CN112843340B

CN112843340B - Carbon-based composite material artificial rib and preparation method thereof

Info

Publication number: CN112843340B
Application number: CN202110062726.8A
Authority: CN
Inventors: 谭周建; 张翔; 刘波; 王斌; 蔡志霞
Original assignee: Hunan Carbon Kang Biotechnology Co ltd
Current assignee: Hunan Carbon Kang Biotechnology Co ltd
Priority date: 2021-01-18
Filing date: 2021-01-18
Publication date: 2022-08-09
Anticipated expiration: 2041-01-18
Also published as: CN112843340A

Abstract

The invention discloses an artificial rib made of carbon-based composite material and a preparation method thereof. Respectively weaving carbon fiber bundles into carbon fiber woven strips and carbon fiber woven tubes, respectively sequentially baking and shaping, performing medium ultrasonic treatment, depositing carbon and/or silicon carbide matrixes, depositing PyC coatings and/or depositing DLC or F-DLC coatings, and finally sleeving and combining to obtain the carbon-based composite material artificial rib. The artificial rib has the characteristics of light weight, good chemical stability, mechanical property close to human bones, good fatigue resistance, good biocompatibility and the like, can be freely adjusted in length after being used for transplantation or repair, can effectively avoid the black skin effect brought by the damaged end face generated by rib cutting in the transplantation or repair process, can not react with human tissues, can bear the acid-base environment in the body, can be tightly combined with the surrounding bone tissues to promote the growth of bones, has good toughness, and avoids the serious risk brought by sudden fracture.

Description

Carbon-based composite material artificial rib and preparation method thereof

Technical Field

The invention relates to an artificial rib, in particular to an artificial rib made of carbon-based composite material, and a preparation method of the artificial rib, and belongs to the technical field of medical biomaterials.

Background

Bone defects have been a difficult problem in the medical field. Chest wall bone defects are commonly seen in treatment prognosis of tumors, infections, radiation injuries and the like, and direct damage of traumatic factors and the like. Clinically, for a wide range of chest wall defects with defect area exceeding 6cm × 6cm, if more than 3 adjacent ribs are combined and spinal injuries are combined, a chest wall bone reconstruction operation is necessary to achieve the following purposes: 1) completely protecting the thoracic cavity and organs in the upper abdomen (for example, preventing the scapula from penetrating into the thoracic cavity, especially after the 5 th to 6 th ribs are cut); 2) ensuring complete respiratory function (dynamic respiratory movement, preventing pulmonary hernia and abnormal breathing); 3) the upper limbs are supported and born, and the shoulder joint movement is ensured; 4) remodeling the shape of the chest wall, ensuring the stability and aesthetic effect of the chest wall structure to the maximum extent and facilitating the recovery of confidence of the patient.

Artificial bone grafting is a common means of chest wall rigid reconstruction, from Beardsley in 1950, first using tantalum plates to repair chest wall defects, to the 20 th century, 80 s, using bone cement Polymethylmethacrylate (PMMA) for chest wall reconstruction, and the subsequent application of stainless steel plates, titanium alloys, and the like. An effective product suitable for chest wall rib reconstruction does not appear up to now. The clinical problems of the existing alternative products are as follows: 1) the PMMA implant manually made in the operation has the advantages that the surface flatness is not high, the edge is rough, the risk of soft tissue hematoma and infection after the operation is high, the impact toughness is poor, the PMMA implant is easy to crack and break under the action of external force, the risk of puncturing important organs of the thoracic cavity is realized, and a certain carcinogenic risk exists. 2) The metal products such as stainless steel have the defects of easy displacement after operation, poor tissue compatibility, influence on subsequent Magnetic Resonance Imaging (MRI) and the like, and the use frequency of the metal products is gradually reduced. 3) Titanium alloys, whether in the form of strips, sheets and webs or in modular systems (such as Matrix-RIB systems and STRATOS systems) also suffer from the following problems: higher elastic modulus leads to restrictive airway dysfunction. The mechanical strength is different from that of a normal rib, and further damage is caused when the rib is impacted by external force. Studies have shown that there is a high incidence of implant related complications (e.g. breakage and migration) within 1 year post-surgery (about 44%), with 37% broken and 7% displaced implants. And thirdly, the postoperation imaging examination is only about strong artifacts, which affect the diagnosis and treatment of subsequent diseases. Fourthly, the tissue ingrowth is not good, and the incidence rate of postoperative infection is about 5 percent.

Therefore, no product in the market can meet the following characteristics that the chest wall bone reconstruction material should have at the same time: 1) the sufficient strength can ensure the stability of the thorax, protect important organs and tissues in the chest and prevent abnormal respiration; 2) the fiber tissue is implantable, the fibrous tissue is allowed to grow on the wall, the property is stable, the infection is not easy to occur, and the cancer is not generated; 3) plasticity is convenient for fitting the outline of the thorax; 4) the compound has ray penetrability, and is convenient for postoperative review and follow-up; 5) the elastic modulus is close to that of natural cortical bone, and the restrictive pulmonary ventilation dysfunction is avoided. The carbon material has good biocompatibility, wherein the carbon fiber, the pyrolytic carbon, the carbon nanotube and the composite material thereof are applied to the aspects of heart valves, bones, growth stents, tumor drugs, biosensors and the like. In particular, carbon fiber composite materials which take carbon materials as a matrix and carbon fibers, fabrics thereof and the like as reinforcements have the characteristics of light weight, good chemical stability, mechanical properties similar to human bones, good fatigue resistance, strong designability, certain plasticity and the like, are taken as ideal materials of artificial bones, and are traced by vast researchers. Research shows that all biological performance indexes of the material meet the requirements of national standard biological safety evaluation and can be applied to clinical medicine. Compared with implant materials such as metal, polymer, ceramic and the like, the implant material has the main advantages that: 1) does not react with human tissues and can bear the subtle change of the acid-base environment in vivo without degeneration; 2) can promote the adhesion of blood platelets and make the organism have certain anticoagulant property; 3) the bone grafting agent is favorable for being tightly combined with surrounding bone tissues and promoting the growth of bones; 4) the elastic modulus is between 1GPa and 40GPa, is very close to that of human bones (1GPa to 30GPa), and can effectively avoid complications such as bone absorption and the like caused by prosthesis stress shielding; 5) the carbon fiber reinforcement has good toughness, so that the fracture behavior is in certain plasticity, and the major risk caused by sudden fracture of the material is avoided; 6) because of the X-ray permeability of the carbon element, the post-examination has no artifacts, and is beneficial to the diagnosis of the postoperative rehabilitation condition.

