CN111925227B - 一种碳纤维复合材料人工气管支架及其制备方法 - Google Patents
一种碳纤维复合材料人工气管支架及其制备方法 Download PDFInfo
- Publication number
- CN111925227B CN111925227B CN202010159572.XA CN202010159572A CN111925227B CN 111925227 B CN111925227 B CN 111925227B CN 202010159572 A CN202010159572 A CN 202010159572A CN 111925227 B CN111925227 B CN 111925227B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- carbon
- composite material
- tubular
- artificial trachea
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 127
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 127
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 210000003437 trachea Anatomy 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 239000011248 coating agent Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000004744 fabric Substances 0.000 claims abstract description 23
- 210000000078 claw Anatomy 0.000 claims abstract description 17
- 239000011208 reinforced composite material Substances 0.000 claims abstract description 12
- 238000009941 weaving Methods 0.000 claims abstract description 12
- 238000003754 machining Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 238000000151 deposition Methods 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 20
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000003085 diluting agent Substances 0.000 description 7
- 238000004080 punching Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 238000005498 polishing Methods 0.000 description 5
- 239000002296 pyrolytic carbon Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 3
- 229920000339 Marlex Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000029058 respiratory gaseous exchange Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 230000017423 tissue regeneration Effects 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 206010016717 Fistula Diseases 0.000 description 1
- 101150015163 GPA3 gene Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000012237 artificial material Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000036770 blood supply Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002224 dissection Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003890 fistula Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- 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
