阅读说明：本技术 一种碳纤维复合材料颅骨修补片及其制备方法 (Carbon fiber composite skull repairing piece and preparation method thereof ) 是由 谭周建 于 2019-09-27 设计创作，主要内容包括：本发明公开了一种碳纤维复合材料颅骨修补片及其制备方法,颅骨修补片由至少一层碳纤维机织布和至少一层碳纤维非织造布叠加构成；碳纤维机织布和碳纤维非织造布的碳纤维间均填充有基体碳和/或碳化硅；该颅骨修补片具有质量轻、生物相容性好、化学稳定性好、力学性能与人体骨相近、疲劳性好、可设计性强、无伪影等特点,特别适合颅骨修补使用。(The invention discloses a skull repairing piece made of carbon fiber composite material and a preparation method thereof, wherein the skull repairing piece is formed by overlapping at least one layer of carbon fiber woven fabric and at least one layer of carbon fiber non-woven fabric; matrix carbon and/or silicon carbide are filled between the carbon fibers of the carbon fiber woven fabric and the carbon fiber non-woven fabric; 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.)

1. The carbon fiber composite skull repairing piece is characterized in that: is formed by overlapping at least one layer of carbon fiber woven fabric and at least one layer of carbon fiber non-woven fabric; and matrix carbon and/or silicon carbide are filled between the carbon fibers of the carbon fiber woven fabric and the carbon fiber non-woven fabric.

2. The carbon fiber composite skull patch according to claim 1, wherein: is formed by overlapping 1-4 layers of carbon fiber woven fabrics and 1-4 layers of carbon fiber non-woven fabrics.

3. The carbon fiber composite skull patch according to claim 1, wherein: the interlamination rotation between any two adjacent layers of carbon fiber woven fabrics is 0-45 degrees.

4. The carbon fiber composite skull patch according to claim 1 or 3, wherein: the carbon fiber woven fabric comprises the surface density of 120g/m²～1000g/m²Plain, twill or satin.

5. The carbon fiber composite skull patch according to claim 1, wherein: the surface roughness of the skull repairing sheet made of the carbon fiber composite material is less than 0.4 mu m.

6. The carbon fiber composite skull patch according to claim 1, wherein: the matrix carbon includes at least one of pyrolytic carbon, resin carbon, and pitch carbon.

7. The carbon fiber composite skull patch according to claim 1, wherein: the carbon fiber woven fabric and the carbon fiber non-woven fabric are riveted by adopting the carbon fiber in a layer-by-layer needling mode or a puncturing mode, and the surface density of the riveting pointsIs 5 points/cm²25 dots/cm²。

8. The carbon fiber composite skull patch according to claim 1, wherein: the center of the carbon fiber composite skull patch is provided with fixing-drainage holes with the hole spacing of 1 cm-3 cm and the hole diameter of 0.1 cm-0.3 mm, and the periphery is provided with fixing holes with the hole spacing of 0.5 cm-1 cm and the hole diameter of 0.1 cm-0.3 mm.

9. The preparation method of the carbon fiber composite skull repairing patch according to any one of claims 1 to 8, characterized by comprising the following steps: the method comprises the following steps:

1) laminating at least one layer of carbon fiber woven fabric and at least one layer of carbon fiber non-woven fabric, and performing mold-assisted molding to obtain a carbon fiber preform;

2) densifying the carbon fiber preform by adopting a chemical vapor infiltration method and/or a dipping-cracking method and/or a reaction infiltration method to generate matrix carbon and/or silicon carbide, and machining to obtain the carbon fiber preform.

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, belonging to the 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 skull repairing materials by adopting the carbon material are not found in the prior art.

Disclosure of Invention

Aiming at the defects of the skull repairing material 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 achieve the technical purpose, the invention provides a carbon fiber composite skull repairing piece which is formed by overlapping at least one layer of carbon fiber woven fabric and at least one layer of carbon fiber non-woven fabric; matrix carbon and/or silicon carbide are filled between the carbon fibers of the carbon fiber woven fabric and the carbon fiber non-woven fabric.

According to the preferred scheme, the carbon fiber composite skull repairing piece is formed by overlapping 1-4 layers of carbon fiber woven fabrics and 1-4 layers of carbon fiber non-woven fabrics. The woven fabric in the carbon fiber composite skull repairing piece is composed of long fibers, the carbon fiber content is high, the strength support is mainly provided, the carbon fiber non-woven fabric is composed of short fibers, the carbon fiber non-woven fabric can be arranged on the surface layer, when the carbon fiber non-woven fabric is arranged on the surface layer, the characteristic of high porosity of the carbon fiber non-woven fabric is utilized, a large number of surfaces can be provided for tissue cell attachment, meanwhile, the short fibers penetrate into the inner layer of the carbon fiber cloth to play a riveting role, and the tissue cell growth is facilitated to the inside of the carbon fibers, so that the binding capacity of the skull. The carbon fiber non-woven fabric can also be arranged between any two layers of carbon fiber woven fabric layers to play a filling role, and the puncturing effect of the short fibers is utilized to realize interlayer riveting, so that pores are generated on the surface of the surface layer carbon fiber woven fabric, and an effective surface is provided for tissue cell attachment. The mechanical strength can be controlled by adjusting the carbon fiber woven fabric.