In addition, since the resection length is generally determined on site according to the circumstances during the surgery for resecting the tumor involving the bone, the reconstruction implant is temporarily trimmed to achieve good matching, and the damage of the implant deteriorates the postoperative rehabilitation effect. If the implant with the adjustable length can be adopted, the operation scheme can be simplified, the operation of a clinician is convenient, and the postoperative rehabilitation quality is improved.

Disclosure of Invention

Aiming at the defects in the prior art, the first object of the invention is to provide a carbon-based composite material artificial rib which is formed by compounding a carbon or silicon carbide material substrate and a carbon fiber fabric reinforcement, and has the characteristics of light weight, good chemical stability, mechanical property close to that of human bones, good fatigue resistance, good biocompatibility and the like, the carbon-based composite material artificial rib is used for transplantation or repair, the length of the carbon-based composite material artificial rib can be freely adjusted, the black skin effect caused by the damaged end face generated by cutting the rib in the transplantation or repair process can be effectively avoided, the artificial rib does not react with human tissues, the acid-base environment in a body can be borne, the carbon-based composite material artificial rib can be tightly combined with the surrounding bone tissues, the growth of bones is promoted, the elastic modulus of the carbon-based composite material artificial rib is very close to that of the human bones, the complications such as bone absorption and the like caused by prosthesis stress shielding can be effectively avoided, and the carbon-based composite material artificial rib has good toughness, avoid the material and break the major risk that brings suddenly, because the X-ray permeability of carbon element for the later stage inspection does not have the artifact, is favorable to the diagnosis of postoperative rehabilitation condition.

The invention also aims to provide a preparation method of the carbon-based composite material artificial rib, which is simple to operate, low in cost and easy for large-scale production.

In order to achieve the technical purpose, the invention provides a preparation method of an artificial rib made of a carbon-based composite material, which comprises the following steps:

a) twisting at least one carbon fiber bundle into a carbon fiber rope, and weaving the carbon fiber rope into a carbon fiber weaving strip; the surface of the carbon fiber in the carbon fiber bundle contains resin; baking and shaping the carbon fiber braided strip through a die in an auxiliary manner, applying tension to the carbon fiber braided strip along the axial direction or applying pressure vertically along a plane or simultaneously applying tension along the axial direction and pressure vertically along the plane in the baking process, and arranging a preformed hole on the surface of the carbon fiber braided strip to obtain a square strip-shaped carbon fiber prefabricated body;

b) carrying out medium ultrasonic treatment on the square strip-shaped carbon fiber preform;

c) fixing the square strip-shaped carbon fiber preform subjected to medium ultrasonic treatment on a profiling die, and obtaining a carbon fiber composite square strip-shaped blank body by chemical vapor deposition of carbon and/or silicon carbide substrate;

d) the surface of the carbon fiber composite square bar-shaped blank is subjected to chemical vapor deposition of a PyC coating (pyrolytic carbon coating) and/or physical vapor deposition of a DLC (diamond-like carbon coating) or F-DLC coating (fluorine-containing diamond-like carbon coating) to obtain a carbon fiber composite artificial rib core;

e) weaving carbon fiber bundles into a carbon fiber woven tube, filling thermoplastic polymer material particles into a tube cavity of the carbon fiber woven tube, utilizing a mold to assist warm-pressing forming, arranging a preformed hole on the surface of the carbon fiber woven tube in the mold-assisted warm-pressing forming process, and taking out the thermoplastic polymer material filled in the carbon fiber woven tube cavity to obtain a carbon fiber woven tube preform;

f) carrying out medium ultrasonic treatment on the carbon fiber braided tube preform;

g) fixing the carbon fiber braided tube preform subjected to medium ultrasonic treatment on a profiling die, and obtaining a carbon fiber composite tubular blank by chemical vapor deposition of carbon and/or silicon carbide substrate;

h) obtaining the carbon fiber composite material artificial rib tube sleeve by chemical vapor deposition of a PyC coating and/or physical vapor deposition of a DLC or F-DLC coating on the surface of the carbon fiber composite material tubular blank;

i) and inserting one end of the carbon fiber composite artificial rib core body into the carbon fiber composite artificial rib pipe sleeve to obtain the artificial rib pipe.

As a preferable scheme, in step a), the carbon fiber bundle is 1k, 3k, 6k, 12k or 24k carbon fiber, wherein 1k represents one thousand carbon fibers. The carbon fiber bundle is composed of a plurality of carbon fibers, and is usually a carbon fiber bundle with specifications of 1k, 3k, 6k, 12k or 24 k.

Preferably, in step a), the diameter of the carbon fiber rope is 0.1mm to 5 mm. The diameter of the carbon fiber rope can be adjusted according to actual needs.

Preferably, in the step a), the mass of the resin on the surface of the carbon fiber is 0.5 to 2% of the mass of the carbon fiber. These resins are common sizing agents for the surface of carbon fibers, such as epoxy resins, phenolic resins, polyimide resins, bismaleimide resins, and the like. The resin remained on the surface of the carbon fiber is not favorable for the carbon fiber material as a biological material, and is easy to rub and fall off under the action of external force. The technical scheme of the invention fully utilizes the resin on the surface of the carbon fiber to realize the baking and shaping of the carbon fiber, and simultaneously the resin is easy to remove in the subsequent process.

Preferably, in the step a), the width of the carbon fiber braided strip is 6mm to 20mm, and the thickness of the carbon fiber braided strip is 2mm to 6 mm. The carbon fiber rope is woven into a strip shape by adopting a conventional weaving process, the shape of the carbon fiber rope is similar to the shape of a human rib, and the width and the thickness of the carbon fiber woven strip can be randomly regulated and controlled.

As a preferable mode, in the step a), the resin is at least one of epoxy resin, phenolic resin, polyimide resin and bismaleimide resin.

Preferably, in step a), the tensile force applied in the axial direction during the baking process is 20N/cm ² ～200N/cm ² 。

As a preferred scheme, in the step a), the pressure is applied vertically along the plane in the baking process, and the pressure is 1N/cm ² ～10N/cm ² 。

In the baking and shaping process, pulling force with proper size is applied in the axial direction or pressure with proper size is applied in the plane vertical direction, so that the arrangement of carbon fibers in the carbon fiber braided fabric is more orderly, the volume content of the fibers can be increased, and the mechanical property of the carbon fiber composite material is effectively improved.

