveting are carried out in the thickness direction to obtain the carbon fiber fabric, and the 6k twisted carbon fiber is knitted into the carbon fiber non-woven fabric with the surface density of 200g/m2The carbon fiber knitted fabric and the two layers of carbon fiber cloth are laminated to form a sandwich structure, needling is carried out in the thickness direction to form riveting, and the riveting point surfaceThe density was 12 dots/cm2Forming a carbon fiber preform through mold auxiliary forming;
2) putting the carbon fiber preform into a vacuum furnace, introducing methane and the like at the temperature of 1000 ℃, introducing nitrogen or hydrogen as diluent gas, wherein the flow ratio of the methane gas to the diluent gas is 1:1), cracking, and then permeating chemical vapor into the carbon fiber blank for 20 hours. And then the prefabricated body is subjected to densification processes such as PCS vacuum pressurization impregnation, curing treatment, cracking and the like. The dipping pressure is 4.0MPa, and the dipping time is 6 hours; the curing temperature is 180 ℃, and the curing time is 30 hours; the cracking temperature is 1100 ℃, and the time is 4 hours; the ceramic temperature is 1400 ℃, the ceramic time is 4 hours, and a green body is obtained.
3) Generating hydroxyapatite on the surface of the blank by adopting a sol-gel method: the sol is prepared by mixing and reacting a phosphorus-containing compound, ethanol and calcium salt, wherein the ratio of Ca ions to P ions is 1.67; 2) the gel temperature is 100 ℃, and the time is 5 hours; 3) the heat treatment temperature is 600 ℃, and the time is 4 hours; 4) the mass of the hydroxyapatite accounts for 10 percent. Processing the shape, punching fixing-drainage holes at the center with hole spacing of 2cm and hole diameter of 0.2mm, punching fixing holes at the periphery with hole spacing of 0.6cm and hole diameter of 0.2mm, and polishing the surface to obtain the final product.
The prepared skull repairing patch has the compression strength of 220MPa, the bending strength of 176MPa and the bending modulus of 20 GPa. The skull repairing piece has high surface porosity, hydroxyapatite can permeate into the pores, and the surface layer of the hydroxyapatite is uniformly adhered.
Example 6
1) A layer of 6k carbon fiber satin cloth (the surface density is 400 g/m)2) And a layer with an areal density of 40g/m2The carbon fiber non-woven fabric is laminated, needle punching, forming and riveting are carried out in the thickness direction to obtain the carbon fiber fabric, and the carbon fiber fabric is weft knitted by 3k twisted carbon fiber to have the surface density of 400g/m2The carbon fiber knitted fabric is laminated with a layer of carbon fiber cloth, and is needled in the thickness direction to form riveting, wherein the areal density of the riveting points is 14 points/cm2Forming a carbon fiber preform through mold auxiliary forming;
2) and (3) carrying out densification processes such as vacuum pressure impregnation, curing treatment, cracking and the like on the carbon fiber preform by using a silicon-containing precursor PCS. The dipping pressure is 5.0MPa, and the dipping time is 8 hours; the curing temperature is 180 ℃, and the curing time is 30 hours; the cracking temperature is 1100 ℃, and the time is 4 hours; the ceramization temperature was 1300 ℃ and the time was 5 hours. Obtaining a green body
3) Processing the blank, punching fixing-drainage holes at the center with hole spacing of 2cm and hole diameter of 0.2mm, punching fixing holes at the periphery with hole spacing of 0.6cm and hole diameter of 0.2mm, and polishing the surface to obtain the final product.
The prepared skull repairing patch has the compressive strength of 185MPa, the bending strength of 162MPa and the bending modulus of 18 GPa. The porosity of the surface of the skull patch is high.
Comparative example 1
1) A layer of 3k carbon fiber plain cloth (the surface density is 200 g/m)2) And carbon fiber weft knitted by 6k twisting to have the surface density of 300g/m2The carbon fiber knitted fabric laminate is subjected to needling in the thickness direction to form riveting, and the areal density of a riveting point is 10 points/cm2Forming a carbon fiber preform through mold auxiliary forming;
2) putting the carbon fiber preform into a vacuum furnace, introducing natural gas at the temperature of 1000 ℃, taking nitrogen as diluent gas, enabling the flow ratio of the natural gas to the nitrogen to be 1:0.5, cracking, enabling chemical vapor to permeate into a carbon fiber blank, and preparing a carbon fiber composite material blank after 40 hours.
3) Coating hydroxyapatite on the surface of the blank by adopting plasma spraying: the particle size of the hydroxyapatite powder is 75 μm; 2) the plasma spraying power is 30 kW; 3) the heat treatment temperature is 700 ℃, and the time is 3 hours; 4) the hydroxyapatite accounts for 8% of the mass, the appearance is processed, a fixing-drainage hole is drilled in the center, the hole interval is 2cm, the hole diameter is 0.2mm, and the surface is polished to obtain the hydroxyapatite.
The prepared skull repairing patch has the compression strength of 160MPa, the bending strength of 110MPa and the bending modulus of 14 GPa. The surface porosity of the skull repairing piece is low, hydroxyapatite cannot penetrate into the skull repairing piece, and the surface layer hydroxyapatite is not adhered uniformly.