- A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
-
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/573—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5001—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with carbon or carbonisable materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5252—Fibers having a specific pre-form
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5252—Fibers having a specific pre-form
- C04B2235/5256—Two-dimensional, e.g. woven structures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/614—Gas infiltration of green bodies or pre-forms
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Veterinary Medicine (AREA)
- Transplantation (AREA)
- Public Health (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Biomedical Technology (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Vascular Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Cardiology (AREA)
- Composite Materials (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
Abstract
本发明公开了一种碳纤维复合材料人工气管支架及其制备方法,人工气管支架具有层次管状结构;管状结构包括连续直壁以及沿连续直壁两侧轴向布设的抱爪结构,其内层为碳纤维增强复合材料层,外层为DLC涂层。人工气管支架是利用碳纤维或碳纤维织物通过编制、增密、机加工、生成DLC涂层等工艺制成,该人工气管支架组织相容性好,力学性能优异,且具有收缩‑扩张功能,且其制备方法工艺简单,可操作性强,有利于实际工业化生产。
Description
技术领域
本发明涉及一种人工气管支架,具体涉及一种碳纤维复合材料人工气管支架及其制备方法,属于生物医用材料技术领域。
背景技术
气管因肿瘤、理化等因素致狭窄影响功能而必须行切除重建。当长度超过 6cm,则吻合口张力高而易产生口瘘等并发症,就需要借人工材料来重建气管。一些研究者设计了涤纶、硅胶材料人工气管;碳纤维复合硅胶网管;聚酯聚丙烯复合材料人工气管;圆形钛珠连接成网孔的人工气管;软性Marlex网制成管状,外表聚丙烯材料加固,在以胶原蛋白充填管壁;网状的聚四氟乙烯材料结合自体组织等。由于气管组织环境的复杂性对气管替代物要求诸多,移植于体内无法与机体达到生物学融合固定,常易伴发脱落、泄漏等,同时,由于现有人工气管基本注重实现管道构造,并不能满足气管在呼吸过程中管腔的收缩与扩张功能,因此现有技术中的绝大部分人工气管至今不能成熟地应用于临床。
发明内容
为了解决现有人工气管存在的不足,本发明的第一个的目的是在于提供一种由碳纤维复合材料构成的组织相容性好,力学性能好,且具有收缩-扩张功能的人工气管支架。
本发明的另一个目的是在于提供一种制备人工气管支架的方法,该方法工艺简单,可操作性强,有利于实际工业化生产。
为了实现上述技术目的,本发明提供了一种碳纤维复合材料人工气管支架,其具有层次管状结构;所述层次管状结构包括连续直壁以及沿连续直壁两侧轴向布设的抱爪结构;所述层次管状结构包括内层碳纤维增强复合材料层和外层 DLC涂层。
优选的方案,所述连续直壁表面均匀设有小孔。连续直壁上分布有圆孔或槽开孔。这些小孔一方面便于柔性管壁固定附着,另一方面可适于新生组织贯彻管壁,多区域接触。较优选的方案,小孔的孔径尺寸为孔间距5mm ~15mm(孔中心与周围孔中心间距)。
