WO2019037659A1 - 一种一体化碳纤维复合材料人工骨及其制备方法 - Google Patents

一种一体化碳纤维复合材料人工骨及其制备方法 Download PDF

Info

Publication number
WO2019037659A1
WO2019037659A1 PCT/CN2018/101008 CN2018101008W WO2019037659A1 WO 2019037659 A1 WO2019037659 A1 WO 2019037659A1 CN 2018101008 W CN2018101008 W CN 2018101008W WO 2019037659 A1 WO2019037659 A1 WO 2019037659A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon fiber
artificial bone
spring
carbon
fiber composite
Prior art date
Application number
PCT/CN2018/101008
Other languages
English (en)
French (fr)
Inventor
谭周建
易旭
Original Assignee
湖南碳康生物科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 湖南碳康生物科技有限公司 filed Critical 湖南碳康生物科技有限公司
Publication of WO2019037659A1 publication Critical patent/WO2019037659A1/zh

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/28—Bones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/08—Carbon ; Graphite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials

Definitions

  • the invention relates to an artificial bone, in particular to an integrated carbon fiber composite artificial bone and a method for preparing carbon fiber composite artificial bone by using carbon fiber weaving technology and profiling technology, and belongs to the field of biomedical materials.
  • CN201510928718.1 discloses a porous artificial bone having a honeycomb grid shape and a preparation method thereof, and mainly prepares a MgSr-TCP honeycomb grid by using an existing 3D printing method for raw materials such as PLGA and MgSr-TCP.
  • the frame, the PLGA slurry and the nano-sized sodium chloride particles are mixed and oscillated, poured into the honeycomb grid frame, freeze-dried and dried to obtain artificial bone.
  • the artificial bone has better hardness and toughness and good biomechanics. Different shapes of frames can be designed to meet individual needs, and more flexible and intelligent.
  • CN200810227420.8 discloses the preparation of a medical metal artificial bone trabeculae, which is mainly used to melt a titanium alloy powder at a high temperature by an electron beam melting device to form a metal artificial bone trabeculae, and its mechanics and The biological characteristics are similar to human bones, the surface friction coefficient is high, the structure is stable, and the application range is wide. It is suitable for the substitute bones of various bone defects, bone filling, bone support, bone reconstruction and bone shaping in the human skeletal system. All of the artificial bone implants currently reported have their own advantages, but there are also some obvious shortcomings.
  • metal materials are easy to electrolyze, easy to wear, easy to fatigue, easy to loose, easy to corrode, bone absorption, medical imaging has artifacts, etc.; polymer materials have aging, poor creep resistance, toxicity, thrombosis, etc. Insufficient, and bioceramic materials have the disadvantages of no plasticity, brittleness, and easy breakage.
  • Carbon materials have good biocompatibility, among which carbon fiber, pyrolytic carbon, carbon nanotubes and their composites are used in heart valves, bones, tendons, growth stents, oncology drugs, biosensors, and the like.
  • the carbon/carbon composite material in which the carbon material is a matrix, the carbon fiber and the fabric thereof are reinforcing bodies has light weight, good biocompatibility, good chemical stability, mechanical properties similar to human bones, and good fatigue resistance.
  • the design is strong and is regarded as an ideal replacement material for the existing artificial bone, which is pursued by the developers. At present, more carbon materials have been used for artificial bone.
  • the Chinese patent (CN201110324420.1) discloses that the intermediate layer structure uses high-strength carbon fiber.
  • the carbon fiber is pre-impregnated with a phenolic resin into a composite reinforcing material; the carbon fiber outer layer is formed by a vapor phase deposition method on the surface of the carbon fiber to form a silicon carbide layer.
  • the epoxy resin is adhered to the outer layer of silicon carbide in the direction of carbon fiber stretching to form an epoxy resin layer, the outer layer of the epoxy resin layer is plasma-sprayed to form a HA layer, and the outer layer of the HA layer is provided with an OPG protein layer, and the artificial bone has high strength.
  • the Chinese patent discloses a method for preparing a personalized carbon-carbon composite artificial bone, selecting a carbon fiber reinforced carbon matrix as a raw material, and performing artificial bone contouring by CT image acquisition, and converting the collected artificial bone contour into Non-uniform rational B-spline surface method is used to treat carbon fiber reinforced carbon matrix to form carbon/carbon composite artificial bone structure, and then argon gas is introduced into vacuum glow discharge chamber to carry out carbon/carbon composite artificial bone surface. After plasma pretreatment, a hydroxyapatite coating was sprayed on the surface to prepare a personalized carbon/carbon composite artificial bone.
  • an object of the present invention is to provide a light weight, good biocompatibility, good mechanical properties, no artifacts in medical images, and particularly high elasticity. Deformation and good toughness, integrated carbon fiber composite artificial bone that can realize partial cartilage function and bending shape.
  • Another object of the present invention is to provide a method for preparing an integrated carbon fiber composite artificial bone having high elastic deformation and good toughness, and capable of realizing partial cartilage function and bending shape by using a carbon fiber weaving technique and a profiling technique.
  • the method is simple and easy to operate, and is advantageous for mass production.
  • the present invention provides an integrated carbon fiber composite artificial bone, comprising a carbon fiber composite spring-like skeleton body and a carbon fiber composite material pin disposed at one or both ends thereof.
  • the integrated carbon fiber composite artificial bone comprises a spring-like skeleton integrated structure with one or both ends and a pin-shaped piece woven from carbon fiber, and a pyrolytic carbon coating, a silicon carbide coating or a heat on the surface thereof.
  • Carbon/silicon carbide hybrid coating Preparation of pyrolytic carbon, silicon carbide or pyrolytic carbon/silicon carbide hybrid coating on the surface of carbon fiber material to form carbon fiber composite material, mainly to modify the surface of carbon fiber, such as improving its wear resistance and increasing its biocompatibility.
