CN111925227A - Carbon fiber composite material artificial trachea stent and preparation method thereof - Google Patents
Carbon fiber composite material artificial trachea stent and preparation method thereof Download PDFInfo
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- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
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Abstract
The invention discloses an artificial trachea bracket made of carbon fiber composite materials and a preparation method thereof, wherein the artificial trachea bracket has a hierarchical tubular structure; the tubular structure comprises a continuous straight wall and claw holding structures axially distributed along two sides of the continuous straight wall, wherein the inner layer of the tubular structure is a carbon fiber reinforced composite material layer, and the outer layer of the tubular structure is a DLC coating. The artificial trachea stent is prepared by weaving, densifying, machining, generating a DLC coating and the like by utilizing carbon fibers or carbon fiber fabrics, has good histocompatibility, excellent mechanical property and a contraction-expansion function, and is simple in preparation method process, strong in operability and beneficial to actual industrial production.
Description
Technical Field
The invention relates to an artificial trachea stent, in particular to a carbon fiber composite artificial trachea stent and a preparation method thereof, and belongs to the technical field of biomedical materials.
Background
The trachea must be removed and reconstructed because of the narrow and affected function caused by tumor, physicochemical factors and the like. When the length exceeds 6cm, the anastomotic stoma has high tension and is easy to generate complications such as fistula, and the trachea needs to be reconstructed by artificial materials. Some researchers have designed artificial trachea made of terylene and silica gel materials; carbon fiber composite silica gel net pipe; an artificial trachea made of polyester polypropylene composite material; the round titanium beads are connected into a mesh artificial trachea; the soft Marlex net is made into a tubular shape, the surface of the Marlex net is reinforced by polypropylene materials, and the pipe wall is filled with collagen; the reticular polytetrafluoroethylene material is combined with autologous tissues and the like. The complexity of the trachea tissue environment has a plurality of requirements on trachea substitutes, the trachea substitutes cannot be biologically fused and fixed with organisms after being transplanted in vivo, and are easy to drop, leak and the like.
Disclosure of Invention
In order to overcome the defects of the conventional artificial trachea, the first object of the invention is to provide an artificial trachea stent which is made of a carbon fiber composite material, has good tissue compatibility and mechanical properties, and has a contraction-expansion function.
The invention also aims to provide a method for preparing the artificial tracheal stent, which has simple process and strong operability and is beneficial to actual industrial production.
In order to achieve the technical purpose, the invention provides a carbon fiber composite material artificial trachea bracket which has a hierarchical tubular structure; the hierarchical tubular structure comprises a continuous straight wall and claw holding structures axially distributed along two sides of the continuous straight wall; the hierarchical tubular structure comprises an inner carbon fiber reinforced composite material layer and an outer DLC coating.
Preferably, the continuous straight wall surface is uniformly provided with small holes. Round holes or slot openings are distributed on the continuous straight wall. The small holes are convenient for the fixed attachment of the flexible pipe wall on one hand, and can be suitable for the neogenetic tissue to penetrate through the pipe wall and contact with multiple regions on the other hand. Preferably, the pore size of the pores is
The hole spacing is 5 mm-15 mm (the distance between the hole center and the hole center around the hole).
According to the preferable scheme, arc-shaped strips are uniformly arranged on two sides of the continuous straight wall, and the arc-shaped strips on the two sides of the continuous straight wall are axially and alternately distributed along the layered tubular structure to form a clasping claw structure in a clasping manner.
The artificial trachea bracket provided by the invention has an integrated structure of the holding claw structure and the continuous straight wall. The holding claw structure is mainly composed of arc-shaped bars on two sides of a continuous straight wall, one end of each arc-shaped bar is connected with one side of the straight wall into a whole, the other end of each arc-shaped bar and the other side of the continuous straight wall are provided with a non-connector, and a gap is reserved between the arc-shaped bars and the other side of the continuous straight wall. The arc-shaped bars are made of carbon fiber composite materials, have good mechanical property, can be dilated and contracted within a certain range, adapt to the dilatation and contraction change of the trachea in the breathing process, form continuous channels between the arc-shaped bars and the continuous straight wall, and are beneficial to blood supply of new tissues.