As a preferable scheme, in the step a), the preformed holes on the surface of the square-strip-shaped carbon fiber preform are regularly arranged along the axial direction of the surface of the square-strip-shaped carbon fiber preform, the hole interval is 5 mm-20 mm, and the aperture size is 0.5 mm-3 mm.

As a preferable scheme, in the step e), the preformed holes on the surface of the carbon fiber woven tube preform are regularly arranged along the axial direction of the surface of the carbon fiber woven tube preform, the hole interval is 5 mm-20 mm, and the aperture size is 0.5 mm-3 mm.

The preformed hole can be through weaving the strip and carbon fiber knitting pipe surface at the carbon fiber and insert the steel needle, through toasting the design back, takes out the steel needle, can obtain the preformed hole, and the preformed hole can be used for fixing. Preparation of preformed hole among the prior art generally forms at material shaping back machining, but follow-up processing can destroy continuous carbon fiber to lead to and mechanical properties to reduce, and follow-up processing can make the processing surface roughness not high, and the edge is comparatively rough, soft tissue hematoma and infection risk appear in the postoperative.

As a preferable scheme, in the step e), the thermoplastic polymer material is at least one of polyethylene, polypropylene, polyvinyl chloride and polystyrene. The thermoplastic polymer is filled in the tube cavity of the carbon fiber braided tube to prevent the structure of the carbon fiber braided tube from seriously deforming in the warm-pressing forming process.

As a preferable scheme, in the step e), the carbon fiber bundles are directly woven into the carbon fiber braided tube, or the carbon fiber bundles are twisted into the carbon fiber ropes, and then the carbon fiber ropes are woven into the carbon fiber braided tube. The carbon fiber bundle contains at least 1k carbon fibers, wherein k represents one thousand.

As a preferable scheme, in the step e), the conditions of the warm-pressing forming are as follows: the pressure is 1N/cm ² ～3N/cm ² The temperature is 60-300 ℃, and the time is 3-10 h.

As a preferable scheme, in the step a), the baking conditions are as follows: the temperature is 150-300 ℃, and the time is 3-10 h. Under appropriate baking conditions, the carbon fiber can be bonded and molded by resin on the surface thereof by high-temperature baking.

In a preferable scheme, in the step b) and the step f), the ultrasonic treatment takes water and/or an organic solvent as a medium, the ultrasonic frequency is 20 kHz-60 kHz, and the power density is 0.3W/cm ² ～1.0W/cm ² The temperature is 30-70 ℃, and the time is 10 min-60 min. Under the preferable ultrasonic treatment condition, the redundant resin particles adhered to the surface of the carbon fiber can be dissolved or fall off, so that the surface of the carbon fiber is smooth and flat, and the phenomenon that the particles fall off under the action of external force continuously after the artificial rib made of the carbon-based composite material is implanted to cause the skin blackening effect is avoided.

As a preferred embodiment, in step c) and step g), the conditions for chemical vapor deposition of the carbon substrate are: the deposition temperature is 850-1600 ℃, the deposition time is 20-200 h, the deposition pressure is 3-10 kPa, and the gas source is hydrocarbon gas. Hydrocarbon gases such as natural gas, methane or propylene, etc.

As a preferred embodiment, the conditions for chemical vapor deposition of the silicon carbide substrate in steps c) and g): the deposition temperature is 900-1300 ℃, the deposition time is 20-200 h, the deposition pressure is 0.5-3 kPa, and the gas source is a gaseous carbon-silicon source. The silicon-carbon source is, for example, trichloromethylsilane

As a preferred embodiment, when depositing carbon and silicon carbide substrates in a chemical vapor deposition process, the silicon carbide substrate may be deposited first and then the carbon substrate, or the carbon substrate may be deposited first and then the silicon carbide substrate may be deposited.

As a preferred embodiment, in step d) and step h), the conditions for chemical vapor deposition of PyC coating are: the deposition temperature is 900-1500 ℃, the deposition time is 10-50 h, the deposition pressure is 0.5-3 kPa, and the gas source is hydrocarbon gas. Hydrocarbon gases such as natural gas, methane or propylene, etc. By controlling the chemical vapor deposition conditions, PyC coatings with a thickness of 5-50 μm can be obtained.

As a preferable scheme, a step of high-temperature impurity removal treatment is further included between the steps c) and d) or between the steps g) and h). Specifically, the carbon fiber composite material blank with the deposited carbon matrix or the silicon carbide matrix is put into a high-temperature furnace for high-temperature treatment, and is heated under the condition of vacuum or protective atmosphere to remove impurities, wherein the step can be selectively adopted or not adopted according to the requirement. Further preferably, the high-temperature treatment conditions are as follows: keeping the temperature at 1500-2300 ℃ for 1-10 h;

as a preferred embodiment, the conditions for physical vapor deposition of the DLC coating in step d) and step h) are: trueThe degree of hollowness is 1 x 10 ^-1 Pa～5×10 ^-1 Pa; the negative bias voltage of the workpiece is 80V-800V; ar flow is 10 sccm-100 sccm; the power of the graphite target is 1 kW-3 kW, and the purity is not lower than 99.99 wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 10min to 300 min; alternatively, the conditions for physical vapor deposition of DLC coatings are: vacuum degree of 1X 10 ^-1 Pa～5×10 ^-1 Pa; the negative bias voltage of the workpiece is 80V-800V; the Ar flow is 10sccm to 100 sccm; the power of the ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 10sccm to 500 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min. By controlling the physical vapor deposition conditions, DLC coatings with a thickness of 0.05-2 μm can be obtained.

As a preferred scheme, in the step d) and the step h), the conditions for physical vapor deposition of the F-DLC coating are as follows: vacuum degree of 1X 10 ^-1 Pa～5×10 ^-1 Pa; the negative bias voltage of the workpiece is 80V-800V; ar flow is 10 sccm-100 sccm; the power of the ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 50sccm to 500 sccm; CF (compact flash) ₄ The gas flow is 10sccm to 200 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min. Hydrocarbon gases such as methane, acetylene or propylene, etc. By controlling the physical vapor deposition conditions, the F-DLC coating with the thickness of 0.05-2 μm can be obtained.

The F-DLC coating has better biocompatibility than the DLC coating or the PyC coating, and can improve the bioinert characteristic of the carbon material, so the F-DLC coating is preferably deposited on the surface of the carbon-based composite material artificial rib blank.

