CN112876269B - Length-adjustable carbon fiber composite artificial rib and preparation method thereof - Google Patents

Length-adjustable carbon fiber composite artificial rib and preparation method thereof Download PDF

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CN112876269B
CN112876269B CN202110064029.6A CN202110064029A CN112876269B CN 112876269 B CN112876269 B CN 112876269B CN 202110064029 A CN202110064029 A CN 202110064029A CN 112876269 B CN112876269 B CN 112876269B
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carbon fiber
strip
carbon
fiber woven
deposition
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CN112876269A (en
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谭周建
张翔
刘波
王斌
蔡志霞
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Hunan Carbon Kang Biotechnology Co ltd
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Hunan Carbon Kang Biotechnology Co ltd
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Abstract

The invention discloses a length-adjustable carbon fiber composite artificial rib and a preparation method thereof. The method comprises the steps of respectively weaving carbon fiber bundles into carbon fiber woven strips and carbon fiber woven tubes, and combining the carbon fiber woven strips or the carbon fiber woven strips with the carbon fiber woven tubes after baking and shaping, and then sequentially carrying out the steps of baking and shaping, medium ultrasonic treatment, carbon and/or silicon carbide matrix deposition, pyC coating deposition and/or DLC or F-DLC coating deposition and the like to obtain the carbon fiber composite material artificial rib. The artificial rib has the characteristics of light weight, good chemical stability, good mechanical property similar to human bones, good fatigue resistance, good biocompatibility and the like, can be used for freely adjusting the length after being transplanted or repaired, can effectively avoid the black skin effect caused by broken end surfaces generated by rib interception in the transplanting or repairing process, does not react with human tissues, can bear an in-vivo acid-base environment, can be tightly combined with surrounding bone tissues to promote the growth of the bones, has good toughness, and avoids great risks caused by sudden fracture.

Description

Length-adjustable carbon fiber composite artificial rib and preparation method thereof
Technical Field
The invention relates to an artificial rib, in particular to a length-adjustable carbon fiber composite artificial rib, and also relates to a preparation method thereof, belonging to the technical field of medical biological materials.
Background
Bone defects have been a difficult problem in the medical field. Chest wall bone defects are commonly found in the treatment of tumors, infections, radiation injuries and the like, and the direct damage of traumatic factors and the like. Clinically, for a large-scale chest wall defect with a defect area exceeding 6cm×6cm, if more than 3 adjacent ribs are damaged and spine damage is combined, chest wall bone reconstruction operation is required to achieve the following purposes: 1) Completely protecting the thoracic and upper abdominal organs (e.g., preventing the scapula from penetrating the thoracic cavity, especially after 5 th to 6 th rib resection); 2) Ensuring complete respiratory function (dynamic respiratory movement, prevention of pulmonary hernias and abnormal breathing); 3) Bearing and supporting the upper limb, ensuring the movement of the shoulder joint; 4) The shape of the chest wall is remodeled, the stability and aesthetic effect of the chest wall structure are guaranteed to the greatest extent, and the patient can recover confidence conveniently.
Artificial bone grafting is a common means of reconstruction of chest wall rigidity, from the 1950 s beadsley 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 surgery, and subsequent applications of stainless steel plates, titanium alloys, and the like. An effective product suitable for rib reconstruction of the chest wall does not appear up to now. The clinical problems of the existing alternative products are as follows: 1) The PMMA implant made by hand in the operation is not only low in surface evenness and rough in edge, but also high in risk of soft tissue hematoma and infection after the operation, and has poor impact toughness, so that the PMMA implant is easy to crack and break when being acted by external force, the risk of puncturing important organs of the thoracic cavity is caused, and meanwhile, certain cancerogenic risk exists. 2) The metal products such as stainless steel and the like have the defects of easy shift after operation, poor tissue compatibility, influence on the subsequent examination such as Magnetic Resonance Imaging (MRI) and the like, and the use frequency of the metal products is gradually reduced. 3) Titanium alloys, whether in general strip, plate and mesh form or in component systems (such as Matrix-RIB systems and STRATOS systems), also present the following problems: (1) the higher modulus of elasticity leads to restrictive ventilation dysfunction. (2) The mechanical strength is different from that of normal ribs, and further damage is caused when the ribs are impacted by external force. Studies have shown that there is a high incidence (about 44%) of implant related complications (such as breakage and displacement) within 1 year after surgery, with 37% implant breakage and 7% displacement. (3) The postoperative imaging examination is purely in strong artifact, and affects the diagnosis and treatment of subsequent diseases. (4) Tissue ingrowth is poor and the incidence of postoperative infection is around 5%.
Therefore, no product can meet the following characteristics of the chest wall bone reconstruction material in the market: 1) The strength is enough, the stability of the chest can be ensured, important organs and tissues in the chest can be protected, and abnormal breathing can be prevented; 2) The implantation property, allowing fibrous tissue to grow along the wall, having stable property, being not easy to generate infection and cancerogenesis; 3) The plasticity is convenient for fitting the shape of the chest; 4) The medical instrument 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 carbon fibers, pyrolytic carbon, carbon nanotubes, composite materials thereof and the like are applied to heart valves, bones, growth stents, tumor medicaments, biosensors and the like. Especially, the carbon fiber composite material which takes the carbon material as a matrix and takes the carbon fiber and the fabric thereof as reinforcements has the characteristics of light weight, good chemical stability, mechanical property similar to human bones, good fatigue resistance, strong designability, certain plasticity and the like, is regarded as an ideal material of artificial bones, and is subject to the following stick of extensive researchers. The research shows that the biological performance indexes of the material meet the requirements of national standard biological safety evaluation, and the material can be applied to clinical medicine. Compared with the 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, can bear subtle changes of the acid-base environment in the body without denaturation; 2) Can promote the adhesion of platelets and enable the organism to have certain anticoagulation property; 3) The bone tissue is favorable for tightly combining with surrounding bone tissue, and the growth of the bone is promoted; 4) The elastic modulus is between 1GPa and 40GPa, is very close to the elastic modulus (1 GPa to 30 GPa) of the human bone, and can effectively avoid complications such as bone absorption and the like caused by stress shielding of the prosthesis; 5) The carbon fiber reinforcement has good toughness, so that the fracture behavior is plastic, and the serious risk caused by sudden fracture of the material is avoided; 6) Due to the X-ray permeability of the carbon element, the post-examination has no artifact, and is beneficial to postoperative rehabilitation condition diagnosis.