Preferably, the carbon fiber reinforced composite material layer is made of a carbon/carbon composite material or a carbon/silicon carbide composite material. The carbon/carbon composite material refers to a carbon fiber reinforced carbon composite material, and the carbon/silicon carbide composite material is a carbon fiber reinforced carbon-silicon carbide composite material.
Preferably, a PyC transition layer is arranged between the inner carbon fiber reinforced composite material layer and the outer DLC coating. The DLC coating is a diamond-like coating. The PyC transition layer is a pyrolytic carbon layer. The PyC transition layer arranged between the carbon fiber reinforced composite material layer and the DLC coating can eliminate the difference between the carbon fiber and the carbon matrix, is favorable for DLC film formation, and improves the film-substrate bonding strength. The DLC coating has the characteristics of high hardness, low friction coefficient and excellent chemical inertness, but the DLC coating is poorer in combination with the carbon fiber composite material layer and is difficult to obtain a uniform DLC coating, while the combination capability between the PyC coating and the carbon fiber composite material layer is good, but the hardness is lower and is only 1 GPa-3 GPa, the surface roughness of the high-temperature deposited PyC coating is high, the part is easy to damage and demould to form carbon dust and is not suitable for being used as a surface layer, therefore, a PyC transition layer is firstly generated on the surface of the carbon fiber reinforced composite material layer, and then the DLC coating is regenerated, and the composite coating with better comprehensive performances such as tissue compatibility, wear resistance and the like can.
Preferably, the thickness of the PyC transition layer is 5 to 50 μm. The control of the thickness of the PyC transition layer is advantageous for improving the bonding strength of the DLC coating to the carbon fiber reinforced composite material layer.
Preferably, the DLC coating has a thickness of 100nm to 3 μm.
Preferably, the thickness of the carbon fiber reinforced composite material layer is 1 mm-3 mm.
The invention also provides a preparation method of the carbon fiber composite material artificial trachea bracket, which adopts the scheme A or the scheme B:
scheme a includes the following steps:
1) weaving carbon fibers into a clamping claw structure, and performing mold auxiliary forming to obtain a tubular carbon fiber preform with the clamping claw structure;
2) densifying matrix carbon and/or silicon carbide on the tubular carbon fiber preform to obtain a tubular carbon fiber composite blank;
3) machining the tubular carbon fiber composite blank to prepare a blank;
4) generating a DLC coating on the surface of the blank, or firstly generating a PyC coating on the surface of the blank and then generating the DLC coating;
scheme B includes the following steps:
1) weaving carbon fiber fabric into a tubular structure, and performing auxiliary molding by using a mold to obtain a tubular carbon fiber preform;
2) densifying matrix carbon and/or silicon carbide on the tubular carbon fiber preform to obtain a tubular carbon fiber composite blank;
3) machining the tubular carbon fiber composite blank to prepare a blank with a claw holding structure;
4) and (3) forming a DLC coating on the surface of the blank, or forming a PyC coating on the surface of the blank and then forming the DLC coating.
According to the preferred scheme, carbon fiber bundles are twisted into carbon fiber ropes, and the carbon fiber ropes are woven into claw holding structures; or, the carbon fiber cloth and the carbon fiber net are compounded and needled into a tubular structure. The specific process of weaving by adopting the carbon fiber bundles is as follows: twisting more than 2 carbon fiber bundles into carbon fiber ropes, and then laying and weaving the carbon fiber ropes in the axial direction and the circumferential direction to form a claw holding structure or a tubular structure (consisting of cross arms); the number of the axial ropes is larger than 5 ropes, and the circumferential single arm is at least 3 ropes. The specific process of weaving by adopting the carbon fiber fabric comprises the following steps: at least 2 layers of carbon fiber cloth and at least 1 layer of carbon fiber net are laminated and needled to form a tubular fabric, and long fibers in the carbon fiber cloth are distributed in the axial direction and the circumferential direction.