The invention also provides an artificial rib made of the carbon-based composite material, which is obtained by the preparation method. The carbon-based composite material artificial rib is formed by assembling the carbon fiber composite material core and the carbon fiber composite material pipe sleeve, one end of the carbon fiber composite material core is inserted into the carbon fiber composite material pipe sleeve, the length of the carbon-based composite material artificial rib can be adjusted by adjusting the length of the carbon fiber composite material core inserted into the carbon fiber composite material pipe sleeve, and the black skin effect caused by the damaged end face of the rib in the process of transplantation or repair can be effectively avoided. The artificial rib is made of carbon fiber composite materials, carbon fibers are used as a reinforcing phase, and carbon materials or silicon carbide materials are used as a matrix, so that the artificial rib has the characteristics of light weight, good chemical stability, mechanical properties similar to those of human bones, good fatigue resistance, strong designability, certain plasticity and the like.

The invention provides a preparation method of an artificial rib made of a carbon-based composite material, which comprises the following specific steps:

a) twisting carbon fiber bundles into carbon fiber ropes, and selecting 1 to a plurality of carbon fiber bundles to be twisted into the ropes according to the diameter requirement of the ropes, wherein the diameter of the carbon fiber ropes is generally 0.1-5 mm; wherein, the carbon fiber bundle is not subjected to resin removal treatment, the surface of the carbon fiber bundle generally contains sizing agent (resin), the sizing agent is commonly epoxy resin, phenolic resin, polyimide resin, bismaleimide resin and the like, and the resin accounts for 0.5-2% of the mass of the carbon fiber; the carbon fiber bundle is a plurality of carbon fibers, and more specifically, it is usually 1k, 3k, 6k, 12k, 24k, etc., where 1k represents one thousand carbon fibers.

b) The carbon fiber rope is woven into a carbon fiber woven strip, the weaving process adopts a common weaving process in the prior art, the width of the carbon fiber woven strip is 6-20 mm, and the thickness of the carbon fiber woven strip is 2-6 mm.

c) Heating, baking and shaping the carbon fiber woven strip by the aid of a mold, applying tensile force to the carbon fiber woven strip along the axial direction, or applying pressure vertically along a plane, or simultaneously applying tensile force along the axial direction and applying pressure vertically along the plane, and inserting steel needles (the head of each steel needle is conical) into the surface of the carbon fiber woven strip to form preformed holes, so as to obtain a square strip-shaped carbon fiber body; the shape of the mould involved in the step is regular straight strip, the shape of the inner cavity is a cuboid cavity, and the mould is made of common materials such as graphite, steel plates and the like; the arrangement and the number of the preformed holes on the surface of the carbon fiber braided strip are determined according to actual needs, specifically, if the preformed holes are regularly arranged along the surface of the carbon fiber braided strip in the axial direction, the hole interval is 5-20 mm, and the aperture size is 0.5-3 mm; the tensile force applied along the axial direction in the baking process is 20N/cm ² ～200N/cm ² The pressure applied vertically along the plane is 1N/cm ² ～10N/cm ² (ii) a The baking conditions are that: the temperature is 150-300 ℃, and the time is 3-10 h; the density of the carbon fiber strip preform is 1.00g/cm ³ ～1.50g/cm ³ 。

d) The square strip-shaped carbon fiber preform is cleaned by medium ultrasonic, residues on the surface of the resin cured are removed, and the ultrasonic frequency is 20-60 kHz; the power density is 0.3W/cm ² ～1.0W/cm ² (ii) a The temperature is 30-70 ℃; the time is 10 min-60 min, and the medium is purified water, acetone or ethanol and the like according to the requirement.

e) Fixing one side surface or two opposite side surfaces of the cleaned square strip-shaped carbon fiber preform on a profiling die, wherein the die is a high-temperature resistant die, and the shape of the die is consistent according to the shape of a rib to be processed if the die is made of graphite; then, the matrix carbon and/or silicon carbide is compacted to form a carbon fiber composite square strip-shaped blank; conditions of the chemical vapor deposition carbon substrate: the deposition temperature is 850-1600 ℃, the deposition time is 20-200 h, the deposition pressure is 3-10 kPa, and the gas source is natural gas, methane or propylene, etc.; conditions for chemical vapor deposition of a silicon carbide substrate: the deposition temperature is 900-1300 ℃, the deposition time is 20-200 h, the deposition pressure is 0.5-3 kPa, and the gas source is trichloromethylsilane, etc.; in chemical vapor deposition of carbon and silicon carbide substrates, the silicon carbide may be deposited first and then the carbon substrate, or the carbon substrate may be deposited first and then the silicon carbide may be deposited.

f) Putting the carbon fiber composite square strip-shaped blank into a high-temperature furnace for high-temperature treatment, and heating under the condition of vacuum or protective atmosphere to remove impurities (the step can be selectively adopted or not adopted according to the requirement); wherein the high-temperature treatment conditions are as follows: keeping the temperature at 1500-2300 ℃ for 1-10 h;

g) preparing a PyC coating or a DLC coating or an F-DLC coating or a PyC coating and a DLC coating/F-DLC coating on the surface of the carbon fiber composite square strip blank to obtain a carbon fiber composite artificial rib core; preparing a PyC coating (with the thickness of 5-50 mu m) by chemical vapor deposition, wherein the deposition temperature is 900-1500 ℃, the deposition time is 10-50 h, the deposition pressure is 0.5-3 kPa, and the gas source is hydrocarbon gas; preparing a DLC coating F-DLC coating (with the thickness of 0.05-2 mu m) by physical vapor deposition, wherein the percentage of F atoms is 5-20%(ii) a The conditions for physical vapor deposition of DLC coatings were: vacuum degree of 1X 10 ^-1 Pa～5×10 ^-1 Pa; the negative bias voltage of the workpiece is 80V-800V; ar flow is 10 sccm-100 sccm; the power of the graphite target is 1 kW-3 kW, and the purity is not lower than 99.99 wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 10min to 300 min; alternatively, the conditions for physical vapor deposition of DLC coatings are: vacuum degree of 1X 10 ^-1 Pa～5×10 ^- ¹ Pa; the negative bias voltage of the workpiece is 80V-800V; ar flow is 10 sccm-100 sccm; the power of the ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 10sccm to 500 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min. The conditions for physical vapor deposition of the F-DLC coating were: vacuum degree of 1X 10 ^-1 Pa～5×10 ^-1 Pa; the negative bias voltage of the workpiece is 80V-800V; ar flow is 10 sccm-100 sccm; the power of the ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 50sccm to 500sccm (the hydrocarbon gas is methane, acetylene, propylene or the like); CF (compact flash) ₄ The gas flow is 10sccm to 200 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min.