  • the integrated carbon fiber composite artificial bone proposed by the invention has a special carbon fiber composite spring-like skeleton, and the spring-shaped skeleton formed by the carbon fiber composite material imparts good elastic deformation property to the artificial bone, can be bent at any 360°, and the carbon fiber composite material pin As the connecting end of the artificial bone and other tissues, it is advantageous for the fixation of the artificial bone, and the artificial bone having the structure can realize the partial function and the curved shape of the cartilage.
  • the artificial bone of the invention has an integrated structure and has an integrated structure, which can reduce the joint position, is convenient to use, and reduces the difficulty of implantation.
  • the carbon fiber composite spring-shaped skeleton body is provided with a carbon material sleeve outside. Since the artificial bone is implanted into the human body, the tissue will grow into the spring-like skeleton portion of the artificial bone, thereby affecting the deformation thereof, and the casing action can effectively prevent the occurrence of this situation.
  • the setting of the carbon material sleeve affects the bending deformation performance of the spring-like skeleton portion of the artificial bone, but the telescopic deformation performance can be ensured, and the diameter of the carbon material sleeve is slightly larger than that of the carbon fiber composite spring-like skeleton to ensure the carbon fiber composite.
  • the material spring-like skeleton still has a certain bending deformation performance, which satisfies the practical application requirements.
  • the carbon fiber composite pin is provided with a plurality of suture holes.
  • the suture hole is mainly used for fixing the artificial bone during the transplantation process.
  • the carbon fiber composite spring-like skeleton body has a circular, elliptical, D-shaped, pea-shaped or square cross section.
  • the integrated carbon fiber composite artificial bone has a bulk density of 0.8 g/cm 3 to 2.0 g/cm 3 .
  • the integrated carbon fiber composite artificial bone has the characteristics of light weight.
  • the invention provides a preparation method of an integrated carbon fiber composite artificial bone, which comprises the following steps:
  • the carbon fiber spring-like skeleton blank is removed from the rod-shaped mold, placed in a vacuum or a protective atmosphere, and purified at a high temperature to obtain a carbon fiber spring-like skeleton;
  • the carbon fiber spring-like skeleton body is placed in a vacuum or a protective atmosphere, and after high-temperature purification, the rod-shaped mold is removed to obtain a carbon fiber spring-like skeleton;
  • the integrated carbon fiber composite artificial bone preparation process of the present invention comprises mechanically punching a carbon fiber crucible as a pin in any step of steps 1) to 4) as a suture hole.
  • the carbon fiber rope is screwed from at least 1 k carbon fiber, and k represents one thousand.
  • the preferred solution is to first weave a carbon fiber crucible with A carbon fiber rope, then reduce the number of carbon fiber rope to B, continue to weave a piece of carbon fiber crucible, then increase the number of carbon fiber rope to A root, continue to weave a piece of carbon fiber crucible, and obtain a thick middle end.
  • Fine carbon fiber ⁇ I or, first weave a carbon fiber ⁇ with A carbon fiber rope, then reduce the number of carbon fiber rope to B, continue to weave a piece of carbon fiber ⁇ , obtain a carbon fiber ⁇ II with one end and a thin end; the carbon fiber ⁇ I Or the thinner end or the thinner portion of the carbon fiber crucible II is wound in parallel in a clockwise or counterclockwise direction on the rod-shaped mold to form a spring-like carbon fiber preform; wherein B ⁇ 3, AB ⁇ 1.
  • the pin piece is mainly used as the connecting end of the artificial bone and the tissue.
  • the carbon fiber can be made by increasing the number of carbon fiber ropes at one or both ends of the carbon fiber raft during the process of weaving the carbon fiber raft. After the end of the crucible is thickened, the fiber portion is made into a spring-like carbon fiber preform, and the pin portion is thickened. Moreover, the lengths of the carbon fiber bundles for the braided pin and the braided spring-like skeleton structure can be arbitrarily adjusted according to actual conditions.
  • the rod-shaped mold is composed of a carbon material or a material capable of forming a carbon material at a high temperature.
  • the choice of carbon material in the mold ensures that the carbon fiber material does not deform or collapse during subsequent carbonization.
  • the rod-shaped mold has a circular, elliptical, D-shaped, pea-shaped or square cross section.
  • the size and shape of the mold cross section can be arbitrarily adjusted according to actual conditions.
  • the temperature of the high temperature treatment is 1200 ° C ⁇ 2600 ° C, and the holding time is 2 h ⁇ 15 h.
  • the braided spring-like skeleton portion of the carbon fiber braided spring-like carbon fiber preform may be woven with a single carbon fiber strand or a plurality of carbon fiber strands.
  • the degree of weaving density of carbon fiber ⁇ can be adjusted according to actual conditions.
  • the carbon fibers of the present invention are polyacrylonitrile-based carbon fibers or are viscose-based, pitch-based, and phenol-based carbon fibers.
  • the chemical vapor infiltration process of the invention the spring-shaped carbon fiber preform is placed in a vacuum furnace, and the carbonaceous gas source (natural gas, methane or propylene, etc.) which is introduced at a temperature of 800 ° C to 1300 ° C is subjected to cracking, chemical vapor phase Deposited in a spring-like carbon fiber preform, after 50 to 300 hours, a carbon fiber spring-like skeleton body is prepared.
  • the carbonaceous gas source natural gas, methane or propylene, etc.
  • the liquid impregnation densification process of the present invention the carbon fiber spring preform is passed through a resin (furan, phenolic and Densification process such as ketone, etc. or asphalt (graphite pitch, coal pitch) vacuum pressure impregnation, solidification treatment, carbonization (resin: 1000 ° C, atmospheric pressure; asphalt: 800 ° C, 100 MPa).
  • the immersion pressure is 1.0 ⁇ 5.0MPa
  • the immersion time is 2 ⁇ 10 hours
  • the curing temperature is 160 ⁇ 230°C
  • the curing time is 10 ⁇ 50 hours
  • the carbonization time is 2 ⁇ 20 hours.