优选的方案,所述连续直壁的两侧均匀设置弧形条状体,且直壁两侧的弧形条状体沿层次管状结构轴向相对交替分布,形成抱合状的抱爪结构。
本发明提供的人工气管支架抱爪结构和连续直壁为一体结构。抱爪结构主要是由连续直壁两侧的弧形条状体构成,弧形条状体的一端与直壁一侧连接成一体,而另一端与连续直壁另一侧为非连接体,之间存在间隙。而弧形条状体由碳纤维复合材料构成,其具有较好的力学性能,可以在一定范围内进行舒张和收缩,适应呼吸过程中气管的舒张和收缩变化,并且弧形条状体之间以及弧形条状体与连续直壁之间形成了连续通道,有利于新生组织的血供。
优选的方案,所述碳纤维增强复合材料层由碳/碳复合材料或碳/碳/碳化硅复合材料构成。碳/碳复合材料指碳纤维增强碳复合材料,碳/碳/碳化硅复合材料为碳纤维增强碳-碳化硅复合材料。
优选的方案,内层碳纤维增强复合材料层和外层DLC涂层之间设有PyC过渡层。DLC涂层为类金刚石涂层。PyC过渡层为热解碳层。在碳纤维增强复合材料层与DLC涂层之间设置PyC过渡层可消除碳纤维和碳基体的差异性,有利于DLC成膜,提高膜基结合强度。DLC涂层具有硬度高,摩擦系数低及优异的化学惰性的特点,但是其与碳纤维复合材料层之间结合较差,且难以获得均匀的 DLC涂层,而PyC涂层与碳纤维复合材料层之间的结合能力好,但是其硬度较低,仅有1GPa~3GPa,且高温沉积的PyC涂层表面粗糙度高,局部容易破损脱模,形成碳屑,不适宜作为表层,因此,先在碳纤维增强复合材料层表面生成 PyC过渡层,再生成DLC涂层,可以形成与组织相容性、耐磨性能等综合性能较好的复合涂层。
优选的方案,所述PyC过渡层的厚度为5μm~50μm。PyC过渡层厚度的控制对DLC涂层与碳纤维增强复合材料层结合强度的提高是有利的。
优选的方案,所述DLC涂层的厚度为100nm~3μm。
优选的方案,碳纤维增强复合材料层的厚度为1mm~3mm。
本发明还提供了一种碳纤维复合材料人工气管支架的制备方法,采用方案A 或方案B:
方案A包括以下步骤:
1)采用碳纤维编织成抱爪结构,并采用模具辅助成型,得到具有抱爪结构的管状碳纤维预制体;
2)对管状碳纤维预制体进行增密基体碳和/或碳化硅,得到管状碳纤维复合材料坯体;
3)对管状碳纤维复合材料坯体进行机加工制成坯件;
4)在坯件表面生成DLC涂层,或者,先在坯件表面生成PyC涂层,再生成DLC涂层;
方案B包括以下步骤:
1)采用碳纤维织物编织成管状结构,并采用模具辅助成型,得到管状碳纤维预制体;
2)对管状碳纤维预制体进行增密基体碳和/或碳化硅,得到管状碳纤维复合材料坯体;
3)对管状碳纤维复合材料坯体进行机加工,制成具有抱爪结构的坯件;
4)在坯件表面生成DLC涂层,或者,先在坯件表面生成PyC涂层,再生成DLC涂层。
优选的方案,将碳纤维束旋拧成碳纤维绳,再将碳纤维绳编织成抱爪结构;或者,将碳纤维布与碳纤维网复合针刺成管状结构。采用碳纤维束编织具体过程:先将2束以上碳纤维束旋拧成碳纤维绳,然后将碳纤维绳沿轴向和周向铺排编织成抱爪结构或管状结构(交叉臂组成);轴向绳数大于5根绳,周向单臂至少3 根绳。采用碳纤维织物编织的具体过程:将至少2层碳纤维布和至少1层碳纤维网叠层针刺而成管状织物,碳纤维布中长纤维分布在轴向和周向。
较优选的方案,所述碳纤维束的纤维数量为1k、3k、6k或12k(k表示一千根)。
较优选的方案,所述碳纤维布是由1k、3k、6k或12k碳纤维束编织而成的具有平纹、斜纹或缎纹的碳纤维布。
较优选的方案,所述碳纤维网面密度为10g/m2~60g/m2。
优选的方案,所述PyC涂层通过化学气相沉积生成,生成条件:采用气体碳源(如天然气、乙炔等常见气体碳源),在900℃~1500℃温度下沉积10h~100h。由于热解沉积的PyC涂层表面粗糙度高,因此对PyC涂层进行表面抛光,降低粗糙度,再进一步生成DLC涂层,可进一步提升膜基结合性能。
优选的方案,所述DLC涂层通过磁控溅射生成,生成条件:真空度为1×10-1Pa ~5×10-1Pa;工件负偏压:10V~200V(优选为20~100V);Ar流量:50sccm ~120sccm;离子源功率:0.5kW~5kW;石墨靶功率:1kW~3kW,石墨靶纯度 99.99wt%;加热温度:80℃~200℃(优选为100℃~150℃);沉积时间:1h~12h;
或者,
所述DLC涂层通过等离子增强化学气相沉积(以下简称PECVD),生成条件:真空度为1×10-1Pa~5×10-1Pa;工件负偏压:10V~200V(优选为40V~150V); Ar流量:50sccm~120sccm;离子源功率:0.5kW~5kW;烃类气体(如CH4、 C2H2)流量:10sccm~500sccm(优选为20sccm~80sccm);加热温度:80℃~300℃ (优选为100℃~250℃);沉积时间:1h~12h。