Comparative example 2
1) One layer with the surface density of 20g/m2The carbon fiber non-woven fabric is knitted by 6k twisted carbon fiber weft knitting to form a layer with the surface density of 300g/m2The carbon fiber knitted fabric laminate is subjected to needling in the thickness direction to form riveting, and the areal density of a riveting point is 10 points/cm2Forming a carbon fiber preform through mold auxiliary forming;
2) putting the carbon fiber preform into a vacuum furnace, introducing natural gas at the temperature of 1000 ℃, taking nitrogen as diluent gas, enabling the flow ratio of the natural gas to the nitrogen to be 1:0.5, cracking, enabling chemical vapor to permeate into a carbon fiber blank, and preparing a carbon fiber composite material blank after 40 hours.
3) Coating hydroxyapatite on the surface of the blank by adopting plasma spraying: the particle size of the hydroxyapatite powder is 75 μm; 2) the plasma spraying power is 30 kW; 3) the heat treatment temperature is 700 ℃, and the time is 3 hours; 4) the hydroxyapatite accounts for 8% of the mass, the appearance is processed, a fixing-drainage hole is drilled in the center, the hole interval is 2cm, the hole diameter is 0.2mm, and the surface is polished to obtain the hydroxyapatite.
The prepared skull patch has the advantages that the compressive strength is 80MPa, the bending strength is 60MPa, the bending modulus is 5GPa, the mechanical strength is obviously reduced compared with that of the skull patch in the embodiment 1, the surface porosity of the skull patch is high, hydroxyapatite can permeate into pores, and the surface layer of the hydroxyapatite is uniformly adhered.
Claims (5)
1. A cranial prosthesis, characterized by: the knitted fabric is formed by overlapping a layer of carbon fiber knitted fabric and one or two layers of carbon fiber cloth; the carbon fiber cloth is formed by overlapping carbon fiber woven cloth and carbon fiber non-woven cloth; matrix carbon and/or silicon carbide are filled between the carbon fiber knitted fabric and the carbon fibers of the carbon fiber cloth; hydroxyapatite is adhered to the pores and the surface of the skull repairing piece; when the skull patch comprises two layers of carbon fiber cloth, the carbon fiber knitted cloth is arranged between the two layers of carbon fiber cloth; the carbon fibers are riveted between the carbon fiber knitted fabric and the carbon fiber cloth and between the carbon fiber woven fabric and the carbon fiber non-woven fabric in a layer-by-layer needling mode or puncturing mode, and the areal density of riveting points is 5 points/cm225 dots/cm2(ii) a The surface density of the carbon fiber non-woven fabric is 10g/m2~60g/m2The carbon fiber knitted fabric is formed by knitting twisted carbon fiber bundles; the twist of the carbon fiber bundle is 10 twist/m-500 twist/m, and the single carbon fiber bundle comprises 1k, 3k, 6k, 12k or 24k carbon fibers.
2. The cranial prosthesis according to claim 1, wherein: the matrix carbon includes at least one of pyrolytic carbon, resin carbon, and pitch carbon.
3. The cranial prosthesis according to claim 1, wherein: the mass of the hydroxyapatite accounts for 5% -15% of the mass of the skull repairing sheet.
4. The cranial prosthesis according to claim 1, wherein: the center of the skull patch is provided with fixing-drainage holes, the hole distance is 1 cm-3 cm, and the hole diameter is 0.1 mm-0.3 mm.
5. The method for preparing a skull patch according to any one of claims 1 to 4, wherein the method comprises the following steps: the method comprises the following steps:
1) laminating a layer of carbon fiber woven fabric and a layer of carbon fiber non-woven fabric to obtain carbon fiber cloth, and laminating a carbon fiber knitted fabric and one or two layers of carbon fiber cloth, wherein the carbon fiber knitted fabric and the carbon fiber cloth, and the carbon fiber woven fabric and the carbon fiber non-woven fabric are riveted by adopting a carbon fiber layer-by-layer needling mode or a puncturing mode, and are formed by auxiliary molding of a mold to form a carbon fiber preform;
2) densifying matrix carbon and/or silicon carbide on the carbon fiber preform by adopting a chemical vapor infiltration method and/or a dipping-cracking method and/or a reaction infiltration method to obtain a blank, further generating hydroxyapatite on the surface of the blank, then carrying out shape processing and punching to obtain the carbon fiber preform.
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| CN1030523C (en) * | 1989-08-15 | 1995-12-20 | 王海林 | Materials for use in skull-fixing |
| WO2006127837A1 (en) * | 2005-05-24 | 2006-11-30 | Milliken & Company | Surface coverings and related methods |
| JP5327934B2 (en) * | 2007-12-06 | 2013-10-30 | 国立大学法人広島大学 | Implant material and manufacturing method thereof |
| CN102174744B (en) * | 2011-01-28 | 2012-11-07 | 东华大学 | Organic/inorganic compound photooxidation resistance protecting agent and application thereof in fiber product |
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