  • the pyrolytic carbon coating of the present invention is prepared by: 1) carbon source gas, natural gas, methane or propylene, etc.; 2) deposition temperature, 900 to 1300 ° C; 3) deposition time, 10 to 100 hours.
  • the silicon carbide coating of the present invention is prepared by: 1) a raw material, trichloromethylsilane and hydrogen; 2) a deposition temperature of 900 to 1200 ° C; and 3) a deposition time of 10 to 120 hours.
  • the pyrolytic carbon/silicon carbide hybrid coating of the present invention is prepared by preparing a pyrolytic carbon coating and then preparing a silicon carbide coating as described above.
  • the integrated carbon fiber composite artificial bone of the invention is composed of carbon/carbon composite material, and the carbon/carbon composite material has good biocompatibility, light weight, mechanical property close to human bone, good fatigue resistance and designability. Strong, medical images without artifacts.
  • the integrated carbon fiber composite artificial bone of the invention has a special structure, and has a special "spring-like" skeleton and a braided pin with good mechanical properties, and the spring-like skeleton gives the artificial bone good elastic deformation performance, 360° arbitrarily bent, and the carbon fiber pin is used as the connecting end of the artificial bone and other tissues, which is beneficial to the fixation of the artificial bone, and the artificial bone having the structure can realize part of the function and bending shape of the cartilage.
  • the carbon fiber composite artificial bone can further be provided with a carbon material sleeve to prevent the artificial bone from being implanted into the human body, and the tissue grows into the spring-like skeleton portion of the artificial bone, thereby affecting the deformation ability.
  • the artificial bone of the invention has an integrated structure and has an integrated structure, which can reduce the joint position, is convenient to use, and reduces the difficulty of implantation.
  • the carbon fiber composite material skeleton of the present invention is woven by carbon fiber, first screwed into a carbon fiber rope, and then woven into a carbon fiber crucible, and finally made of a spring-like carbon fiber preform from carbon fiber crucible, and the prepared spring-like structure not only maintains the carbon fiber itself. It has light weight, good mechanical properties, good toughness, and good elastic deformation performance similar to spring.
  • the prepared artificial bone spring joint has a tensile rigidity coefficient of 0.1 ⁇ 5kg/mm, an elongation of 10 ⁇ 100%, and a bending deformation angle. 0 to 360°, while the conventional carbon/carbon composite is a block and cannot be elastically deformed.
  • the integrated carbon fiber composite artificial bone of the invention is combined with the carbon fiber weaving technology and the profiling technology, and the method is simple in operation and easy to be processed, and is favorable for mass production.
  • Example 1 is a photograph of a carbon fiber composite artificial bone prepared in Example 1, a is an artificial bone having pin pieces at both ends and the pin pieces are not perforated, b is an artificial bone provided with pin holes at both ends, and a sleeve is provided ;
  • Example 2 is a photograph of the carbon fiber composite artificial bone prepared in Example 2 (the pin piece is provided at one end, and the pin piece is not perforated).
  • tubular carbon fiber preform is placed in a natural gas atmosphere, chemical vapor deposition at a temperature of 1100 ° C for 200 hours, a green body density of 1.2 g / cm 3 , that is, a carbon fiber spring-like skeleton body;
  • the carbon fiber spring-like skeleton blank is removed from the rod-shaped mold, placed in an argon atmosphere, heated to 2200 ° C, and the holding time is 10 h, to carry out the impurity removal treatment, that is, a carbon fiber spring-like skeleton;
  • the carbon fiber spring-like skeleton uses methane as a carbon source, and is chemically vapor deposited at a temperature of 1150 ° C for 50 hours to prepare a pyrolytic carbon coating, which is an artificial rib.
  • the tensile rigidity coefficient of the spring-like skeleton is 0.2 kg/mm
  • the elongation is 60%
  • the maximum deformation angle is 180°.
  • the spring-like skeleton is bent at an angle of 8° after the carbon material sleeve is inserted outside the artificial rib.
  • the carbon fiber spring-like carbon fiber preform is made of phenolic resin as impregnating agent, and subjected to vacuum pressure impregnation, solidification treatment, carbonization and other densification processes.
  • the main parameters are: impregnation pressure 3.0 MPa, time 5 hours; curing at 200 ° C 20 Hour; carbonized at atmospheric pressure for 4 hours at 1000 °C. After 3 cycles, the density of the green body is 1.5 g/cm 3 ; that is, a carbon fiber spring-like skeleton body is obtained;
  • the carbon fiber spring-like skeleton blank is removed from the rod-shaped mold, placed in an argon atmosphere, heated to 2000 ° C, and the holding time is 12 h, to carry out the impurity removal treatment, that is, a carbon fiber spring-like skeleton;
  • the carbon fiber spring-like skeleton is made of trichloromethylsilane and hydrogen as raw materials, and chemical vapor deposition time is carried out at a temperature of 1100 ° C for 30 hours to prepare a silicon carbide coating on the surface of the carbon fiber spring-like skeleton.
  • the tensile rigidity coefficient of the spring-like skeleton is 1 kg/mm
  • the elongation is 40%
  • the maximum deformation angle is 60°.
  • the tubular carbon fiber preform first uses propylene as a carbon source and nitrogen as a diluent gas, and the chemical vapor deposition time is 120 hours at a temperature of 900 °C. Then, the phenolic resin is used as the impregnating agent, and the densification process such as vacuum pressure impregnation, solidification treatment, carbonization, etc., the main parameters are: impregnation pressure 4.0 MPa, time 3 hours; curing at 220 ° C for 15 hours; at 950 ° C temperature , carbonization at atmospheric pressure for 6 hours, liquid phase immersion for 2 cycles, preparation of a bulk density of 1.8 g / cm 3 , that is, a carbon fiber spring-like skeleton blank;
  • the carbon fiber spring-like skeleton blank is removed from the rod-shaped mold, placed in an argon atmosphere, heated to 2100 ° C, and the holding time is 10 h to perform the impurity removal treatment, thereby obtaining a carbon fiber spring-like skeleton;
  • the tensile rigidity coefficient of the spring-like skeleton is 4 kg/mm
  • the elongation is 20%
  • the maximum deformation angle is 30°.