In addition, since it is generally necessary to judge the resection length in situ according to specific conditions during the operation of resecting a bone-related tumor, the implant for reconstruction may be temporarily trimmed in order to achieve a good matching, and the postoperative rehabilitation effect may be deteriorated due to breakage of the implant. If an implant with adjustable length can be adopted, the operation scheme can be simplified, the operation of a clinician is facilitated, and the postoperative rehabilitation quality is improved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a length-adjustable carbon fiber composite material artificial rib formed by compounding a carbon or silicon carbide material matrix and a carbon fiber fabric reinforcement, which has the characteristics of light weight, good chemical stability, close mechanical property to human bones, good fatigue resistance, good biocompatibility and the like.
Another object of the present invention is to provide a method for manufacturing artificial ribs of carbon fiber composite material with adjustable length, which is simple to operate, low in cost and easy for mass production.
In order to achieve the technical aim, the invention provides a preparation method of an artificial rib made of a carbon fiber composite material with adjustable length, which comprises the following steps:
1) Twisting at least one bundle of carbon fiber bundles into carbon fiber ropes, and weaving the carbon fiber ropes into carbon fiber woven strips; the surfaces of the carbon fibers in the carbon fiber bundles contain resin; the method comprises the steps of (1) carrying out auxiliary baking and shaping on a carbon fiber braided strip through a die, applying a tensile force to the carbon fiber braided strip along the axial direction or applying a compressive force vertically along a plane or applying a tensile force and a compressive force vertically along the plane simultaneously along the axial direction in the baking process, and arranging preformed holes on the surface of the carbon fiber braided strip to obtain a square strip-shaped carbon fiber preform;
2) Weaving carbon fiber bundles into carbon fiber woven tubes, taking square-strip-shaped carbon fiber preformed bodies as cores and taking the carbon fiber woven tubes as sleeves, sleeving and combining the square-strip-shaped carbon fiber preformed bodies and the carbon fiber woven tubes into an assembly, baking and shaping the assembly with the aid of a die, vertically applying pressure to the assembly along a plane in the baking process, and arranging preformed holes on the surfaces of the carbon fiber woven tubes to obtain the carbon fiber preformed bodies of the assembly; or taking the carbon fiber woven strip as a core body, taking the carbon fiber woven tube as a sleeve, sleeving and combining the carbon fiber woven strip and the sleeve into an assembly, baking and shaping the assembly with the aid of a die, vertically applying pressure to the assembly along a plane or simultaneously vertically applying pressure to the assembly along the plane and axially applying tension to the carbon fiber woven strip in the baking process, and arranging preformed holes on the surfaces of the carbon fiber woven strip and the carbon fiber woven tube to obtain the carbon fiber prefabricated body of the assembly;
3) Carrying out ultrasonic treatment on the carbon fiber preform of the assembly through a medium;
4) Fixing the assembly carbon fiber preform subjected to medium ultrasonic treatment on a profiling die, and obtaining an assembly carbon fiber composite rib blank body through chemical vapor deposition of carbon and/or silicon carbide matrixes;
5) And (3) pyrolyzing a carbon coating (PyC coating) on the surface of the composite carbon fiber composite material blank by chemical vapor deposition and/or depositing a diamond-like carbon coating (DLC coating) or a fluorine-containing diamond-like carbon coating (F-DLC coating) by physical vapor deposition.
As a preferred embodiment, in step 1), the carbon fiber bundles are 1k, 3k, 6k, 12k or 24k carbon fibers, wherein 1k represents one thousand carbon fibers. The carbon fiber bundles are composed of a plurality of carbon fibers, and are usually carbon fiber bundles of 1k, 3k, 6k, 12k or 24 k.
In a preferred embodiment, in step 1), the carbon fiber rope has a diameter of 0.1mm to 5mm. The diameter of the carbon fiber rope can be adjusted according to actual needs.
In a preferred embodiment, in step 1), 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 carbon fiber surface-usual sizing agents, specifically such as epoxy resins, phenolic resins, polyimide resins, bismaleimide resins, and the like. The resin remained on the surface of the carbon fiber is unfavorable for the carbon fiber material as a biological material, and is easy to be rubbed off by 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 be removed later.
In a preferred embodiment, in step 1), the carbon fiber woven strip has a width of 6mm to 20mm and a thickness of 2mm to 6mm. The carbon fiber rope is woven into a strip shape by adopting a conventional weaving process, the appearance of the carbon fiber rope is similar to the appearance of a rib of a human body, and the width and the thickness of the carbon fiber woven strip can be regulated and controlled at will.
In a preferred embodiment, in step 1), the resin is at least one of epoxy resin, phenolic resin, polyimide resin, and bismaleimide resin.
As a preferable scheme, in the steps 1) and 2), the pulling force is applied along the axial direction in the baking process to be 20N/cm 2 ～200N/cm 2 。
As a preferred embodiment, in the steps 1) and 2), the pressure applied vertically along the plane during the baking is 1N/cm 2 ～10N/cm 2 。
In the baking and shaping process, the carbon fibers in the carbon fiber braided fabric are arranged more orderly by applying a tensile force with proper magnitude in the axial direction or a compressive force with proper magnitude in the plane vertical direction, the fiber volume content can be increased, and the mechanical property of the carbon fiber composite material is effectively improved.
In the step 1), the preformed holes on the surface of the square-strip-shaped carbon fiber preform are regularly distributed along the axial direction of the surface of the square-strip-shaped carbon fiber preform, the hole spacing is 5 mm-20 mm, and the pore size is 0.5 mm-3 mm.
In the step 2), the preformed holes on the surface of the carbon fiber woven strip are regularly distributed along the axial direction of the surface of the carbon fiber woven strip, the hole spacing is 5 mm-20 mm, and the pore size is 0.5 mm-3 mm.
In the step 2), the preformed holes on the surface of the carbon fiber woven tube are regularly distributed along the axial direction of the surface of the carbon fiber woven tube, the hole spacing is 5 mm-20 mm, and the pore size is 0.5 mm-3 mm.