More preferably, the number of the carbon fiber bundle is 1k, 3k, 6k or 12k (k represents one thousand).
More preferably, the carbon fiber cloth is a plain, twill or satin carbon fiber cloth woven from 1k, 3k, 6k or 12k carbon fiber bundles.
Preferred embodiment, theThe surface density of the carbon fiber net is 10g/m2～60g/m2。
Preferably, the PyC coating is formed by chemical vapor deposition under the following conditions: depositing a gas carbon source (such as natural gas, acetylene and other common gas carbon sources) at 900-1500 ℃ for 10-100 h. Because the surface roughness of the PyroC coating deposited by pyrolysis is high, the surface of the PyC coating is polished to reduce the roughness, and then a DLC coating is further generated, so that the film-substrate bonding performance can be further improved.
Preferably, the DLC coating is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 1X 10-1Pa～5×10-1Pa; negative bias of the workpiece: 10V to 200V (preferably 20 to 100V); ar flow rate: 50sccm to 120 sccm; ion source power: 0.5kW to 5 kW; graphite target power: 1 kW-3 kW, and the purity of the graphite target is 99.99 wt%; heating temperature: 80-200 deg.c (preferably 100-150 deg.c); deposition time: 1h to 12 h;
alternatively, the first and second electrodes may be,
the DLC coating is generated by plasma enhanced chemical vapor deposition (hereinafter referred to as PECVD) under the following conditions: vacuum degree of 1X 10-1Pa～5×10-1Pa; negative bias of the workpiece: 10V to 200V (preferably 40V to 150V); ar flow rate: 50sccm to 120 sccm; ion source power: 0.5kW to 5 kW; hydrocarbon gas (e.g. CH)4、C2H2) Flow rate: 10sccm to 500sccm (preferably 20sccm to 80 sccm); heating temperature: 80-300 deg.c (preferably 100-250 deg.c); deposition time: 1 to 12 hours.
The process for densifying carbon and/or silicon carbide of the present invention is primarily by chemical vapor deposition. Only silicon carbide may be produced, or only carbon may be produced; 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 deposited and then the matrix carbon may be formed. The process for generating the matrix carbon comprises the following steps: putting the carbon fiber preform into a vacuum furnace, introducing a gas source (carbon source gas is natural gas, methane or propylene and the like, nitrogen or hydrogen is 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 ℃, and cracking for 50-200 h. A preparation process for generating matrix silicon carbide; putting the carbon fiber preform into a deposition furnace, introducing a gas source (trichloromethyl silane (MTS) at the temperature of 900-1300 ℃, taking hydrogen as a carrier gas and a diluent gas, and cracking for 10-100 h, wherein the flow ratio of trichloromethyl silane to hydrogen is 1: 1-10. 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 machining of the invention refers to the processing technologies of grinding, cutting and the like.
After the PyC coating is generated on the surface of the blank, the polishing and cleaning treatment is carried out, and then the DLC coating is generated. The bonding force between the coatings can be improved.
The carbon fiber preform molding die of the present invention is made of a carbon material such as graphite, a carbon/carbon composite material, and the like.
The carbon fiber weaving process is a carbon fiber processing process which is common in the field.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the artificial trachea stent main body provided by the invention is made of carbon fiber composite materials, has light weight, high specific strength and good biocompatibility, and has obvious advantages compared with common terylene and silica gel materials and the like.
2) The artificial trachea support provided by the invention is provided with the claw-type structure, can realize circumferential expansion and contraction, meets the functional reconstruction of a trachea, and overcomes the defect that the artificial trachea support in the prior art cannot meet the contraction and expansion functions of a lumen of the trachea in the breathing process, so that the artificial trachea support is difficult to apply to clinic.
3) The artificial trachea bracket provided by the invention is provided with a large number of reserved areas, is suitable for providing blood transportation for attached tissues, promotes tissue regeneration, and is beneficial to the reconstruction of biological functions of the trachea.