Abstract

一种一体化碳纤维复合材料人工骨及其制备方法，人工骨包括碳纤维复合材料弹簧状骨架主体及其一端或两端设置的碳纤维复合材料销片。其制备方法是以碳纤维为原材料，通过编织工艺制备弹簧状碳纤维预制体，再通过增密、高温纯化处理及制备耐磨涂层，即得碳纤维复合材料人工骨；该人工骨具有质轻、生物相容性好、力学性能好等特点，特别具有高弹性形变及良好韧性，可实现软骨部分功能及弯曲造型，实用性强。

Description

一种一体化碳纤维复合材料人工骨及其制备方法 技术领域
本发明涉及一种人工骨，具体涉及一种一体化碳纤维复合材料人工骨及利用碳纤维编织技术和仿形技术制备碳纤维复合材料人工骨的方法，属于生物医用材料领域。
 背景技术
创伤、肿瘤、感染以及发育异常引起的骨缺损一直是个困扰医学科学家的难题。人工骨骨移植是现在治疗临床骨缺损的常用手段。目前，在骨科领域临床使用的人工骨骼生物材料主要有金属材料、陶瓷、高分子材料，这方面的文献报道也比较多。如日本在中国申请的专利（申请号CN02807099.2）公开了一种由β-磷酸钙形成的多孔陶瓷人工骨骼材料，其可以通过植入骨髓细胞，具有较好的相容性。中国专利（申请号CN201510928718.1）公开了一种具有蜂窝网格状的多孔人工骨及其制备方法，主要由PLGA和MgSr-TCP等原料采用现有的3D打印法制备MgSr-TCP蜂窝网格框架，再将PLGA的浆料和纳米级氯化钠颗粒混合震荡，灌注入蜂窝网格框架中，冷冻干燥，烘干，得到人工骨，该人工骨的硬度、韧性较佳，生物力学好，且可设计不同形状的框架，满足个体化需求，更加灵活与智能化。中国专利（申请号CN200810227420.8）公开了一种医用金属人工骨小梁的制备，其主要是通过电子束熔融化设备来使钛合金粉末高温熔融，制成金属人工骨小梁，其力学和生物学特征类似人骨，表面摩擦系数高、结构稳定，应用范围广泛，适用于人体骨骼系统中各种骨缺损、骨填充、骨支撑、骨再造及骨整形的代用骨。目前报道的所有人工骨植入物，均有自己的优点，但也存在一些明显的缺点。如金属材料存在易电解、易磨损、易疲劳、易松动、易腐蚀、骨质吸收、医学影像有伪影等不足；高分子材料存在着老化、抗蠕变性能差、毒性反应、血栓形成等不足，而生物陶瓷材料存在着无塑性、质脆、易折断等缺点。
碳材料具有很好的生物相容性，其中碳纤维、热解碳、碳纳米管及其复合物等在心脏瓣膜、骨骼、肌腱、生长支架、肿瘤药物、生物传感器等方面得到应用。特别是由碳材料为基体、碳纤维及其织物等为增强体的碳/碳复合材料具有质量轻、生物相容性好、化学稳定性好、力学性能与人体骨相近、抗疲劳性好、可设计性强等特点，视为现有的人工骨的理想替换材料，受到研发者们的追棒。目前，已有较多的碳材料用于人工骨。如中国专利（CN201110324420.1）公开了中间层结构采用高强度碳纤维，为加强硬度和韧性，碳纤维用酚醛树脂预浸成为复合增强材料；碳纤维外层采用气相沉降法在碳纤维表面形成碳化硅层，环氧树脂沿碳纤维拉伸方向粘贴在碳化硅外层上形成环氧树脂层，环氧树脂层外层等离子喷涂HA形成HA层，HA层外层设有OPG蛋白层，该人工骨具有强度高、硬度好、韧性好、耐腐蚀、承载力高、组织相容性好、结实耐用、塑形性好等特点。中国专利（CN201210261732.7）公开了一种个性化碳-碳复合材料人工骨的制备方法，选择碳纤维增强碳基体作为原料，通过CT图像的采集进行人工骨轮廓，将采集的人工骨轮廓转换成非均匀有理B样条曲面的方法对碳纤维增强碳基体进行处理，形成碳/碳复合材料人工骨结构，再在真空辉光放电室中通入氩气进行对碳/碳复合材料人工骨表面进行等离子预处理后，在其表面喷涂羟基磷灰石涂层，制备出个性化碳/碳复合材料人工骨。
 技术问题
这些碳/碳复合材料虽然具有质量轻、生物相容性好、化学稳定性好、力学性能与人体骨相近等特点，但是不能实现弹性变形，无法实现软骨的部分功能和弯曲造型等功能，限制了其应用范围。
 技术解决方案
针对现有的碳/碳复合材料制备的人工骨存在的缺陷，本发明的一个目的是在于提供一种质轻、生物相容性好、力学性能好、医学影像无伪影，特别具有高弹性形变及良好韧性，可实现软骨部分功能及弯曲造型的一体化碳纤维复合材料人工骨。
本发明的另一个目的是在于提供一种利用碳纤维编织技术和仿形技术相结合制备具有高弹性形变及良好韧性，可实现软骨部分功能及弯曲造型的一体化碳纤维复合材料人工骨的方法，该方法操作简单，易于化，有利于大规模生产。
为了实现上述技术目的，本发明提供了一种一体化碳纤维复合材料人工骨，包括碳纤维复合材料弹簧状骨架主体及其一端或两端设置的碳纤维复合材料销片。
优选的方案，所述一体化碳纤维复合材料人工骨包括由碳纤维编织而成的一端或两端含销片的弹簧状骨架一体化结构及其表面的热解碳涂层、碳化硅涂层或热解碳/碳化硅混合涂层。在碳纤维材料表面制备热解碳、碳化硅或热解碳/碳化硅混合涂层，从而形成碳纤维复合材料，主要是对碳纤维的表面改性如提高其耐磨性、增加其生物相容性等。
本发明提出的一体化碳纤维复合材料人工骨具有特殊的碳纤维复合材料弹簧状骨架，碳纤维复合材料形成的弹簧状骨架赋予了人工骨良好弹性形变性能，可以360°任意弯曲，而碳纤维复合材料销片作为人工骨与其他组织的连接端，有利于人工骨的固定，具有该结构的人工骨可实现软骨的部分功能和弯曲造型。且本发明的人工骨整体成型，具有一体化结构，可以减少连接部位，使用方便，降低植入难度。