The preformed hole can be obtained by inserting steel needles into the surfaces of the carbon fiber woven strips and the carbon fiber woven tubes and taking out the steel needles after baking and shaping, and the preformed hole can be used for fixation. The preparation of preformed hole among the prior art is generally formed after the material takes shape the machining, but follow-up processing can destroy continuous carbon fiber to lead to and mechanical properties reduces, and follow-up processing can make the processing surface roughness not high, and the edge is comparatively rough, and soft tissue hematoma and infection risk appear after the art.
In a preferred embodiment, in step 2), the carbon fiber bundles are directly woven into a carbon fiber woven tube, or the carbon fiber bundles are twisted into a carbon fiber rope, and then the carbon fiber rope is woven into a carbon fiber woven tube. The carbon fiber bundles comprise at least 1k carbon fibers, wherein k represents one thousand.
As a preferred embodiment, in step 1) and step 2), the baking conditions are: the temperature is 150-300 ℃ and the time is 3-10 h. Under proper baking conditions, the carbon fiber surface can be bonded and formed by resin through high-temperature baking.
As a preferred scheme, in the step 3), the ultrasonic treatment uses water and/or 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 10-60 min. Under the preferable ultrasonic treatment condition, the adhered redundant resin particles on the surface of the carbon fiber can be dissolved or shed to make the surface of the carbon fiber smoothThe artificial rib is smooth, and the black skin effect caused by the falling off of particles due to the continuous external force effect of the artificial rib made of the carbon fiber composite material after implantation is avoided.
As a preferred embodiment, in step 4), the conditions for 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. Hydrocarbon gases such as natural gas, methane or propylene, and the like.
As a preferred embodiment, in step 4), the conditions for chemical vapor deposition of the 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 a gaseous carbon silicon source. The carbon-silicon source is, for example, trichloromethylsilane
As a preferred embodiment, in step 5), 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. Hydrocarbon gases such as natural gas, methane or propylene, and the like.
As a preferred embodiment, the chemical vapor deposition of carbon and silicon carbide substrates may be performed by depositing silicon carbide first and then depositing the carbon substrate, or by depositing the carbon substrate first and then depositing the silicon carbide. By controlling the chemical vapor deposition conditions, a PyC coating with a thickness of 5 μm to 50 μm can be obtained.
As a preferable scheme, the method further comprises a step of high-temperature impurity removal treatment between the step 4) and the step 5). Specifically, a carbon fiber composite material blank with a carbon matrix or a silicon carbide matrix deposited is placed into a high-temperature furnace for high-temperature treatment, and is heated under the condition of vacuum or protective atmosphere to remove impurities, and the step can be adopted or not according to the requirement. Further preferably, wherein the high temperature treatment conditions are: preserving heat for 1-10 h at 1500-2300 ℃;
as a preferred embodiment, in step 5), the conditions for physical vapor deposition of 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 99.99wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 10 min-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 hydrocarbon gas is 10 sccm-500 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min. DLC coatings with a thickness of 0.05 μm to 2 μm can be obtained by controlling the physical vapor deposition conditions.
As a preferred embodiment, in step 5), the conditions for physical vapor deposition of the F-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 ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 50 sccm-500 sccm; CF (compact flash) 4 The gas flow is 10 sccm-200 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min. Hydrocarbon gases such as methane, acetylene, propylene, or the like. F-DLC coating with thickness of 0.05 μm-2 μm can be obtained by controlling physical vapor deposition conditions.
The F-DLC coating has better biocompatibility than the DLC coating or the PyC coating, and can improve the biological inert characteristic of the carbon material, so that the F-DLC coating is preferably deposited on the surface of the artificial rib blank of the carbon fiber composite material.
The invention also provides a length-adjustable carbon fiber composite artificial rib, which is obtained by the preparation method. The carbon fiber composite material artificial rib is formed by assembling the carbon fiber composite material core body and the carbon fiber composite material pipe sleeve, one end of the carbon fiber composite material core body is inserted into the carbon fiber composite material pipe sleeve, the length of the carbon fiber composite material artificial rib can be adjusted by adjusting the length of the carbon fiber composite material core body inserted into the carbon fiber composite material pipe sleeve, and the black skin effect caused by broken end faces generated by rib interception in the transplanting or repairing process can be effectively avoided. The carbon fiber composite artificial rib is made of a carbon fiber composite material, takes carbon fiber as a reinforcing phase, and takes carbon material or silicon carbide material as a matrix, and has the characteristics of light weight, good chemical stability, mechanical properties similar to human bones, good fatigue resistance, strong designability, certain plasticity and the like.
The invention provides a preparation method of a first length-adjustable carbon fiber composite artificial rib, which comprises the following specific steps:
1) Twisting carbon fiber bundles into a carbon fiber rope, and selecting 1 bundle to a plurality of bundles of carbon fibers to twist into a rope according to the diameter requirement of the rope, wherein the diameter of the carbon fiber rope is generally 0.1-5 mm; the carbon fiber bundles are not subjected to resin removal treatment, and the surfaces of the carbon fiber bundles generally contain sizing agents (resins), wherein the sizing agents are commonly epoxy resin, phenolic resin, polyimide resin, bismaleimide resin and the like, and the resins account for 0.5-2% of the mass of the carbon fibers; the carbon fiber bundles are plural, more specifically, 1k, 3k, 6k, 12k, 24k, or the like is common, and 1k represents one thousand carbon fibers.
2) The carbon fiber rope is woven into a carbon fiber woven strip, the weaving process adopts the common weaving process in the prior art, the width of the carbon fiber woven strip is 6 mm-20 mm, and the thickness is 2 mm-6 mm.