h) Will carbon fiber bundle directly weaves into carbon fiber braided tube, perhaps twist carbon fiber bundle into carbon fiber rope, weave carbon fiber braided tube with carbon fiber rope again, carbon fiber bundle contains at least 1k carbon fiber, wherein, k represents a thousand, adopts weaving technology for common carbon fiber weaving technology among the prior art, at the inside thermoplasticity macromolecular material granule of packing of the lumen of carbon fiber braided tube, it is at least one among polyethylene, polypropylene, polyvinyl chloride, the polystyrene to state thermoplasticity macromolecular material, the thermoplasticity macromolecule plays to fill supplementary forming effect to utilize the supplementary warm-pressing of mould to take shape, the condition of warm-pressing shaping is: the pressure is 1N/cm ² ～3N/cm ² Setting preformed holes on the surface of the carbon fiber braided tube in the mold-assisted warm-pressing forming process at the temperature of 60-300 ℃ for 3-10 h, wherein the preformed holes are regularly distributed along the surface of the carbon fiber braided tube in the axial direction, the hole intervals are 5-20 mm, and the pore diameter is 0.5-3 mm; then taking out the thermoplastic polymer material filled in the carbon fiber braided tube cavity to obtain the carbon fiber braided tubeA green body;

d) carrying out medium ultrasonic treatment, substrate carbon densification and/or silicon carbide densification and high-temperature treatment on the carbon fiber woven tube blank body according to the steps d) -g), and preparing a PyC coating or a DLC coating or an F-DLC coating or a PyC coating and a DLC coating/F-DLC coating to obtain the carbon fiber composite material artificial rib tube sleeve;

e) and inserting one end of the carbon fiber composite artificial rib core body into the carbon fiber composite artificial rib pipe sleeve to obtain the artificial rib pipe.

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

the carbon-based composite material artificial rib provided by the invention is formed by combining the carbon fiber composite material braided strip and the carbon fiber composite material braided tube, the carbon fiber composite material braided strip can be telescopically adjusted in the carbon fiber composite material braided tube, the length can be freely adjusted in the using process, and the skin-blacking effect caused by damaged end faces due to interception in the operation is avoided.

The artificial rib is used for transplantation or repair, does not react with human tissues, can bear acid-base environment in vivo, can be tightly combined with surrounding bone tissues, promotes the growth of bones, has elastic modulus very close to the human bones, can effectively avoid complications such as bone absorption and the like caused by prosthesis stress shielding, has good toughness, avoids major risks caused by sudden fracture of materials, has no artifacts in later-stage examination due to the X-ray permeability of carbon elements, and is favorable for postoperative rehabilitation diagnosis.

The artificial rib made of the carbon-based composite material provided by the invention has excellent mechanical properties and completely meets the requirements of rib transplantation or repair. The effective density of the artificial rib core made of the carbon fiber composite material is 1.50g/cm ³ ～2.00g/cm ³ (ii) a Bending property: the strength is more than 40MPa, and the modulus is 2 GPa-10 GPa; tensile property: the strength is more than 150MPa, and the modulus is 5 GPa-30 GPa; impact toughnessProperty: is more than 8J/cm ² . The bending modulus of the carbon-based composite material artificial rib tube sleeve is 10 GPa-20 GPa, and the impact toughness is more than 10J/cm ² 。

The preparation method of the carbon-based composite material artificial rib provided by the invention is simple to operate, low in cost and easy for large-scale production.

Drawings

Fig. 1 is a combination view of an artificial rib made of carbon-based composite material.

Fig. 2 is a split view of an artificial rib made of carbon-based composite material.

FIG. 3 is a scanning electron microscope image of the surface topography of carbon fibers of square strip-shaped carbon fiber preforms of example 1 and comparative example 2 cleaned with and without ultrasonic cleaning of a medium; wherein, fig. 3a is ultrasonic cleaning without medium, and fig. 3b is ultrasonic cleaning with medium.

Detailed Description

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

Example 1

a) The preparation method of the carbon-based composite material artificial rib comprises the following specific steps:

twisting carbon fiber bundles into carbon fiber ropes, selecting 3 bundles of 6k carbon fibers, and twisting into ropes, wherein the diameter of each carbon fiber rope is 1 mm; wherein, the carbon fiber bundle is not subjected to resin removal treatment, and the surface of the carbon fiber bundle contains epoxy resin accounting for 1 percent of the mass of the carbon fiber.

b) 15 carbon fiber ropes are woven into carbon fiber woven strips with the width of 12mm and the thickness of 2 mm.

c) Heating, baking and shaping the carbon fiber braided strip by the aid of a mold, vertically applying pressure to the carbon fiber braided strip along a plane in the baking process, and inserting steel needles (the head of each steel needle is conical) into the surfaces of the carbon fiber braided strip to form preformed holes so as to obtain a square strip-shaped carbon fiber body; the preformed holes on the surface of the carbon fiber braided strip are regularly distributed along the surface of the carbon fiber braided strip in the axial direction, the hole interval is 12mm, and the aperture size is 1.5 mm; the pressure applied vertically along the plane during the baking process is 5N/cm ² (ii) a The baking conditions are as follows: the temperature is 200 ℃ and the time is 5 h; the density of the carbon fiber strip preform is1.26g/cm ³ 。

d) Ultrasonically cleaning the square strip-shaped carbon fiber preform by using a medium to remove residues on the cured surface of the resin, wherein the ultrasonic frequency is 40 kHz; the power density is 0.5W/cm ² (ii) a The temperature is 50 ℃; the time is 20min, and the medium is ethanol. Fixing the surfaces of two opposite sides of the carbon fiber prefabricated body on a profiling die, and then compacting matrix carbon to form a carbon fiber composite material artificial rib core body blank; conditions of the chemical vapor deposition carbon substrate: the deposition temperature is 1100 ℃, the deposition time is 100h, the deposition pressure is 6kPa, and the gas source is methane. Placing the carbon fiber composite artificial rib core body blank into a high-temperature furnace for high-temperature treatment, and heating under the condition of vacuum or protective atmosphere to remove impurities; wherein the high-temperature treatment conditions are as follows: the temperature is 1500 ℃, and the temperature is kept for 5 h. Preparing a PyC coating and a DLC coating on the surface of the carbon fiber composite artificial rib core body blank; preparing a pyrolytic carbon coating by chemical vapor deposition, wherein the deposition temperature is 1200 ℃, the deposition time is 20 hours, the deposition pressure is 2kPa, and the gas source is methane; DLC coatings were prepared by physical vapor deposition with the conditions: vacuum degree of 2X 10 ^-1 Pa; the negative bias voltage of the workpiece is 200V; ar flow is 50 sccm; the power of the graphite target is 2kW, and the purity is not lower than 99.99 wt%; the revolution speed of the material table is 15 r/min; the heating temperature is 130 ℃; the deposition time was 30 min.