4) The DLC coating on the surface of the artificial tracheal stent provided by the invention has good biocompatibility and high hardness, and can effectively prevent the inner-layer carbon fiber composite material matrix from falling and diffusing and avoid inhibiting tissue regeneration.
5) According to the preparation method of the artificial trachea bracket, the continuous carbon fibers are distributed on the bracket for reinforcement, and the bracket is designed into a straight wall and multi-arm continuous trachea profiling structure, so that the small-size support strength is guaranteed, and the rigidity organic combination of the flexible cantilever and the straight wall is realized.
6) The preparation method of the artificial trachea stent has simple process and strong operability, and is beneficial to actual industrial production.
Drawings
Fig. 1 is an artificial trachea stent (suitable for full dissection): the left figure is a single tube; middle cross section; the right drawing is the main branch bifurcation.
Fig. 2 is a real object diagram of the artificial trachea stent: a is in a rope weaving tubular shape, b is in a cloth net tubular shape, and c is in a rope weaving holding claw shape.
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) Firstly, 2 bundles of 3k carbon fibers are twisted into carbon fiber ropes, then 15 carbon fiber ropes are axially selected, 5 carbon fiber ropes are axially single-walled, carbon fiber rope fabrics are woven, and then the carbon fiber rope fabrics are fixed on a tubular carbon/carbon composite material mold to form a claw-shaped carbon fiber preform.
2) Placing the carbon fiber preform in a deposition furnace, and performing chemical vapor deposition for 100 hours at the temperature of 850 ℃ by taking propylene as a carbon source and nitrogen as diluent gas, wherein the flow ratio of the propylene to the nitrogen is 1:1 to obtain a carbon fiber composite material blank;
3) removing the die, and processing (including cutting, punching and the like) to obtain carbon fiber composite material blanks with the aperture of 1mm and the space interval of 5 mm;
4) then chemical vapor deposition PyC (pyrolytic carbon coating) is carried out, and the process parameters are as follows: depositing at 1200 ℃ for 20h by using natural gas as a carbon source, wherein the thickness of the obtained coating is 18 mu m;
5) after surface polishing and cleaning, the DLC coating is prepared by magnetron sputtering, and the process parameters are as follows: degree of vacuum of 3X 10- 1Pa; negative bias of the workpiece: 30) (ii) a Ar flow rate: 50 sccm; ion source power: 3 kW; graphite target power: 1kW of the mixed gas is discharged from the gas discharge pipe,the purity of the graphite target is 99.99 wt%; heating temperature: 100 ℃; deposition time: and 6 h.
The artificial tracheal stent prepared in this example: the surface hardness is 12GPa, the film-substrate bonding strength is 32N, and the maximum expansion area of the section is more than 10%.
Example 2
1) 2 layers of 200g/m23k carbon fiber plain cloth and 1 layer of 20g/m2And (3) compounding the carbon fiber net into a carbon fiber fabric by needling, and then fixing the carbon fiber rope fabric on a tubular graphite mold to form a tubular carbon fiber preform.
2) Placing the carbon fiber preform in a deposition furnace, taking methane as a carbon source and hydrogen as a diluent gas at the temperature of 1100 ℃, wherein the flow ratio of a gas source is methane: hydrogen is 1:2, and chemical vapor deposition is carried out for 200h, thus obtaining a carbon fiber composite material blank;
3) removing the mold, and forming an encircling tubular carbon fiber composite blank after processing (grooving and punching); punching
The distance is 10 mm.
4) Then carrying out chemical vapor deposition on the pyrolytic carbon coating, wherein the process parameters are as follows: the deposition temperature is 1300 ℃, natural gas is used as a carbon source, the deposition is carried out for 10 hours, and the thickness of PyC is about 12 mu m;
5) after surface polishing and cleaning, preparing the DLC coating by adopting PECVD, wherein the process parameters are as follows: degree of vacuum of 2X 10-1Pa; negative bias of the workpiece: 40V; ar flow rate: 60 sccm; ion source power: 3 kW; c2H2Flow rate: 150 sccm; heating temperature: 200 ℃; deposition time: and (4) 12 h.