3) The method comprises the steps of heating, baking and shaping a carbon fiber woven strip with the aid of a mold, applying a tensile force to the carbon fiber woven strip along the axial direction, or applying a pressure vertically along a plane in the baking process, or applying a tensile force and a pressure vertically along the plane simultaneously along the axial direction, inserting steel needles (the heads of which are conical) into the surface of the carbon fiber woven strip, and arranging preformed holes to obtain a square strip-shaped carbon fiber preform; the shape of the die involved in the step is a regular straight bar shape, the shape of the inner cavity is a cuboid cavity, and the die material is 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 woven strip are determined according to actual needs, specifically, the preformed holes are regularly arranged along the axial direction of the surface of the carbon fiber woven strip, the hole spacing is 5 mm-20 mm, and the aperture size is 0.5 mm-3 mm; the pulling force applied along the axial direction in the baking process is 20N/cm 2 ～200N/cm 2 The pressure applied vertically along the plane was 1N/cm 2 ～10N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature is 150-300 ℃ and the time is 3-10 h; the density of the carbon fiber strip preform was 1.00g/cm 3 ～1.50g/cm 3 。
4) Braiding carbon fiber bundles into carbon fiber braided tubes, such as directly braiding carbon fiber bundles into carbon fiber braided tubes, or twisting carbon fiber bundles into carbon fiber ropes, and braiding carbon fiber ropes into carbon fiber braided tubes; the carbon fiber bundles comprise at least 1k carbon fibers, wherein k represents one thousand carbon fibers, and the weaving process is common in the prior art;
5) Taking a square-strip-shaped carbon fiber preform as a core body, taking a carbon fiber woven tube as a sleeve, sleeving and combining the square-strip-shaped carbon fiber preform and the sleeve into an assembly, specifically inserting the carbon fiber woven tube into one end of the square-strip-shaped carbon fiber preform subjected to baking and shaping, penetrating the carbon fiber woven tube through the carbon fiber woven tube as much as possible in the baking and shaping process, facilitating shaping, assisting the assembly in baking and shaping through a die, vertically applying pressure to the assembly along a plane in the baking process, and arranging preformed holes on the surface of the carbon fiber woven tube to obtain the carbon fiber preform of the assembly; the arrangement and the number of the preformed holes on the surface of the carbon fiber woven tube are determined according to actual needs, specifically, the preformed holes are regularly arranged along the axial direction of the surface of the carbon fiber woven tube, the hole spacing is 5 mm-20 mm, and the aperture size is 0.5 mm-3 mm; the pressure applied vertically along the plane during baking was 1N/cm 2 ～10N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature is 150-300 ℃ and the time is 3-10 h; the density of the composite carbon fiber preform was 1.00g/cm 3 ～1.50g/cm 3 。
Or taking the carbon fiber braided strip as a core body and the carbon fiber braided tube as a sleeve, sleeving and combining the carbon fiber braided strip and the sleeve into an assembly, specifically inserting one end of the carbon fiber braided strip into the carbon fiber braided tube, penetrating the carbon fiber braided strip through the carbon fiber braided tube as much as possible in the baking and shaping process, facilitating shaping, baking and shaping the assembly by a mold, vertically applying pressure to the assembly along a plane or simultaneously vertically applying pressure to the assembly along the plane and applying tension to the carbon fiber braided strip along the axial direction in the baking process, and arranging preformed holes on the surfaces of the carbon fiber braided strip and the carbon fiber braided tube to obtain the carbon fiber prefabricated body of the assembly; the arrangement and the number of the preformed holes on the surfaces of the carbon fiber woven strips and the carbon fiber woven tubes are determined according to actual needs, such as the preformed holes along the carbon fibersThe surfaces of the woven strips and the carbon fiber woven tubes are axially and regularly distributed, the hole spacing is 5 mm-20 mm, and the aperture size is 0.5 mm-3 mm; the pulling force applied along the axial direction in the baking process is 20N/cm 2 ～200N/cm 2 The pressure applied vertically along the plane was 1N/cm 2 ～10N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature is 150-300 ℃ and the time is 3-10 h; the density of the composite carbon fiber preform was 1.00g/cm 3 ～1.50g/cm 3 。
6) The carbon fiber preform of the assembly is ultrasonically cleaned by adopting a medium to remove residues on the cured surface of the resin, and the ultrasonic frequency is 20 kHz-60 kHz; the power density was 0.3W/cm 2 ～1.0W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 30-70 ℃; the time is 10 min-60 min, and the medium is purified water, acetone or ethanol, etc. according to the requirement.
7) Fixing one side surface or two opposite side surfaces of the combined carbon fiber preform on a profiling die, wherein the die is a high-temperature-resistant die, and if graphite is adopted, the shape of the die is consistent with the shape of a rib to be processed; then, the matrix carbon and/or silicon carbide is densified to form an artificial rib blank of the carbon fiber composite material with adjustable length; conditions for chemical vapor deposition of carbon substrates: 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 silicon carbide substrates: 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; when carbon and silicon carbide substrates are deposited by chemical vapor deposition, the silicon carbide may be deposited first followed by the carbon substrate, or the carbon substrate may be deposited first followed by the silicon carbide.
8) Placing the artificial rib green body of the carbon fiber composite material into a high-temperature furnace for high-temperature treatment, and heating under vacuum or protective atmosphere to remove impurities (the step can be adopted or not according to the requirement); wherein the high temperature treatment conditions are as follows: preserving heat for 1-10 h at 1500-2300 ℃;
9) Preparing a PyC coating or a DLC coating or an F-DLC coating or a PyC coating+DLC coating/F-DLC coating; in the process of preparing the coating, the carbon fiber woven strip or the carbon fiber strip preform is as much as possibleThe carbon fiber woven tube is extracted, so that the surface of a carbon fiber woven strip or a carbon fiber strip preform can be uniformly coated; preparing a PyC coating (thickness is 5-50 μm) 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 (the thickness is 0.05 mu m-2 mu m) by physical vapor deposition, wherein the F atom percentage is 5% -20%; 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 99.99wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 10 min-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 hydrocarbon gas is 10 sccm-500 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min. The conditions for physical vapor deposition of F-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 ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 50 sccm-500 sccm (the hydrocarbon gas is methane, acetylene or propylene, etc.); CF (compact flash) 4 The gas flow is 10 sccm-200 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the carbon fiber composite material artificial rib provided by the invention is composed of the carbon fiber braided strips and the carbon fiber braided tube, the carbon fiber braided strips can be telescopically regulated in the carbon fiber braided tube, the length can be freely regulated in the use process, and the skin-blacking effect caused by broken end surfaces due to interception in the operation is avoided.
The carbon fiber composite material artificial rib provided by the invention is formed by compounding a carbon or silicon carbide material matrix and a carbon fiber fabric reinforcement, has the characteristics of light weight, good chemical stability, mechanical properties similar to those of human bones, good fatigue resistance, good biocompatibility and the like, is used for transplanting or repairing, does not react with human tissues, can bear an in-vivo acid-base environment, can be tightly combined with surrounding bone tissues, promotes bone growth, has an elastic modulus very similar to that of human bones, can effectively avoid complications such as bone absorption and the like caused by stress shielding of a prosthesis, has good toughness, avoids great risks caused by sudden fracture of the material, and is beneficial to diagnosis of postoperative rehabilitation conditions due to X-ray permeability of carbon elements.