本发明增密碳和/或碳化硅的过程主要是采用化学气相沉积。可以只生成碳化硅,也可以只生成碳;也可以先生成基体碳,再生成碳化硅,或者同时生成基体碳和碳化硅,或者先沉积碳化硅,再生成基体碳。生成基体碳的工艺:将碳纤维预制体放入真空炉中,在850℃~1300℃温度下,通入的气源(碳源气体为天然气、甲烷或丙烯等,氮气或氢气为稀释气体,碳源气体与稀释气体的流量比为 1:0~2),裂解50h~200h。生成基体碳化硅制备工艺;将碳纤维预制体放入沉积炉中,在900℃~1300℃温度下,通入的气源(三氯甲基硅烷(MTS),氢气为载气和稀释气体,三氯甲基硅烷与氢气的流量比为1:1~10),裂解10h~100h。同时生成基体碳和碳化硅的工艺:将碳基体气源和三氯甲基硅烷同时通入,其他条件与生成基体碳的工艺条件相同。
本发明的机加工指的是打磨、切割等加工工艺。
本发明在坯件表面生成PyC涂层后,进行抛光和清洗处理,再生成DLC涂层。可以提高涂层之间的结合力。
本发明的碳纤维预制体成型模具采用碳材料制成,如石墨,碳/碳复合材料等。
本发明的碳纤维编织工艺为本领域常见的碳纤维加工工艺。
相对现有技术,本发明技术方案带来的有益效果:
1)本发明提出的人工气管支架主体由碳纤维复合材料制成,轻质、比强度高、生物相容性好,相对一般的涤纶、硅胶材料等具有明显优势。
2)本发明提出的人工气管支架设置抱爪式结构,可实现周向的扩张与收缩,满足气管功能性重建,克服现有技术中人工气管支架不能满足气管在呼吸过程中管腔的收缩与扩张功能,而导致难以应用于临床的缺陷。
3)本发明提出的人工气管支架设有大量预留区域,适合为附着组织提供血运,促进组织新生,有利于气管生物功能性重建。
4)本发明提出的人工气管支架表面的DLC涂层,具有良好的生物相容性,硬度高,可有效阻挡内层碳纤维复合材料基体脱落扩散,避免抑制组织新生。
5)本发明提出的人工气管支架制备方法,通过采用连续碳纤维在支架上分布的增强,设计成直壁与多臂连续气管仿形结构,保障了小尺寸的支撑强度,实现了柔性悬臂和直壁刚性的有机结合。
6)本发明的人工气管支架制备方法,工艺简单,可操作性强,有利于实际工业化生产。
附图说明
【图1】为人工气管支架(适用于全切):左图为单管;中图横截面;右图为主支分叉。
【图2】为人工气管支架实物图:a为绳织管状,b为布网管状,c为绳织抱爪。
具体实施方式
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2束3k碳纤维旋拧成的碳纤维绳,然后将碳纤维绳轴向选15根,轴向单壁5根,编织成碳纤维绳织物,随后件碳纤维绳织物固定在管状的碳/碳复合材料模具上形成抱爪状碳纤维预制体。
2)将碳纤维预制体置于沉积炉中,在850℃的温度下,丙烯为碳源,氮气为稀释气体,丙烯与氮气流量比为1:1,化学气相沉积100h,即得碳纤维复合材料坯体;
3)移除模具,并加工(包括切割和打孔等)后,孔径1mm,空间间距5mm 得碳纤维复合材料坯件;
4)然后进行化学气相沉积PyC(热解碳涂层),工艺参数为:沉积温度1200℃,天然气为碳源,沉积20h,所得涂层厚度为18μm;
5)经表面抛光和清洗后,采用磁控溅射制备DLC涂层,工艺参数为:真空度3×10- 1Pa;工件负偏压:30V;Ar流量:50sccm;离子源功率:3kW;石墨靶功率:1kW,石墨靶纯度99.99wt%;加热温度:100℃;沉积时间:6h。
该实施例制备的人工气管支架:表面硬度为12GPa,膜基结合强度为32N,截面最大伸缩面积大于10%。
实施例2
1)将2层200g/m2的3k碳纤维平纹布与1层20g/m2碳纤维网针刺复合成碳纤维织物,然后将碳纤维绳织物固定在管状石墨模具上形成管状碳纤维预制体。
2)将碳纤维预制体置于沉积炉中,在1100℃的温度下,甲烷为碳源氢气为稀释气体,气源流量比为甲烷:氢气=1:2,化学气相沉积200h,即得碳纤维复合材料坯体;
4)然后进行化学气相沉积热解碳涂层,工艺参数为:沉积温度1300℃,天然气为碳源,沉积10h,PyC厚度约为12μm;
5)经表面抛光和清洗后,采用PECVD制备DLC涂层,工艺参数为:真空度2×10-1Pa;工件负偏压:40V;Ar流量:60sccm;离子源功率:3kW;C2H2流量:150sccm;加热温度:200℃;沉积时间:12h。
该实施例制备的人工气管支架:表面硬度为20GPa,膜基结合强度为56N,截面最大伸缩面积大于25%。
实施例3
1)将3层120g/m2的1k碳纤维斜纹布与2层10g/m2碳纤维网交叉针刺复合成碳纤维织物,然后将碳纤维绳织物固定在管状石墨模具上形成管状碳纤维预制体。
2)将碳纤维预制体置于沉积炉中,在1100℃的温度下,甲烷为碳源,MTS 为硅源,氢气为载气和稀释气体,气源流量比为甲烷:MTS:氢气=1:1:5,化学气相沉积100h,即得碳纤维复合材料坯体;
4)然后进行化学气相沉积热解碳涂层,工艺参数为:沉积温度1300℃,天然气为碳源,沉积30h,PyC厚度30μm;
5)经表面抛光和清洗后,采用磁控溅射制备DLC涂层,工艺参数为:真空度3×10- 1Pa;工件负偏压:30V;Ar流量:50sccm;离子源功率:3kW;石墨靶功率:1kW,石墨靶纯度99.99wt%;加热温度:100℃;沉积时间:6h。