The artificial tracheal stent prepared in this example: the surface hardness is 20GPa, the film-substrate bonding strength is 56N, and the maximum expansion area of the section is more than 25%.
Example 3
1) 3 layers of 120g/m21k carbon fiber twill cloth and 2 layers of 10g/m2The carbon fiber net is compounded into carbon fiber fabric by crossing and needling, and then the carbon fiber rope fabric is fixed on the tubular graphite mould to form a tubular carbon fiber prefabricated body.
2) Placing the carbon fiber preform in a deposition furnace, wherein at the temperature of 1100 ℃, methane is used as a carbon source, MTS is a silicon source, hydrogen is used as a carrier gas and a diluent gas, and the flow ratio of the gas source is methane: MTS: hydrogen is 1:1:5, and chemical vapor deposition is carried out for 100 hours, thus obtaining a carbon fiber composite material blank;
3) removing the mold, and forming a claw-shaped carbon fiber composite blank after processing (grooving and punching); punching
The distance is 8 mm.
4) Then carrying out chemical vapor deposition on the pyrolytic carbon coating, wherein the process parameters are as follows: the deposition temperature is 1300 ℃, natural gas is used as a carbon source, the deposition is carried out for 30 hours, and the thickness of PyC is 30 mu m;
5) after surface polishing and cleaning, the DLC coating is prepared by magnetron sputtering, and the process parameters are as follows: degree of vacuum of 3X 10- 1Pa; negative bias of the workpiece: 30) (ii) a Ar flow rate: 50 sccm; ion source power: 3 kW; graphite target power: 1kW, and the purity of the graphite target is 99.99 wt%; heating temperature: 100 ℃; deposition time: and 6 h.
The artificial tracheal stent prepared in this example: the surface hardness is 25GPa, the film-substrate bonding strength is 45N, and the maximum expansion area of the section is more than 15%.
Example 4
1) 2 layers of 200g/m23k carbon fiber plain cloth and 1 layer of 20g/m2And (3) compounding the carbon fiber net into a carbon fiber fabric by needling, and then fixing the carbon fiber rope fabric on a tubular graphite mold to form a tubular carbon fiber preform.
2) Placing the carbon fiber preform in a deposition furnace, taking methane as a carbon source and hydrogen as a diluent gas at the temperature of 1100 ℃, wherein the flow ratio of a gas source is methane: hydrogen is 1:2, and chemical vapor deposition is carried out for 200h, thus obtaining a carbon fiber composite material blank;
3) removing the mold, and forming an encircling tubular carbon fiber composite blank after processing (grooving and punching); punching
The distance is 10 mm.
4) After surface polishing and cleaning, preparing the DLC coating by adopting PECVD, wherein the process parameters are as follows: degree of vacuum of 2X 10-1Pa; negative bias of the workpiece: 40V; ar flow rate: 60 sccm; ion source power: 3 kW; c2H2Flow rate: 150 sccm; heating temperature: 200 ℃; deposition time: and (4) 12 h.
The artificial tracheal stent prepared in this example: the surface hardness is 10GPa, the film-substrate bonding strength is 20N, and the maximum expansion area of the section is more than 25%.
Claims (10)
1. The utility model provides a carbon-fibre composite artificial trachea support which characterized in that:
has a hierarchical tubular structure;
the hierarchical tubular structure comprises a continuous straight wall and claw holding structures axially distributed along two sides of the continuous straight wall;
the hierarchical tubular structure comprises an inner carbon fiber reinforced composite material layer and an outer DLC coating.
2. The artificial trachea stent made of carbon fiber composite materials according to claim 1, wherein:
the continuous straight wall surface is uniformly provided with small holes.