The artificial rib made of the carbon fiber composite material provided by the invention has excellent mechanical properties, and completely meets the rib transplanting or repairing requirements. The effective density of the artificial rib core body made of the carbon fiber composite material is 1.50g/cm 3 ～2.00g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending properties: the strength is more than 40MPa, and the modulus is 2 GPa-10 GPa; tensile properties: the strength is more than 150MPa, and the modulus is 5 GPa-30 GPa; impact toughness: > 8J/cm 2 . The bending modulus of the artificial rib sleeve made of the carbon fiber composite material is 10 GPa-20 GPa, and the impact toughness is more than 10J/cm 2 。
The preparation method of the artificial rib made of the carbon fiber composite material provided by the invention is simple to operate, low in cost and easy for mass production.
Drawings
FIG. 1 is a schematic diagram of an artificial rib assembly of a length-adjustable carbon fiber composite material.
FIG. 2 is a split view of an artificial rib of a length-adjustable carbon fiber composite material.
FIG. 3 is a scanning electron microscope image of the surface topography of carbon fibers of the assembly carbon fiber preform of example 1 and comparative example 2 with and without media ultrasonic cleaning; 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 invention, but not to limit the scope of the claims.
Example 1
The preparation method of the artificial rib made of the length-adjustable carbon fiber composite material comprises the following specific steps:
1) Twisting carbon fiber bundles into a carbon fiber rope, selecting 3 bundles of 12k carbon fibers to twist into a rope, wherein the diameter of the carbon fiber rope is 1mm; wherein, the carbon fiber bundles are not subjected to resin removal treatment, and the surface of the carbon fiber bundles contains epoxy resin accounting for 1 percent of the mass of the carbon fibers.
2) 10 carbon fiber ropes are woven into carbon fiber woven strips with the width of 12mm and the thickness of 3 mm.
3) The carbon fiber woven strip is heated, baked and shaped by the aid of a die, pressure is vertically applied to the carbon fiber woven strip along a plane in the baking process, and a steel needle (the head of which is a conical steel needle) is inserted into the surface of the carbon fiber woven strip to form a preformed hole, so that a square strip-shaped carbon fiber preform is obtained; the preformed holes on the surface of the carbon fiber woven strip are regularly distributed along the axial direction of the surface of the carbon fiber woven strip, the hole spacing is 15mm, and the aperture size is 2.5mm; the pressure applied vertically along the plane during baking was 5N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature is 200 ℃ and the time is 5 hours; the density of the carbon fiber strip preform was 1.25g/cm 3 。
4) And weaving the carbon fiber bundles into a tubular structure, specifically weaving 90 bundles of 3k carbon fibers into a tubular structure with a section circumference of 30mm, and obtaining the carbon fiber woven tube.
5) Taking a square-strip-shaped carbon fiber preform as a core body, taking a carbon fiber woven tube as a sleeve, sleeving and combining the square-strip-shaped carbon fiber preform and the sleeve into an assembly, specifically inserting the carbon fiber woven tube into one end of the square-strip-shaped carbon fiber preform subjected to baking and shaping, penetrating the carbon fiber woven tube through the carbon fiber woven tube as much as possible in the baking and shaping process, facilitating shaping, assisting the assembly in baking and shaping through a die, vertically applying pressure to the assembly along a plane in the baking process, and arranging preformed holes on the surface of the carbon fiber woven tube to obtain the carbon fiber preform of the assembly; the preformed holes on the surface of the carbon fiber woven tube are regularly distributed along the axial direction of the surface of the carbon fiber woven tube, the hole spacing is 15mm, and the aperture size is 2.5mm; the pressure applied vertically along the plane during baking was 5N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature was 200℃and the time was 5 hours.
6) Composite carbon fiber preformRemoving resin curing surface residues by adopting medium ultrasonic cleaning, wherein the ultrasonic frequency is 40kHz; the power density was 0.5W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 50 ℃; the time is 20min, and the medium is ethanol.
7) Fixing the opposite side surfaces of the combined carbon fiber preform on a profiling die, and then compacting matrix carbon to form a length-adjustable carbon fiber composite artificial rib blank; conditions for chemical vapor deposition of carbon substrates: the deposition temperature is 1100 ℃, the deposition time is 100h, the deposition pressure is 6kPa, and the gas source is methane.
8) Placing the artificial rib green body of the carbon fiber composite material 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 heat preservation is carried out for 5 hours.
9) Preparing a PyC coating and a DLC coating; in the process of preparing the coating, the carbon fiber woven strips or the carbon fiber strip preform is extracted from the carbon fiber tube preform as much as possible, so that the surface of the carbon fiber woven strips or the carbon fiber strip preform can be uniformly prepared with the coating; 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 coating is prepared by physical vapor deposition under the following conditions: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 200V; ar flow is 50sccm; the power of the graphite target is 2kW, and the purity is not lower than 99.99wt%; the revolution speed of the material table is 15r/min; the heating temperature is 130 ℃; the deposition time was 30min.
The effective density of the prepared carbon fiber composite material artificial rib core body with the adjustable length of the carbon fiber composite material artificial rib is 1.62g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending properties: the strength is 54MPa, and the modulus is 3GPa; tensile properties: strength is 192MPa, modulus is 10GPa; impact toughness: 11J/cm 2 . The bending modulus of the artificial rib sleeve made of the carbon fiber composite material is 13GPa, and the impact toughness is 13J/cm 2 。
Example 2
The preparation method of the artificial rib made of the length-adjustable carbon fiber composite material comprises the following specific steps:
1) Twisting carbon fiber bundles into a carbon fiber rope, selecting 3 bundles of 12k carbon fibers to twist into a rope, wherein the diameter of the carbon fiber rope is 1mm; wherein, the carbon fiber bundles are not subjected to resin removal treatment, and the surface of the carbon fiber bundles contains epoxy resin accounting for 1 percent of the mass of the carbon fibers.
2) 10 carbon fiber ropes are woven into carbon fiber woven strips with the width of 12mm and the thickness of 3 mm.