优选的方案，所述碳纤维复合材料弹簧状骨架主体外部设有碳材料管套。由于人工骨植入人体后，组织会长入人工骨弹簧状骨架部分，从而影响其变形，套管作用能够有效防止该情况的发生。碳材料管套的设置会影响人工骨弹簧状骨架部分的弯曲变形性能，但能保证其伸缩变形性能，且碳材料管套直径大小要比碳纤维复合材料弹簧状骨架截面要稍大，保证碳纤维复合材料弹簧状骨架仍具有一定的弯曲变形性能，满足实际应用要求。
优选的方案，所述碳纤维复合材料销片上设有若干缝合孔。缝合孔主要是用于人工骨在移植过程中的固定。
优选的方案，所述碳纤维复合材料弹簧状骨架主体截面为圆形、椭圆形、D形、豌豆形或方形。
优选的方案，所述一体化碳纤维复合材料人工骨的体积密度为0.8g/cm 3~ 2.0g/cm 3。一体化碳纤维复合材料人工骨具有质轻的特点。
本发明提供了一种一体化碳纤维复合材料人工骨的制备方法，其包括以下步骤：
1）将复数根碳纤维旋拧成碳纤维绳，再将至少三根碳纤维绳编织成碳纤维辫，所述碳纤维辫的一端或中间部分按顺时针或逆时针方向平行缠绕在棒状模具上形成弹簧状碳纤维预制体；
2）所述弹簧状碳纤维预制体采用化学气相渗透和/或液体浸渍增密后，即得碳纤维弹簧状骨架坯体；
3）所述碳纤维弹簧状骨架坯体移除棒状模具后，置于真空或保护气氛中，高温纯化处理，即得碳纤维弹簧状骨架；
或者，所述碳纤维弹簧状骨架坯体，置于真空或保护气氛中，高温纯化后，移除棒状模具，即得碳纤维弹簧状骨架；
4）在管状骨架表面制备热解碳涂层、碳化硅涂层或热解碳/碳化硅混合涂层，即得人工骨；或者，在人工骨的碳纤维复合材料弹簧状骨架外部套入碳材料管套。
优选的方案，本发明的一体化碳纤维复合材料人工骨制备过程中在步骤1）~4）任意步骤中包括对作为销片的碳纤维辫上进行机械打孔，作为缝合孔。
优选的方案，所述碳纤维绳由至少1k碳纤维旋拧而成，k表示一千根。
优选的方案，先用A根碳纤维绳编织一段碳纤维辫，再减少碳纤维绳数量至B根，继续编织一段碳纤维辫，再增加碳纤维绳数量至A根，继续编织一段碳纤维辫，得到两端粗中间细的碳纤维辫I；或者，先用A根碳纤维绳编织一段碳纤维辫，再减少碳纤维绳数量至B根，继续编织一段碳纤维辫，获得一端细一端粗的碳纤维辫II；将所述碳纤维辫I或碳纤维辫II的较细端或中间较细部分按顺时针或逆时针方向平行缠绕在棒状模具上形成弹簧状碳纤维预制体；其中，B≥3，A-B≥1。本发明的技术方案中销片主要作为人工骨与组织的连接端，为保证销片的力学性能，可以在编织碳纤维辫过程中，将碳纤维辫的一端或两端通过增加碳纤维绳数量来使碳纤维辫端头增粗，从而将纤维辫制成弹簧状碳纤维预制体后，销片部分得到增粗。且用于编织销片和编织弹簧状骨架结构碳纤维辫长度都可以根据实际情况进行任意调控。
优选的方案，所述棒状模具由碳材料或在高温下能生成碳材料的材料构成。模具选择碳材料可以保证在后续的碳化过程中碳纤维材料不变形或塌陷。
优选的方案，所述棒状模具的截面为圆形、椭圆、D形、豌豆形或方形。模具截面的大小和形状可以根据实际情况任意调节。
优选的方案，高温处理的温度为1200℃~2600℃，保温时间为2h~15h。
优选的方案，采用碳纤维辫编织弹簧状碳纤维预制体过程中编织弹簧状骨架部分可以采用单根碳纤维辫或多根碳纤维辫进行编织。且碳纤维辫的编织致密程度可以根据实际情况进行调节。
本发明的碳纤维为聚丙烯腈基碳纤维或者为粘胶基、沥青基和酚醛基碳纤维等。
本发明的化学气相渗透工艺：将弹簧状碳纤维预制体放入真空炉中，在800℃~1300℃温度下，通入的含碳气源（天然气、甲烷或丙烯等）经过裂解后，化学气相沉积在弹簧状碳纤维预制体中，经过50~300小时，制备成碳纤维弹簧状骨架坯体。
本发明的液体浸渍增密工艺：碳纤维弹簧预制体经过树脂（呋喃、酚醛和
Figure 69fa
酮等）或沥青（石墨沥青、煤沥青）真空加压浸渍、固化处理、碳化（树脂：1000℃，常压；沥青：800℃，100MPa）等致密化工艺。浸渍压力1.0~5.0MPa，浸渍时间2~10小时；固化温度160~230℃，固化时间10~50小时，碳化时间2~20小时。
本发明的热解碳涂层制备：1）碳源气体，天然气、甲烷或丙烯等；2）沉积温度，900~1300℃；3）沉积时间，10~100小时。
本发明的碳化硅涂层制备：1）原料，三氯甲基硅烷和氢气；2）沉积温度，900~1200℃；3）沉积时间，10~120小时。
本发明的热解碳/碳化硅混合涂层制备：如按上述方法先制备热解碳涂层再制备碳化硅涂层。
 有益效果
相对现有技术，本发明的技术方案带来的有益技术效果：
1）本发明的一体化碳纤维复合材料人工骨由碳/碳复合材料构成，碳/碳复合材料具有生物相容性良好、质轻、力学性能与人体骨相近、抗疲劳性好、可设计性强、医学影像无伪影等特点。