e) The method comprises the following steps of directly weaving 75 bundles of 3k carbon fibers into a carbon fiber woven tube with the section circumference of 24mm, filling polyethylene particles into a tube cavity of the carbon fiber woven tube, and utilizing a mold to assist warm-pressing forming under the conditions of: the pressure is 2N/cm ² Setting reserved holes on the surface of the carbon fiber braided tube in the auxiliary warm-pressing forming process of the die, wherein the reserved holes are regularly distributed along the axial direction of the surface of the carbon fiber braided tube at the interval of 12mm and the aperture size of 1.5mm, and the temperature is 80 ℃ and the time is 3 hours; then taking out the thermoplastic polymer material filled in the tube cavity of the carbon fiber braided tube to obtain a carbon fiber braided tube blank;

f) ultrasonically cleaning a carbon fiber braided tube blank by using a medium, and removing residues on the cured surface of resin, wherein the ultrasonic frequency is 40 kHz; the power density is 0.5W/cm ² (ii) a The temperature is 50 ℃; the time is 20min, and the medium is ethanol. Carbon fiber tubeFixing the opposite two side surfaces of the blank on a profiling die, and then compacting matrix carbon to form a carbon fiber composite material artificial rib pipe sleeve blank; conditions of the chemical vapor deposition carbon substrate: the deposition temperature is 1100 ℃, the deposition time is 100h, the deposition pressure is 6kPa, and the gas source is methane. Placing the carbon fiber composite material artificial rib tube sleeve blank into a high-temperature furnace for high-temperature treatment, and heating under the condition of vacuum or protective atmosphere to remove impurities; wherein the high-temperature treatment conditions are as follows: the temperature is 1500 ℃, and the temperature is kept for 5 h. Preparing a PyC coating and a DLC coating on the surface of the carbon fiber composite material artificial rib tube sleeve blank; preparing a pyrolytic carbon coating by chemical vapor deposition, wherein the deposition temperature is 1200 ℃, the deposition time is 20 hours, the deposition pressure is 2kPa, and the gas source is methane; DLC coatings were prepared by physical vapor deposition with the conditions: vacuum degree of 2X 10 ^-1 Pa; the negative bias voltage of the workpiece is 200V; ar flow is 50 sccm; the power of the graphite target is 2kW, and the purity is not lower than 99.99 wt%; the revolution speed of the material table is 15 r/min; the heating temperature is 130 ℃; the deposition time was 30 min.

g) And inserting one end of the core body of the carbon fiber composite artificial rib into the pipe sleeve of the carbon fiber composite artificial rib to obtain the carbon-based composite artificial rib with the length capable of being adjusted in a telescopic mode.

The effective density of the carbon fiber composite material artificial rib core of the prepared carbon-based composite material artificial rib is 1.65g/cm ³ (ii) a Bending property: the strength is 56MPa, and the modulus is 3 GPa; tensile property: strength 187MPa, modulus 11 GPa; impact toughness: 12J/cm ² . The bending of the carbon fiber composite material artificial rib pipe sleeve is 13GPa, and the impact toughness is 12J/cm ² 。

Example 2

Steps a), b), d) to g) are as in example 1.

c) Heating, baking and shaping the carbon fiber braided strip by the aid of a mold, applying a tensile force to the carbon fiber braided strip along the axial direction in the baking process, and inserting steel needles (the head of each steel needle is conical) into the surfaces of the carbon fiber braided strip to form preformed holes so as to obtain a square strip-shaped carbon fiber body; the preformed holes on the surface of the carbon fiber braided strip are regularly distributed along the surface of the carbon fiber braided strip in the axial direction, the hole interval is 12mm, and the aperture size is 1.5 mm; in the baking processThe tensile force exerted along the axial direction is 60N/cm ² (ii) a The baking conditions are as follows: the temperature is 200 ℃ and the time is 5 h; the density of the carbon fiber strip preform is 1.35g/cm ³ 。

The effective density of the carbon fiber composite material artificial rib core of the prepared carbon-based composite material artificial rib is 1.69g/cm ³ (ii) a Bending property: strength is 68MPa, and modulus is 5 GPa; tensile property: strength 230MPa, modulus 15 GPa; impact toughness: 12J/cm ² . The bending of the carbon fiber composite material artificial rib pipe sleeve is 13GPa, and the impact toughness is 12J/cm ² 。

Example 3

Steps a), b), d) to g) are as in example 1.

c) Heating, baking and shaping the carbon fiber braided strip by the aid of a mold, simultaneously applying tensile force to the carbon fiber braided strip along the axial direction and vertically applying pressure along a plane in the baking process, and inserting steel needles (the head of each steel needle is conical) into the surface of the carbon fiber braided strip to form preformed holes so as to obtain a square strip-shaped carbon fiber body; the preformed holes on the surface of the carbon fiber braided strip are regularly distributed along the surface of the carbon fiber braided strip in the axial direction, the hole interval is 12mm, and the aperture size is 1.5 mm; the tensile force applied along the axial direction in the baking process is 60N/cm ² The pressure applied vertically along the plane is 5N/cm ² (ii) a The baking conditions are as follows: the temperature is 200 ℃ and the time is 5 h; the density of the carbon fiber strip preform is 1.54g/cm ³ 。

The effective density of the carbon fiber composite material artificial rib core of the prepared carbon-based composite material artificial rib is 1.75g/cm ³ (ii) a Bending property: strength is 82MPa, and modulus is 6 GPa; tensile property: strength is 258MPa, and modulus is 18 GPa; impact toughness: 16J/cm ² . The bending of the carbon fiber composite material artificial rib pipe sleeve is 13GPa, and the impact toughness is 12J/cm ² 。