3) The carbon fiber woven strip is heated, baked and shaped through the assistance of a die, a tensile force is applied to the carbon fiber woven strip along the axial direction in the baking process, and a steel needle (the head of which is a conical steel needle) is inserted into the surface of the carbon fiber woven strip to form a preformed hole, so that a square strip-shaped carbon fiber preform is obtained; the preformed holes on the surface of the carbon fiber woven strip are regularly distributed along the axial direction of the surface of the carbon fiber woven strip, the hole spacing is 15mm, and the aperture size is 2.5mm; the pulling force applied along the axial direction in the baking process is 60N/cm 2 The baking conditions are as follows: the temperature is 200 ℃ and the time is 5 hours; the density of the carbon fiber strip preform was 1.34g/cm 3 。
4) And weaving the carbon fiber bundles into a tubular structure, specifically weaving 90 bundles of 3k carbon fibers into a tubular structure with a section circumference of 30mm, and obtaining the carbon fiber woven tube.
5) Taking a square-strip-shaped carbon fiber preform as a core body, taking a carbon fiber woven tube as a sleeve, sleeving and combining the square-strip-shaped carbon fiber preform and the sleeve into an assembly, specifically inserting the carbon fiber woven tube into one end of the square-strip-shaped carbon fiber preform subjected to baking and shaping, penetrating the carbon fiber woven tube through the carbon fiber woven tube as much as possible in the baking and shaping process, facilitating shaping, assisting the assembly in baking and shaping through a die, vertically applying pressure to the assembly along a plane in the baking process, and arranging preformed holes on the surface of the carbon fiber woven tube to obtain the carbon fiber preform of the assembly; the preformed holes on the surface of the carbon fiber woven tube are regularly distributed along the axial direction of the surface of the carbon fiber woven tube, the hole spacing is 15mm, and the aperture size is 2.5mm; the pressure applied vertically along the plane during baking was 5N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature was 200℃and the time was 5 hours.
6) The carbon fiber preform of the assembly is ultrasonically cleaned by adopting a medium to remove residues on the cured surface of the resin, wherein the ultrasonic frequency is 40kHz; the power density was 0.5W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 50 ℃; the time is 20min, and the medium is ethanol.
7) Fixing the opposite side surfaces of the combined carbon fiber preform on a profiling die, and then compacting matrix carbon to form a length-adjustable carbon fiber composite artificial rib blank; conditions for chemical vapor deposition of carbon substrates: the deposition temperature is 1100 ℃, the deposition time is 100h, the deposition pressure is 6kPa, and the gas source is methane.
8) Placing the artificial rib green body of the carbon fiber composite material 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 heat preservation is carried out for 5 hours.
9) Preparing a PyC coating and a DLC coating; in the process of preparing the coating, the carbon fiber woven strips or the carbon fiber strip preform is extracted from the carbon fiber tube preform as much as possible, so that the surface of the carbon fiber woven strips or the carbon fiber strip preform can be uniformly prepared with the coating; 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 coating is prepared by physical vapor deposition under the following conditions: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 200V; ar flow is 50sccm; the power of the graphite target is 2kW, and the purity is not lower than 99.99wt%; the revolution speed of the material table is 15r/min; the heating temperature is 130 ℃; the deposition time was 30min.
The effective density of the prepared carbon fiber composite material artificial rib core body with the adjustable length of the carbon fiber composite material artificial rib is 1.67g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending properties: strength 65MPa, modulus 6GPa; tensile properties: strength 222MPa, modulus 5GPa; impact toughness: 12J/cm 2 . The bending modulus of the artificial rib sleeve made of the carbon fiber composite material is 13GPa, and the impact toughness is 13J/cm 2 。
Example 3
The preparation method of the artificial rib made of the length-adjustable carbon fiber composite material comprises the following specific steps:
1) Twisting carbon fiber bundles into a carbon fiber rope, selecting 3 bundles of 12k carbon fibers to twist into a rope, wherein the diameter of the carbon fiber rope is 1mm; wherein, the carbon fiber bundles are not subjected to resin removal treatment, and the surface of the carbon fiber bundles contains epoxy resin accounting for 1 percent of the mass of the carbon fibers.
2) 10 carbon fiber ropes are woven into carbon fiber woven strips with the width of 12mm and the thickness of 3 mm.
3) The carbon fiber woven strip is heated, baked and shaped through the assistance of a die, tension is applied to the carbon fiber woven strip along the axial direction and pressure is applied to the carbon fiber woven strip along the plane vertically in the baking process, and a steel needle (the head of which is a conical steel needle) is inserted into the surface of the carbon fiber woven strip to form a preformed hole, so that a square strip-shaped carbon fiber preform is obtained; the preformed holes on the surface of the carbon fiber woven strip are regularly distributed along the axial direction of the surface of the carbon fiber woven strip, the hole spacing is 15mm, and the aperture size is 2.5mm; the pulling force applied along the axial direction in the baking process is 60N/cm 2 The pressure applied vertically along the plane was 5N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature is 200 ℃ and the time is 5 hours; the density of the carbon fiber strip preform was 1.52g/cm 3 。
4) And weaving the carbon fiber bundles into a tubular structure, specifically weaving 90 bundles of 3k carbon fibers into a tubular structure with a section circumference of 30mm, and obtaining the carbon fiber woven tube.
5) Taking a square-strip-shaped carbon fiber preform as a core body, taking a carbon fiber woven tube as a sleeve, sleeving and combining the square-strip-shaped carbon fiber preform and the sleeve into an assembly, specifically inserting the carbon fiber woven tube into one end of the square-strip-shaped carbon fiber preform subjected to baking and shaping, penetrating the carbon fiber woven tube through the carbon fiber woven tube as much as possible in the baking and shaping process, facilitating shaping, assisting the assembly in baking and shaping through a die, vertically applying pressure to the assembly along a plane in the baking process, and arranging preformed holes on the surface of the carbon fiber woven tube to obtain the carbon fiber preform of the assembly; the preformed holes on the surface of the carbon fiber woven tube are regularly distributed along the axial direction of the surface of the carbon fiber woven tube, the hole spacing is 15mm, and the aperture size is 2.5mm; the pressure applied vertically along the plane during baking was 5N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature was 200℃and the time was 5 hours.
6) The carbon fiber preform of the assembly is ultrasonically cleaned by adopting a medium to remove residues on the cured surface of the resin, wherein the ultrasonic frequency is 40kHz; the power density was 0.5W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 50 ℃; the time is 20min, and the medium is ethanol.