2）本发明的一体化碳纤维复合材料人工骨具有特殊的结构，其具有特殊的“弹簧状”骨架和力学性能较好的辫子状销片，弹簧状骨架赋予了人工骨良好弹性形变性能，可以360°任意弯曲，而碳纤维销片作为人工骨与其他组织的连接端，有利于人工骨的固定，具有该结构的人工骨可实现软骨的部分功能和弯曲造型。碳纤维复合材料人工骨可以进一步设置碳材料管套，防止人工骨植入人体后，组织长入人工骨弹簧状骨架部分，而影响其变形能力。
3）本发明的人工骨整体成型，具有一体化结构，可以减少连接部位，使用方便，降低植入难度。
4）本发明的碳纤维复合材料骨架通过碳纤维编织而成，先旋拧成碳纤维绳，再编织成碳纤维辫，最后由碳纤维辫制成弹簧状碳纤维预制体，制备的弹簧状结构不但保持了碳纤维本身具有的质轻、力学性好、韧性好，而且具有类似弹簧的良好弹性变形性能，制备的人工骨弹簧节的拉伸刚性系数0.1~5kg/mm，伸出率10~100%，弯曲变形角度0～360°，而常规的碳/碳复合材料为块体，不能实现弹性变形。
5）本发明的一体化碳纤维复合材料人工骨通过碳纤维编织技术和仿形技术相结合，方法操作简单，易于化，有利于大规模生产。
 附图说明
【图1】为实施例1制备的碳纤维复合材料人工骨照片，a为两端含销片，销片未打孔的人工骨，b为两端销片打孔，且设置管套的人工骨；
【图2】为实施例2制备的碳纤维复合材料人工骨照片（一端含销片，销片未打孔）。
 本发明的实施方式
以下实施例旨在进一步说明本发明内容，而不是限制本发明权利要求的保护范围。
实施例1
1）先将12k聚丙烯腈基碳纤维旋拧成的碳纤维绳，然后将5根12k的碳纤维绳编织成一段碳纤维辫（约20mm），减少碳纤维绳数量，用3根碳纤维绳编织成一段碳纤维辫，再增加碳纤维数量，用5根碳纤维绳编织成一段碳纤维辫（约20mm），获得两端粗，中间细的碳纤维辫，所述碳纤维辫将中间较细的一段按顺时针平行紧密缠绕在截面为矩形（截面大小与人肋骨相同）的碳材料模具上，形成弹簧状碳纤维预制体，整个预制体长度与人工肋骨长度相近。碳纤维辫较粗一段通过机械打孔，作为缝合孔。
2）所述管状碳纤维预制体置于天然气气氛中，在1100℃的温度下，化学气相沉积200小时，坯体密度为1.2g/cm 3，即得碳纤维弹簧状骨架坯体；
3）所述碳纤维弹簧状骨架坯体移除棒状模具后，置于氩气保护气氛中，加热至2200℃，保温时间为10h，以进行除杂处理，即得碳纤维弹簧状骨架；
4）碳纤维弹簧状骨架采用甲烷做碳源，在1150℃的温度下，化学气相沉积50小时，制备热解碳涂层，即得人工肋骨。
该实施例制备的人工肋骨中弹簧状骨架拉伸刚性系数拉伸刚性系数0.2kg/mm，伸出率60%，弯曲可实现最大变形角度180°。
在人工肋骨外部套入碳材料管套后弹簧状骨架弯曲变形角度8°。
实施例2
1）将12k聚丙烯腈基碳纤维和6k聚丙烯腈基碳纤维分别旋拧成碳纤维绳，1根12k聚丙烯腈基碳纤维绳和4根6k聚丙烯腈基碳纤维绳编织一段碳纤维辫（约20mm），再由1根12k聚丙烯腈基碳纤维绳和2根6k将两根碳纤维辫一段碳纤维辫，将碳纤维辫较细端按顺时针平行紧密缠绕在截面为D形的碳材料模具上（截面大小与人肋骨相近），形成弹簧状碳纤维预制体，整个预制体长度与人工肋骨长度相近。碳纤维辫较粗一段通过机械打孔，作为缝合孔。
2）碳纤维弹簧状碳纤维预制体采用酚醛树脂做浸渍剂，经过真空加压浸渍、固化处理、碳化等致密化工艺，其主要参数为：浸渍压力3.0MPa，时间5小时；在200℃下固化20小时；在1000℃温度下，常压碳化4小时。经过3个周期，制备坯体密度为1.5g/cm 3；即得碳纤维弹簧状骨架坯体；
3）所述碳纤维弹簧状骨架坯体移除棒状模具后，置于氩气保护气氛中，加热至2000℃，保温时间为12h，以进行除杂处理，即得碳纤维弹簧状骨架；
4）碳纤维弹簧状骨架采用三氯甲基硅烷和氢气作为原料，在1100℃的温度下化学气相沉积时间30小时，在碳纤维弹簧状骨架表面制备碳化硅涂层，即得
人工肋骨。
该实施例制备的人工肋骨中弹簧状骨架拉伸刚性系数拉伸刚性系数1kg/mm，伸出率40%，弯曲可实现最大变形角度60°。
实施例3
1）先将三根3k聚丙烯腈基碳纤维旋拧成碳纤维绳，然后将五根该碳纤维绳编织成碳纤维辫，将三根碳纤维辫的一端按逆时针平行紧密缠绕在截面为矩形的碳材料模具上（截面大小与人肋骨相近），形成弹簧状碳纤维预制体，整个预制体长度与人工肋骨长度相近。碳纤维辫较粗一段通过机械打孔，作为缝合孔。
2）所述管状碳纤维预制体先采用丙烯做碳源、氮气做稀释气体，在900℃的温度下化学气相沉积时间120小时。然后采用酚醛树脂做浸渍剂，经过真空加压浸渍、固化处理、碳化等致密化工艺，其主要参数为：浸渍压力4.0MPa，时间3小时；在220℃下固化15小时；在950℃温度下，常压碳化6小时，液相浸渍2个周期，制备坯体密度为1.8g/cm 3，即得碳纤维弹簧状骨架坯体；
3）所述碳纤维弹簧状骨架坯体移除棒状模具后，置于氩气保护气氛中，加热至2100℃，保温时间为10h，以进行除杂处理，即得碳纤维弹簧状骨架；
4）在管状骨架表面先采用甲烷做碳源，在1120℃的温度下，化学气相沉积30小时，然后采用三氯甲基硅烷和氢气作为原料，在1100℃的温度下化学气相沉积时间20小时。制备热解碳和碳化硅复合涂层，即得人工肋骨。
该实施例制备的人工肋骨中弹簧状骨架拉伸刚性系数拉伸刚性系数4kg/mm，伸出率20%，弯曲实现最大变形角度30°。