Example 4

The preparation method of the carbon-based composite material artificial rib comprises the following specific steps:

a) twisting carbon fiber bundles into carbon fiber ropes, selecting 3 bundles of 12k carbon fibers, and twisting into ropes, wherein the diameter of each carbon fiber rope is 2 mm; wherein, the carbon fiber bundle is not subjected to resin removal treatment, and the surface of the carbon fiber bundle contains polyimide resin accounting for 1.2 percent of the mass of the carbon fiber.

b) 10 carbon fiber ropes are woven into carbon fiber woven strips with the width of 12mm and the thickness of 3 mm.

c) Heating, baking and shaping the carbon fiber braided strip by the aid of a mold, vertically applying pressure to the carbon fiber braided strip along a plane in the baking process, and inserting steel needles (the head of each steel needle is conical) into the surfaces of the carbon fiber braided strip to form preformed holes so as to obtain a square strip-shaped carbon fiber body; the preformed holes on the surface of the carbon fiber braided strip are regularly distributed along the surface of the carbon fiber braided strip in the axial direction, the hole interval is 15mm, and the aperture size is 2.5 mm; the pressure applied vertically along the plane during the baking process is 5N/cm ² (ii) a The baking conditions are as follows: the temperature is 200 ℃ and the time is 5 h; the density of the carbon fiber strip preform is 1.24g/cm ³ 。

d) Ultrasonically cleaning the square strip-shaped carbon fiber preform by using a medium to remove residues on the cured surface of the resin, wherein the ultrasonic frequency is 50 kHz; the power density is 0.8W/cm ² (ii) a The temperature is 60 ℃; the time is 10min, and the medium is acetone. Fixing the surfaces of two opposite sides of the carbon fiber prefabricated body on a profiling die, and then compacting matrix carbon and silicon carbide to form a carbon fiber composite material artificial rib core body blank; conditions of the chemical vapor deposition carbon substrate: the deposition temperature is 1500 ℃, the deposition time is 200h, the deposition pressure is 8kPa, and the gas source is natural gas; conditions for chemical vapor deposition of a silicon carbide substrate: the deposition temperature is 1150 ℃, the deposition time is 60 hours, the deposition pressure is 2kPa, and the gas source is trichloromethylsilane. Preparing an F-DLC coating on the surface of the carbon fiber composite artificial rib core body blank under the following conditions: vacuum degree of 3X 10 ^-1 Pa; the negative bias voltage of the workpiece is 80V; ar flow is 60 sccm; the power of the ion source is 2 kW; the hydrocarbon gas flow rate was 200sccm (acetylene); CF (compact flash) ₄ The gas flow rate is 40 sccm; the heating temperature is 220 ℃; the deposition time was 40 min.

e) Twisting 3 bundles of 6k carbon fibers into carbon fiber ropes, weaving 45 carbon fiber ropes into a carbon fiber woven tube with a section circumference of 30mm, filling polystyrene particles in a tube cavity of the carbon fiber woven tube, and utilizing a mold to assist warm-pressing forming, wherein the warm-pressing forming condition is as follows: the pressure is 3N/cm ² Setting reserved holes on the surface of the carbon fiber braided tube in the mold-assisted warm pressing forming process at the temperature of 100 ℃ for 3 hours, wherein the reserved holes are regularly distributed along the surface axial direction of the carbon fiber braided tube, the hole interval is 15mm, and the pore diameter is 2.5 mm; then taking out the thermoplastic polymer material filled in the tube cavity of the carbon fiber braided tube to obtain a carbon fiber braided tube blank;

f) ultrasonically cleaning a carbon fiber braided tube blank by using a medium, and removing residues on the cured surface of resin, wherein the ultrasonic frequency is 50 kHz; the power density is 0.8W/cm ² (ii) a The temperature is 60 ℃; the time is 10min, and the medium is acetone. Fixing the opposite two side surfaces of the carbon fiber braided tube blank on a profiling die, and then compacting matrix carbon and silicon carbide to form a carbon fiber composite material artificial rib tube sleeve blank; conditions of the chemical vapor deposition carbon substrate: the deposition temperature is 1500 ℃, the deposition time is 200h, the deposition pressure is 8kPa, and the gas source is natural gas; conditions for chemical vapor deposition of a silicon carbide substrate: the deposition temperature is 1150 ℃, the deposition time is 60 hours, the deposition pressure is 2kPa, and the gas source is trichloromethylsilane. Preparing an F-DLC coating on the surface of the carbon fiber composite material artificial rib tube sleeve blank under the following conditions: vacuum degree of 3X 10 ^-1 Pa; the negative bias voltage of the workpiece is 80V; ar flow is 60 sccm; the power of the ion source is 2 kW; the hydrocarbon gas flow rate was 200sccm (acetylene); CF (compact flash) ₄ The gas flow rate is 40 sccm; the heating temperature is 220 ℃; the deposition time was 40 min.

The effective density of the carbon fiber composite material artificial rib core of the prepared carbon-based composite material artificial rib is 1.93g/cm ³ (ii) a Bending property: strength 97MPa, modulus 10 GPa; tensile property: strength 245MPa, modulus 19 GPa; impact toughness: 15J/cm ² . The bending of the carbon fiber composite material artificial rib sleeve is 18GPa, and the impact toughness is 14J/cm ² 。

Comparative example 1

steps a) to g) are as in example 1 except that no pressure is applied perpendicularly to the plane of the woven carbon fiber strip and no pressure is applied perpendicularly to the plane of the assembly during the baking and setting process of step c).

The effective density of the carbon fiber composite material artificial rib core of the prepared carbon-based composite material artificial rib is 1.46g/cm ³ (ii) a Bending property: strength 42MPa, modulus 2 GPa; tensile property: strength 116MPa, modulus 5 GPa; impact toughness: 8J/cm ² . The bending of the carbon fiber composite material artificial rib pipe sleeve is 13GPa, and the impact toughness is 12J/cm ² 。

Comparative example 2

the other steps were as in example 1 except that the step of ultrasonic cleaning of the square strip-shaped carbon fiber preform with the medium in step d) was not performed.

The carbon fiber surface contains obvious granular resin without medium ultrasonic cleaning treatment, and the granular resin is easy to fall off to cause a black skin effect. And the surface of the carbon fiber is smooth and flat through medium ultrasonic cleaning treatment, and the granular resin is obviously reduced.