7) Fixing the opposite side surfaces of the combined carbon fiber preform on a profiling die, and then compacting matrix carbon to form a length-adjustable carbon fiber composite artificial rib blank; conditions for chemical vapor deposition of carbon substrates: the deposition temperature is 1100 ℃, the deposition time is 100h, the deposition pressure is 6kPa, and the gas source is methane.
8) Placing the artificial rib green body of the carbon fiber composite material 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 heat preservation is carried out for 5 hours.
9) Preparing a PyC coating and a DLC coating; in the process of preparing the coating, the carbon fiber woven strips or the carbon fiber strip preform is extracted from the carbon fiber tube preform as much as possible, so that the surface of the carbon fiber woven strips or the carbon fiber strip preform can be uniformly prepared with the coating; 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 coating is prepared by physical vapor deposition under the following conditions: vacuum degree of 2X 10 -1 Pa; the negative bias voltage of the workpiece is 200V; ar flow is 50sccm; the power of the graphite target is 2kW, and the purity is not lower than 99.99wt%; the revolution speed of the material table is 15r/min; the heating temperature is 130 ℃; the deposition time was 30min.
The effective density of the prepared carbon fiber composite material artificial rib core woven strip with adjustable length is 1.72g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending properties: strength 78MPa, modulus 8GPa; tensile properties: strength 242MPa, modulus 15GPa; impact toughness: 16J/cm 2 . The bending of the artificial rib sleeve braided tube made of the carbon fiber composite material is 13GPa, and the impact toughness is 13J/cm 2 。
Example 4
The preparation method of the artificial rib made of the length-adjustable carbon fiber composite material comprises the following specific steps:
1) Twisting carbon fiber bundles into a carbon fiber rope, and selecting 3 bundles of 24k carbon fibers to twist into a rope, wherein the diameter of the carbon fiber rope is 2mm; wherein, the carbon fiber bundles are not subjected to resin removal treatment, and polyimide resin on the surfaces of the carbon fiber bundles accounts for 1.2% of the mass of the carbon fibers.
2) The 12 carbon fiber ropes are woven into carbon fiber woven strips with the width of 16mm and the thickness of 4 mm.
3) Twisting 3 bundles of 6k carbon fibers into carbon fiber ropes, and weaving 60 carbon fiber ropes into a carbon fiber tube preform with the section circumference of 40 mm.
4) Taking a carbon fiber woven strip as a core body, taking a carbon fiber woven tube as a sleeve, sleeving and combining the carbon fiber woven strip and the sleeve into an assembly, specifically inserting one end of the carbon fiber woven strip into the carbon fiber woven tube, penetrating the carbon fiber woven strip through the carbon fiber woven tube as much as possible in the baking and shaping process, facilitating shaping, baking and shaping the assembly by a mold in an auxiliary manner, simultaneously applying pressure to the assembly vertically along a plane and applying tensile force to the carbon fiber woven strip axially in the baking process, and arranging preformed holes on the surfaces of the carbon fiber woven strip and the carbon fiber woven tube to obtain the carbon fiber preform of the assembly; the carbon fiber braided strips and the carbon fiber braided tube surface preformed holes are regularly distributed along the axial direction of the carbon fiber braided strips and the carbon fiber braided tube surface, the hole spacing is 15mm, and the aperture size is 3mm; the pulling force applied along the axial direction in the baking process is 50N/cm 2 The pressure applied vertically along the plane was 4N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The baking conditions are as follows: the temperature is 210 ℃ and the time is 5 hours; the density of the composite carbon fiber preform was 1.43g/cm 3 。
5) The carbon fiber preform of the assembly is ultrasonically cleaned by adopting a medium to remove residues on the cured surface of the resin, wherein the ultrasonic frequency is 50kHz; the power density was 0.8W/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 60 ℃; the time is 10min, and the medium is acetone.
6) Fixing one side surface of the combined carbon fiber preform on a profiling die, and then sequentially compacting matrix carbon and silicon carbide to form a length-adjustable carbon fiber composite artificial rib blank; conditions for chemical vapor deposition of carbon substrates: the deposition temperature is 1500 ℃, the deposition time is 200 hours, the deposition pressure is 8kPa, and the gas source is natural gas; conditions for chemical vapor deposition of silicon carbide substrates: the deposition temperature is 1150 ℃, the deposition time is 60 hours, the deposition pressure is 2kPa, and the gas source is trichloromethylsilane.
7) Preparing an F-DLC coating; in the process of preparing the coating, the carbon fiber woven strips or the carbon fiber strip preform is extracted from the carbon fiber tube preform as much as possible, so that the carbon fiber woven strips or the carbon fiber tube preform can be obtainedThe surface of the fiber strip preform can also be uniformly coated; F-DLC coating is prepared by physical vapor deposition under the following conditions: vacuum degree of 3X 10 -1 Pa; the negative bias voltage of the workpiece is 80V; ar flow is 60sccm; the ion source power is 2kW; the hydrocarbon gas flow rate is 200sccm (acetylene); CF (compact flash) 4 The gas flow rate is 40sccm; the heating temperature is 220 ℃; the deposition time was 40min.
The effective density of the prepared carbon fiber composite material artificial rib core body with the adjustable length of the carbon fiber composite material artificial rib is 1.92g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending properties: the strength is 95MPa, and the modulus is 12GPa; tensile properties: strength 232MPa, modulus 19GPa; impact toughness: 15J/cm 2 . The bending of the artificial rib sleeve made of the carbon fiber composite material is 18GPa, and the impact toughness is 14J/cm 2 。
Comparative example 1
The preparation method of the artificial rib made of the length-adjustable carbon fiber composite material comprises the following specific steps:
steps 1) to 9) as in example 1, except that no pressure is applied to the woven strips of carbon fibres perpendicularly to the plane and no pressure is applied to the assembly perpendicularly to the plane during the bake-setting of steps 3) and 5).
The effective density of the prepared carbon fiber composite material artificial rib core body with the adjustable length of the carbon fiber composite material artificial rib is 1.45g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Bending properties: strength 40MPa, modulus 2GPa; tensile properties: strength 117MPa, modulus 5GPa; impact toughness: 8J/cm 2 . The bending of the artificial rib sleeve made of the carbon fiber composite material is 18GPa, and the impact toughness is 14J/cm 2 。
Comparative example 2
The preparation method of the artificial rib made of the length-adjustable carbon fiber composite material comprises the following specific steps:
other steps are as in example 1 except that step 6) the step of ultrasonically cleaning the assembled carbon fiber preform with a medium is not performed.