3. The artificial trachea stent made of carbon fiber composite materials according to claim 1, wherein: arc-shaped bars are uniformly arranged on two sides of the continuous straight wall, and the arc-shaped bars on two sides of the continuous straight wall are axially and alternately distributed along the layered tubular structure relatively to form a clasping claw structure in a clasping shape.
4. The artificial trachea stent made of carbon fiber composite materials according to claim 1, wherein: the carbon fiber reinforced composite material layer is made of a carbon/carbon composite material or a carbon/silicon carbide composite material.
5. The artificial trachea stent made of carbon fiber composite materials according to claim 1, wherein: a PyC transition layer is arranged between the inner carbon fiber reinforced composite material layer and the outer DLC coating.
6. The artificial trachea stent made of carbon fiber composite materials according to claim 5, wherein:
the thickness of the PyC transition layer is 5-50 μm;
the thickness of the DLC coating is 100 nm-3 mu m;
the thickness of the carbon fiber reinforced composite material layer is 1 mm-3 mm.
7. The method for preparing the carbon fiber composite material artificial trachea bracket according to any one of claims 1 to 6, which is characterized by comprising the following steps: using scheme a or scheme B:
scheme a includes the following steps:
1) weaving carbon fibers into a clamping claw structure, and performing mold auxiliary forming to obtain a tubular carbon fiber preform with the clamping claw structure;
2) densifying matrix carbon and/or silicon carbide on the tubular carbon fiber preform to obtain a tubular carbon fiber composite blank;
3) machining the tubular carbon fiber composite blank to prepare a blank;
4) generating a DLC coating on the surface of the blank, or firstly generating a PyC coating on the surface of the blank and then generating the DLC coating;
scheme B includes the following steps:
1) weaving carbon fiber fabric into a tubular structure, and performing auxiliary molding by using a mold to obtain a tubular carbon fiber preform;
2) densifying matrix carbon and/or silicon carbide on the tubular carbon fiber preform to obtain a tubular carbon fiber composite blank;
3) machining the tubular carbon fiber composite blank to prepare a blank with a claw holding structure;
4) and (3) forming a DLC coating on the surface of the blank, or forming a PyC coating on the surface of the blank and then forming the DLC coating.
8. Preparation of carbon fiber composite artificial trachea stent according to claim 7The preparation method is characterized by comprising the following steps: twisting the carbon fiber bundles into carbon fiber ropes, and weaving the carbon fiber ropes into claw holding structures; or, compounding and needling the carbon fiber cloth and the carbon fiber net into a tubular structure; the number of fibers of the carbon fiber bundle is 1k, 3k, 6k or 12 k; the carbon fiber cloth is woven by 1k, 3k, 6k or 12k carbon fiber bundles and has plain, twill or satin; the surface density of the carbon fiber net is 10g/m2～60g/m2。
9. The method for preparing the carbon fiber composite material artificial trachea stent according to claim 7, is characterized in that: the PyC coating is formed by chemical vapor deposition under the following conditions: depositing for 10-100 h at 900-1500 ℃ by adopting a gas carbon source.
10. The method for preparing the carbon fiber composite material artificial trachea stent according to claim 7, is characterized in that: the DLC coating is generated by magnetron sputtering, and the generation conditions are as follows: vacuum degree of 1X 10-1Pa～5×10-1Pa; negative bias of the workpiece: 10V-200V; ar flow rate: 50sccm to 120 sccm; ion source power: 0.5kW to 5 kW; graphite target power: 1 kW-3 kW, and the purity of the graphite target is 99.99 wt%; heating temperature: 80-200 ℃; deposition time: 1h to 12 h;
alternatively, the first and second electrodes may be,
the DLC coating is generated by plasma enhanced chemical vapor deposition, and the generation conditions are as follows: vacuum degree of 1X 10-1Pa～5×10-1Pa; negative bias of the workpiece: 10V-200V; ar flow rate: 50sccm to 120 sccm; ion source power: 0.5kW to 5 kW; hydrocarbon gas flow rate: 10sccm to 500 sccm; heating temperature: 80-300 ℃; deposition time: 1 to 12 hours.
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