Claims

1. A preparation method of an artificial rib made of carbon-based composite material is characterized by comprising the following steps: the method comprises the following steps:

a) twisting at least one carbon fiber bundle into a carbon fiber rope, and weaving the carbon fiber rope into a carbon fiber weaving strip; the surface of the carbon fiber in the carbon fiber bundle contains resin; baking and shaping the carbon fiber braided strip by using a die in an auxiliary manner, applying tension to the carbon fiber braided strip along the axial direction or vertically applying pressure along a plane or simultaneously applying tension along the axial direction and pressure vertically applying pressure along the plane in the baking process, and arranging a preformed hole on the surface of the carbon fiber braided strip to obtain a square strip-shaped carbon fiber prefabricated body; the mass of the resin on the surface of the carbon fiber is 0.5-2% of the mass of the carbon fiber; during the baking process, the tensile force is applied along the axial direction and is 20N/cm ² ～200N/cm ² Is vertically applied along a planeThe magnitude of the applied pressure is 1N/cm ² ～10N/cm ² ；

b) Carrying out medium ultrasonic treatment on the square strip-shaped carbon fiber preform; wherein the ultrasonic treatment uses water and/or organic solvent as medium, the ultrasonic frequency is 20 kHz-60 kHz, and the power density is 0.3W/cm ² ～1.0W/cm ² The temperature is 30-70 ℃, and the time is 10-60 min;

d) obtaining the carbon fiber composite material artificial rib core body on the surface of the carbon fiber composite material square strip-shaped blank through chemical vapor deposition of a PyC coating and/or through physical vapor deposition of a DLC or F-DLC coating;

f) carrying out medium ultrasonic treatment on the carbon fiber braided tube preform; wherein the ultrasonic treatment uses water and/or organic solvent as medium, the ultrasonic frequency is 20 kHz-60 kHz, and the power density is 0.3W/cm ² ～1.0W/cm ² The temperature is 30-70 ℃, and the time is 10-60 min;

g) fixing the carbon fiber braided tube prefabricated body subjected to medium ultrasonic treatment on a profiling die, and depositing a carbon and/or silicon carbide substrate by chemical vapor to obtain a carbon fiber composite material tubular blank;

2. The method for preparing the artificial rib made of the carbon-based composite material according to claim 1, wherein the method comprises the following steps:

in the step a), the carbon fiber bundle is 1k, 3k, 6k, 12k or 24k carbon fibers, wherein 1k represents one thousand carbon fibers;

in the step a), the diameter of the carbon fiber rope is 0.1-5 mm;

in the step a), the width of the carbon fiber braided strip is 6-20 mm, and the thickness of the carbon fiber braided strip is 2-6 mm;

in the step a), the resin is at least one of epoxy resin, phenolic resin, polyimide resin and bismaleimide resin.

3. The method for preparing the artificial rib made of the carbon-based composite material according to claim 1, wherein the method comprises the following steps:

in the step a), the preformed holes on the surface of the square strip-shaped carbon fiber preform are axially and regularly arranged along the surface of the square strip-shaped carbon fiber preform, the hole interval is 5-20 mm, and the aperture is 0.5-3 mm;

in the step e), the preformed holes on the surface of the carbon fiber woven tube preform are regularly arranged along the axial direction of the surface of the carbon fiber woven tube preform, the hole interval is 5-20 mm, and the aperture size is 0.5-3 mm.

4. The method for preparing the artificial rib made of the carbon-based composite material according to claim 1, wherein the method comprises the following steps:

in the step e), the thermoplastic polymer material is at least one of polyethylene, polypropylene, polyvinyl chloride and polystyrene;

in the step e), the carbon fiber bundles are directly woven into the carbon fiber woven pipe, or the carbon fiber bundles are twisted into carbon fiber ropes, and then the carbon fiber ropes are woven into the carbon fiber woven pipe; the carbon fiber bundle comprises at least 1k carbon fibers, wherein k represents one thousand;

in the step e), the warm-pressing forming conditions are as follows: the pressure is 1N/cm ² ～3N/cm ² The temperature is 60-300 ℃, and the time is 3-10 h.

5. The method for preparing the artificial rib made of the carbon-based composite material according to claim 1, wherein the method comprises the following steps:

in the step a), the baking conditions are as follows: the temperature is 150-300 ℃, and the time is 3-10 h.

6. The method for preparing the artificial rib made of the carbon-based composite material according to claim 1, wherein the method comprises the following steps:

in step c) and step g), the conditions of the chemical vapor deposition of the carbon substrate: the deposition temperature is 850-1600 ℃, the deposition time is 20-200 h, the deposition pressure is 3-10 kPa, and the gas source is hydrocarbon gas;

in steps c) and g), the conditions for chemical vapour deposition of the silicon carbide substrate are as follows: the deposition temperature is 900-1300 ℃, the deposition time is 20-200 h, the deposition pressure is 0.5-3 kPa, and the gas source is a gaseous carbon-silicon source.

7. The method for preparing the artificial rib made of the carbon-based composite material according to claim 1, wherein the method comprises the following steps:

in step d) and step h), the conditions for chemical vapor deposition of the PyC coating are: the deposition temperature is 900-1500 ℃, the deposition time is 10-50 h, the deposition pressure is 0.5-3 kPa, and the gas source is hydrocarbon gas;

in step d) and step h), the conditions for physical vapor deposition of the DLC coating are: vacuum degree of 1X 10 ^-1 Pa～5×10 ^-1 Pa; the negative bias voltage of the workpiece is 80V-800V; ar flow is 10 sccm-100 sccm; the power of the graphite target is 1 kW-3 kW, and the purity is not lower than 99.99 wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 10min to 300 min; alternatively, the conditions for physical vapor deposition of DLC coatings are: vacuum degree of 1X 10 ^-1 Pa～5×10 ^-1 Pa; the negative bias voltage of the workpiece is 80V-800V; ar flow is 10 sccm-100 sccm; the power of the ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 10sccm to 500 sccm; the heating temperature is 80-300 ℃; the deposition time is 10min to 300 min;

in the step d) and the step h), the conditions for physical vapor deposition of the F-DLC coating are as follows: vacuum degree of 1X 10 ^-1 Pa～5×10 ^- ¹ Pa; the negative bias voltage of the workpiece is 80V-800V; ar flow is 10 sccm-100 sccm; the power of the ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 50sccm to 500 sccm; CF (compact flash) ₄ The gas flow is 10sccm to 200 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min.

8. An artificial rib made of carbon-based composite material is characterized in that: the preparation method of any one of claims 1 to 7.