Without the ultrasonic cleaning treatment of the medium, the surface of the carbon fiber contains obvious granular resin, and the granular resin is easy to fall off to cause the black skin effect. And the surface of the carbon fiber is smooth and flat through medium ultrasonic cleaning treatment, so that the granular resin is obviously reduced.

Claims (8)

1. A preparation method of an artificial rib made of a carbon fiber composite material with adjustable length is characterized by comprising the following steps: the method comprises the following steps:
1) Twisting at least one bundle of carbon fiber bundles into carbon fiber ropes, and weaving the carbon fiber ropes into carbon fiber woven strips; the surfaces of the carbon fibers in the carbon fiber bundles contain resin; the method comprises the steps of (1) carrying out auxiliary baking and shaping on a carbon fiber braided strip through a die, applying a tensile force to the carbon fiber braided strip along the axial direction or applying a compressive force vertically along a plane or applying a tensile force and a compressive force vertically along the plane simultaneously along the axial direction in the baking process, and arranging preformed holes on the surface of the carbon fiber braided strip to obtain a square strip-shaped carbon fiber preform; wherein during baking, the pulling force is applied along the axial direction to a value of 20N/cm 2 ~200N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the During baking, pressure was applied vertically along the plane to a magnitude of 1N/cm 2 ~10N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The mass of the resin on the surface of the carbon fiber is 0.5% -2% of the mass of the carbon fiber;
2) Weaving carbon fiber bundles into carbon fiber woven tubes, taking square-strip-shaped carbon fiber preformed bodies as cores and taking the carbon fiber woven tubes as sleeves, sleeving and combining the square-strip-shaped carbon fiber preformed bodies and the carbon fiber woven tubes into an assembly, baking and shaping the assembly with the aid of a die, vertically applying pressure to the assembly along a plane in the baking process, and arranging preformed holes on the surfaces of the carbon fiber woven tubes to obtain the carbon fiber preformed bodies of the assembly; or taking the carbon fiber woven strip as a core body, taking the carbon fiber woven tube as a sleeve, sleeving and combining the carbon fiber woven strip and the sleeve into an assembly, baking and shaping the assembly with the aid of a die, vertically applying pressure to the assembly along a plane or simultaneously vertically applying pressure to the assembly along the plane and axially applying tension to the carbon fiber woven strip in the baking process, and arranging preformed holes on the surfaces of the carbon fiber woven strip and the carbon fiber woven tube to obtain the carbon fiber prefabricated body of the assembly; wherein during baking, the pulling force is applied along the axial direction to a value of 20N/cm 2 ~200N/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the During baking, pressure was applied vertically along the plane to a magnitude of 1N/cm 2 ~10N/cm 2 ；
3) Carrying out ultrasonic treatment on the carbon fiber preform of the assembly through a medium; the ultrasonic treatment uses 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 10-60 min;
4) Fixing the assembly carbon fiber preform subjected to medium ultrasonic treatment on a profiling die, and obtaining an assembly carbon fiber composite rib blank body through chemical vapor deposition of carbon and/or silicon carbide matrixes;
5) And (3) performing chemical vapor deposition on a PyC coating and/or performing physical vapor deposition on a DLC or F-DLC coating on the surface of the composite carbon fiber composite material blank.
2. The method for preparing the artificial rib made of the carbon fiber composite material with adjustable length according to claim 1, wherein the method comprises the following steps:
in the step 1), the carbon fiber bundles are 1k, 3k, 6k, 12k or 24k carbon fibers, wherein 1k represents one thousand carbon fibers;
in the step 1), the diameter of the carbon fiber rope is 0.1 mm-5 mm;
in the step 1), the width of the carbon fiber woven strip is 6-20 mm, and the thickness is 2-6 mm;
in the step 1), 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 fiber composite material with adjustable length according to claim 1, wherein the method comprises the following steps:
in the step 1), preformed holes on the surface of the square-strip-shaped carbon fiber preform are regularly distributed along the axial direction of the surface of the square-strip-shaped carbon fiber preform, the hole spacing is 5 mm-20 mm, and the pore size is 0.5 mm-3 mm;
in the step 2), preformed holes on the surface of the carbon fiber woven strip are regularly distributed along the axial direction of the surface of the carbon fiber woven strip, the intervals of the holes are 5 mm-20 mm, and the pore size is 0.5 mm-3 mm;
in the step 2), preformed holes on the surface of the carbon fiber woven tube are regularly distributed along the axial direction of the surface of the carbon fiber woven tube, the intervals of the holes are 5 mm-20 mm, and the pore size is 0.5 mm-3 mm.
4. The method for preparing the artificial rib made of the carbon fiber composite material with adjustable length according to claim 1, wherein the method comprises the following steps:
in the step 2), the carbon fiber bundles are directly woven into a carbon fiber woven tube, or the carbon fiber bundles are twisted into a carbon fiber rope, and then the carbon fiber rope is woven into the carbon fiber woven tube; the carbon fiber bundles comprise at least 1k carbon fibers, wherein k represents one thousand.
5. The method for preparing the artificial rib made of the carbon fiber composite material with adjustable length according to claim 1, wherein the method comprises the following steps: in the steps 1) and 2), 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 fiber composite material with adjustable length according to claim 1, wherein the method comprises the following steps:
in step 4), the conditions for 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 step 4), the conditions for chemical vapor deposition of the 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 a gaseous carbon silicon source.
7. The method for preparing the artificial rib made of the carbon fiber composite material with adjustable length according to claim 1, wherein the method comprises the following steps:
in step 5), 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 5), the conditions for physical vapor deposition of 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 99.99wt%; the revolution speed of the material table is 10 r/min-30 r/min; the heating temperature is 80-200 ℃; the deposition time is 10 min-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 10 sccm-500 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min;
in step 5), the conditions for physical vapor deposition of the F-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 ion source is 0.5 kW-5 kW; the flow rate of the hydrocarbon gas is 50 sccm-500 sccm; CF (compact flash) 4 The gas flow is 10 sccm-200 sccm; the heating temperature is 80-300 ℃; the deposition time is 10 min-300 min.
8. The utility model provides an adjustable carbon fiber composite artificial rib of length which characterized in that: the method according to any one of claims 1 to 7.
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