In the preferable scheme, the interlamination rotation between any two adjacent layers of carbon fiber woven fabrics is 0-45 degrees. The mechanical property of the composite material can be improved by rotating a certain angle.

In a preferable scheme, the surface roughness of the skull repairing piece made of the carbon fiber composite material is less than 0.4 mu m. The skull patch can be used for tissue cell growth conveniently due to the introduction of the carbon fiber non-woven fabric to maintain a certain porosity, improving the histocompatibility and the binding capacity with tissues, reducing local shedding due to small surface roughness.

In a preferred embodiment, the matrix carbon includes at least one of pyrolytic carbon, resin carbon, and pitch carbon.

According to the preferable scheme, 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 the surface density of a riveting point is 5 points/cm²25 dots/cm². If the multilayer carbon fiber woven cloth and the multilayer carbon fiber non-woven cloth are not overlapped alternately, the riveting method is also adopted between the layers. When the carbon fiber woven fabric and the carbon fiber non-woven fabric are stacked, the short fibers of the carbon fiber non-woven fabric can be used for riveting. The riveting can improve the strength between the carbon fiber woven cloth and the carbon fiber non-woven clothThe bonding strength and the comprehensive mechanical property are improved.

In a preferred scheme, the center of the carbon fiber composite skull patch is provided with fixing-drainage holes, the hole spacing is 1 cm-3 cm, the hole diameter is 0.1 cm-0.3 mm, the periphery of the carbon fiber composite skull patch is provided with fixing holes, the hole spacing is 0.5 cm-1 cm, and the hole diameter is 0.1 cm-0.3 mm. The fixing-drainage hole arranged in the center is mainly used as a suture line for connecting the fixing point and the drainage hole for local effusion. The fixing holes around facilitate the fixation of the screws on the autologous bone tissue.

Preferably, the carbon fiber woven cloth has an areal density of 120g/m²～1000g/m²Plain, twill or satin. More preferably 200g/m²～600g/m²。

Preferably, the surface density of the carbon fiber non-woven fabric is 10g/m²～60g/m². More preferably 20g/m²～40g/m²。

The invention also provides a preparation method of the carbon fiber composite skull repairing piece, which comprises the following steps:

1) laminating at least one layer of carbon fiber woven fabric and at least one layer of carbon fiber non-woven fabric (riveting can be carried out in the thickness direction), and carrying out auxiliary molding through a mold to obtain a carbon fiber preform;

2) densifying the carbon fiber preform by adopting a chemical vapor infiltration method and/or a dipping-cracking method and/or a reaction infiltration method to generate matrix carbon and/or silicon carbide, and machining to obtain the carbon fiber preform.

The carbon fiber preform forming die adopts common die materials in the prior art, such as aluminum alloy, carbon materials and the like.

The method can also carry out the step of high-temperature impurity removal treatment on the blank after the matrix carbon and/or the silicon carbide is generated, or carry out no treatment.

The invention relates to a process for generating matrix carbon by chemical vapor infiltration, which 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 dipping and cracking, 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 ℃, 50-200 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 chemical vapor infiltration, 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 producing a silicon carbide substrate by dipping and cracking, 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 invention relates to a process for generating a silicon carbide-carbon matrix by chemical vapor infiltration, which comprises the following steps: the matrix carbon may be first formed and then the silicon carbide may be formed, or both the matrix carbon and the silicon carbide may be formed, or the silicon carbide may be first formed and then the carbon may be formed. The process for simultaneously producing carbon and 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 carbon.

The process for producing the silicon carbide-carbon matrix by dipping and cracking 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 dipping the resin/asphalt and the silicon-containing precursor, wherein other conditions are the same as the process conditions of compact carbon, the temperature of the silicon-based ceramic is 1200-1600 ℃, and the time is 2-10 hours.

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 high-temperature impurity removal and thermal refining process comprises the following steps: the temperature is 1500-2300 ℃, and the holding time is 1-10 hours.

The machining process of the invention comprises surface finishing, punching, polishing and other treatment processes.

Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:

the carbon fiber composite skull repairing piece has the characteristics of light weight, good biocompatibility, good chemical stability, mechanical property similar to that of human bones, good fatigue property, strong designability, no artifact and the like, and is particularly suitable for repairing the skull.

The carbon fiber composite skull patch has a laminated structure of a plurality of layers of carbon fiber woven fabrics and carbon fiber non-woven fabrics, has good mechanical property and certain porosity, is beneficial to tissue cells to grow inside, and improves the binding capacity with tissues.

The carbon fiber composite skull patch has good mechanical properties, such as bending strength of more than or equal to 200MPa, bending modulus of 10 GPa-20 GPa and tensile strength of 100 MPa-150 MPa.

The carbon fiber composite skull repairing piece is formed by combining carbon fiber weaving 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.

Drawings

FIG. 1 is a physical diagram of a carbon fiber composite skull patch; wherein, the holes uniformly distributed in the center of the skull repairing piece made of the carbon fiber composite material are fixing-drainage holes, and the two rows of dislocation holes on the periphery are fixing holes.

Detailed Description

The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.