Claims (10)

  1. 一种一体化碳纤维复合材料人工骨，其特征在于：包括碳纤维复合材料弹簧状骨架主体及其一端或两端设置的碳纤维复合材料销片。
  2. 根据权利要求1所述的一体化碳纤维复合材料人工骨，其特征在于：所述一体化碳纤维复合材料人工骨包括由碳纤维编织而成的一端或两端含销片的弹簧状骨架一体化结构及其表面的热解碳涂层、碳化硅涂层或热解碳/碳化硅混合涂层。
  3. 根据权利要求1所述的一体化碳纤维复合材料人工骨，其特征在于：
    所述碳纤维复合材料弹簧状骨架主体外部设有碳材料管套；
    所述碳纤维复合材料销片上设有若干缝合孔。
  4. 根据权利要求1或3所述的一体化碳纤维复合材料人工骨，其特征在于：所述碳纤维复合材料弹簧状骨架主体截面为圆形、椭圆形、D形、豌豆形或方形。
  5. 根据权利要求1、2或3所述的一体化碳纤维复合材料人工骨，其特征在于：所述一体化碳纤维复合材料人工骨的体积密度为0.8g/cm 3~2.0g/cm 3。
  6. 权利要求1~5任一项一体化碳纤维复合材料人工骨的制备方法，其特征在于：包括以下步骤：
    1）将复数根碳纤维旋拧成碳纤维绳，再将至少三根碳纤维绳编织成碳纤维辫，所述碳纤维辫的一端或中间部分按顺时针或逆时针方向平行缠绕在棒状模具上形成弹簧状碳纤维预制体；
    2）所述弹簧状碳纤维预制体采用化学气相渗透和/或液体浸渍增密后，即得碳纤维弹簧状骨架坯体；
    3）所述碳纤维弹簧状骨架坯体移除棒状模具后，置于真空或保护气氛中，高温纯化处理，即得碳纤维弹簧状骨架；
    或者，所述碳纤维弹簧状骨架坯体，置于真空或保护气氛中，高温纯化处理后，移除棒状模具，即得碳纤维弹簧状骨架；
    4）在管状骨架表面制备热解碳涂层、碳化硅涂层或热解碳/碳化硅混合涂层，即得人工骨；或者，在人工骨的碳纤维复合材料弹簧状骨架外部套入碳材料管套。
  7. 根据权利要求6所述的碳纤维复合材料人工骨的制备方法，其特征在于：所述碳纤维绳由至少1k碳纤维旋拧而成，k表示一千根。
  8. 根据权利要求6所述的碳纤维复合材料人工骨的制备方法，其特征在于：
    先用A根碳纤维绳编织一段碳纤维辫，再减少碳纤维绳数量至B根，继续编织一段碳纤维辫，再增加碳纤维绳数量至A根，继续编织一段碳纤维辫，得到两端粗中间细的碳纤维辫I；或者，先用A根碳纤维绳编织一段碳纤维辫，再减少碳纤维绳数量至B根，继续编织一段碳纤维辫，获得一端细一端粗的碳纤维辫II；将所述碳纤维辫I或碳纤维辫II的较细端或中间较细部分按顺时针或逆时针方向平行缠绕在棒状模具上形成弹簧状碳纤维预制体；其中，B≥3，A-B≥1。
  9. 根据权利要求6所述的碳纤维复合材料人工骨的制备方法，其特征在于：所述棒状模具由碳材料或在高温下能生成碳材料的材料构成；
    所述棒状模具的截面为圆形、椭圆形、D形、豌豆形或方形。
  10. 根据权利要求6~9任一项所述的碳纤维复合材料人工骨的制备方法，其特征在于：所述高温处理的温度为1200℃~2600℃，保温时间为2h~15h。
PCT/CN2018/101008 2017-08-23 2018-08-17 一种一体化碳纤维复合材料人工骨及其制备方法 WO2019037659A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710730863.8 2017-08-23
CN201710730863.8A CN107536659B (zh) 2017-08-23 2017-08-23 一种一体化碳纤维复合材料人工骨及其制备方法

Publications (1)

Publication Number Publication Date
WO2019037659A1 true WO2019037659A1 (zh) 2019-02-28

Family

ID=60958880

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/101008 WO2019037659A1 (zh) 2017-08-23 2018-08-17 一种一体化碳纤维复合材料人工骨及其制备方法

Country Status (2)

Country Link
CN (1) CN107536659B (zh)
WO (1) WO2019037659A1 (zh)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107536659B (zh) * 2017-08-23 2019-09-17 湖南碳康生物科技有限公司 一种一体化碳纤维复合材料人工骨及其制备方法
CN111925227B (zh) * 2020-01-19 2022-04-08 湖南碳康生物科技有限公司 一种碳纤维复合材料人工气管支架及其制备方法
CN112190761B (zh) * 2020-09-28 2022-10-18 湖南碳康生物科技有限公司 一种碳基复合材料人工骨修补材料及其制备方法
CN112876269B (zh) * 2021-01-18 2023-04-28 湖南碳康生物科技有限公司 一种长度可调节碳纤维复合材料人工肋骨及其制备方法
CN113152018B (zh) * 2021-03-12 2023-03-28 张凤英 一种碳化硅基体碳纤维复合材料人工肋骨处理装置
CN113831147A (zh) * 2021-10-09 2021-12-24 上海世碳复合材料科技有限公司 一种碳碳复合材料人造骨骼

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5306310A (en) * 1991-08-27 1994-04-26 Man Ceramics Gmbh Vertebral prosthesis
WO2007074896A1 (ja) * 2005-12-28 2007-07-05 Japan Science And Technology Agency 組織再生用複合化スカフォールド
CN101889912A (zh) * 2010-08-05 2010-11-24 上海交通大学 生物陶瓷涂层钛丝烧结多孔钛人工骨的制备方法
CN102718535A (zh) * 2012-07-05 2012-10-10 湖南金博复合材料科技有限公司 碳/碳/碳化硅复合材料及制备方法
CN102784017A (zh) * 2012-07-09 2012-11-21 济南大学 一种由复合材料制成的人造骨的制备工艺
CN102940904A (zh) * 2012-11-26 2013-02-27 西安工程大学 一种针织成型技术制备骨移植材料的方法
CN205144792U (zh) * 2015-09-17 2016-04-13 复旦大学附属华山医院 仿生型人工肩袖补片
CN107518962A (zh) * 2017-08-23 2017-12-29 长沙雅康生物科技有限公司 一种碳纤维复合材料人工骨及其制备方法
CN107536659A (zh) * 2017-08-23 2018-01-05 长沙雅康生物科技有限公司 一种一体化碳纤维复合材料人工骨及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2419831A1 (en) * 2002-02-28 2003-08-28 Macropore Biosurgery, Inc. Methods for governing bone growth
DE10335131A1 (de) * 2003-07-31 2005-02-24 Blue Membranes Gmbh Verfahren und Herstellung von porösen kohlenstoffbasierten Formkörpern
FI20031120A0 (fi) * 2003-07-31 2003-07-31 Bci Bioabsorbable Concepts Ltd Monifunktionaalinen implanttilaite
CN100584390C (zh) * 2006-03-08 2010-01-27 中国科学院金属研究所 一种骨组织工程支架材料
WO2007127295A2 (en) * 2006-04-25 2007-11-08 Teleflex Medical Incorporated Calcium phosphate polymer composite and method
CN101536936B (zh) * 2009-02-24 2011-05-04 上海大学 一种基于光固化成形的仿生支架多孔结构的制造工艺
CN102309361A (zh) * 2010-07-08 2012-01-11 北京市奥斯比利克新技术开发有限公司 弹性支撑体及其制造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5306310A (en) * 1991-08-27 1994-04-26 Man Ceramics Gmbh Vertebral prosthesis
WO2007074896A1 (ja) * 2005-12-28 2007-07-05 Japan Science And Technology Agency 組織再生用複合化スカフォールド
CN101889912A (zh) * 2010-08-05 2010-11-24 上海交通大学 生物陶瓷涂层钛丝烧结多孔钛人工骨的制备方法
CN102718535A (zh) * 2012-07-05 2012-10-10 湖南金博复合材料科技有限公司 碳/碳/碳化硅复合材料及制备方法
CN102784017A (zh) * 2012-07-09 2012-11-21 济南大学 一种由复合材料制成的人造骨的制备工艺
CN102940904A (zh) * 2012-11-26 2013-02-27 西安工程大学 一种针织成型技术制备骨移植材料的方法
CN205144792U (zh) * 2015-09-17 2016-04-13 复旦大学附属华山医院 仿生型人工肩袖补片
CN107518962A (zh) * 2017-08-23 2017-12-29 长沙雅康生物科技有限公司 一种碳纤维复合材料人工骨及其制备方法
CN107536659A (zh) * 2017-08-23 2018-01-05 长沙雅康生物科技有限公司 一种一体化碳纤维复合材料人工骨及其制备方法

Also Published As

Publication number Publication date
CN107536659A (zh) 2018-01-05
CN107536659B (zh) 2019-09-17

Similar Documents

Publication Publication Date Title
WO2019037657A1 (zh) 一种碳纤维复合材料人工骨及其制备方法
WO2019037659A1 (zh) 一种一体化碳纤维复合材料人工骨及其制备方法
Shao et al. 3D robocasting magnesium-doped wollastonite/TCP bioceramic scaffolds with improved bone regeneration capacity in critical sized calvarial defects
US3877080A (en) Acicular silicon carbide dispersion in pyrolytic graphite matrix for use in biomedical implants
Zhang et al. Bioinspired structure of bioceramics for bone regeneration in load-bearing sites
EP3222748B1 (en) Medical porous tantalum metal material and preparation method therefor
WO2012142952A1 (zh) 多孔钽棒
Feng et al. Toughening and strengthening mechanisms of porous akermanite scaffolds reinforced with nano-titania
CN112190375B (zh) 一种高生物活性的碳纤维/碳复合材料c形人工气管支架及其制备方法
Christel et al. Carbon-reinforced composites in orthopedic surgery
Sridhar Nanobioceramic coatings for biomedical applications
CN112315627A (zh) 带有骨小梁的含氧化层锆铌合金胫骨平台假体及制备方法
WO2020237705A1 (zh) 个性化3d打印多孔钛基钽涂层接骨板及其制备方法
Suping et al. Effects of coatings on the mechanical properties of carbon fiber reinforced HAP composites
CN110606746B (zh) 一种颅骨修补片及其制备方法
CN113831147A (zh) 一种碳碳复合材料人造骨骼
US8167955B2 (en) Carbon fiber reinforced carbon foams for repair and reconstruction of bone defects
CN112206355B (zh) 一种仿形人工骨及其制备方法
CN105147383A (zh) 一种多孔钽金属空心螺钉及其应用
CN205814410U (zh) 一种骨折固定用多孔钽金属螺钉
CN107586146B (zh) 一种碳纤维增韧羟基磷灰石生物陶瓷材料的方法
CN111233457B (zh) 一种基于碳纤维为造孔剂和增强体制备多孔镁掺杂ha基复合材料的方法
CN213883674U (zh) 一种碳纤维/碳复合材料t形人工肋骨连接件
CN210186109U (zh) 骨缺损人工修复体
CN105796170A (zh) 一种骨折固定用多孔钽金属螺钉及其应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18847364

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC, EPO FORM 1205A DATED 01/10/20

122 Ep: pct application non-entry in european phase

Ref document number: 18847364

Country of ref document: EP

Kind code of ref document: A1