该实施例制备的人工气管支架:表面硬度为25GPa,膜基结合强度为45N,截面最大伸缩面积大于15%。
实施例4
1)将2层200g/m2的3k碳纤维平纹布与1层20g/m2碳纤维网针刺复合成碳纤维织物,然后将碳纤维绳织物固定在管状石墨模具上形成管状碳纤维预制体。
2)将碳纤维预制体置于沉积炉中,在1100℃的温度下,甲烷为碳源氢气为稀释气体,气源流量比为甲烷:氢气=1:2,化学气相沉积200h,即得碳纤维复合材料坯体;
4)经表面抛光和清洗后,采用PECVD制备DLC涂层,工艺参数为:真空度2×10-1Pa;工件负偏压:40V;Ar流量:60sccm;离子源功率:3kW;C2H2流量:150sccm;加热温度:200℃;沉积时间:12h。
该实施例制备的人工气管支架:表面硬度为10GPa,膜基结合强度为20N,截面最大伸缩面积大于25%。
Claims (10)
1.一种碳纤维复合材料人工气管支架,其特征在于:
具有层次管状结构;
所述层次管状结构包括连续直壁以及沿连续直壁两侧轴向布设的抱爪结构;
所述层次管状结构包括内层碳纤维增强复合材料层和外层DLC涂层。
2.根据权利要求1所述的一种碳纤维复合材料人工气管支架,其特征在于:
所述连续直壁表面均匀设有小孔。
3.根据权利要求1所述的一种碳纤维复合材料人工气管支架,其特征在于:所述连续直壁的两侧均匀设置弧形条状体,且直壁两侧的弧形条状体沿层次管状结构轴向相对交替分布,形成抱合状的抱爪结构。
4.根据权利要求1所述的一种碳纤维复合材料人工气管支架,其特征在于:所述碳纤维增强复合材料层由碳/碳复合材料或碳/碳/碳化硅复合材料构成。
5.根据权利要求1所述的一种碳纤维复合材料人工气管支架,其特征在于:内层碳纤维增强复合材料层和外层DLC涂层之间设有PyC过渡层。
6.根据权利要求5所述的一种碳纤维复合材料人工气管支架,其特征在于:
所述PyC过渡层的厚度为5μm~50μm;
所述DLC涂层的厚度为100nm~3μm;
所述碳纤维增强复合材料层厚度为1mm~3mm。
7.权利要求1~6任一项所述的碳纤维复合材料人工气管支架的制备方法,其特征在于:采用方案A或方案B:
方案A包括以下步骤:
1)采用碳纤维编织成抱爪结构,并采用模具辅助成型,得到具有抱爪结构的管状碳纤维预制体;
2)对管状碳纤维预制体进行增密基体碳和/或碳化硅,得到管状碳纤维复合材料坯体;
3)对管状碳纤维复合材料坯体进行机加工制成坯件;
4)在坯件表面生成DLC涂层,或者,先在坯件表面生成PyC涂层,再生成DLC涂层;
方案B包括以下步骤:
1)采用碳纤维织物编织成管状结构,并采用模具辅助成型,得到管状碳纤维预制体;
2)对管状碳纤维预制体进行增密基体碳和/或碳化硅,得到管状碳纤维复合材料坯体;
3)对管状碳纤维复合材料坯体进行机加工,制成具有抱爪结构的坯件;
4)在坯件表面生成DLC涂层,或者,先在坯件表面生成PyC涂层,再生成DLC涂层。
8.根据权利要求7所述的碳纤维复合材料人工气管支架的制备方法,其特征在于:将碳纤维束旋拧成碳纤维绳,再将碳纤维绳编织成抱爪结构;或者,将碳纤维布与碳纤维网复合针刺成管状结构;所述碳纤维束的纤维数量为1k、3k、6k或12k;所述碳纤维布是由1k、3k、6k或12k碳纤维束编织而成的具有平纹、斜纹或缎纹的碳纤维布;所述碳纤维网面密度为10g/m2~60g/m2。
9.根据权利要求7所述的碳纤维复合材料人工气管支架的制备方法,其特征在于:所述PyC涂层通过化学气相沉积生成,生成条件:采用气体碳源,在900℃~1500℃温度下沉积10h~100h。
10.根据权利要求7所述的碳纤维复合材料人工气管支架的制备方法,其特征在于:所述DLC涂层通过磁控溅射生成,生成条件:真空度为1×10-1Pa~5×10-1Pa;工件负偏压:10V~200V;Ar流量:50sccm~120sccm;离子源功率:0.5kW~5kW;石墨靶功率:1kW~3kW,石墨靶纯度99.99wt%;加热温度:80℃~200℃;沉积时间:1h~12h;
或者,
所述DLC涂层通过等离子增强化学气相沉积生成,生成条件:真空度为1×10-1Pa~5×10-1Pa;工件负偏压:10V~200V;Ar流量:50sccm~120sccm;离子源功率:0.5kW~5kW;烃类气体流量:10sccm~500sccm;加热温度:80℃~300℃;沉积时间:1h~12h。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2020100594664 | 2020-01-19 | ||
CN202010059466 | 2020-01-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111925227A CN111925227A (zh) | 2020-11-13 |
CN111925227B true CN111925227B (zh) | 2022-04-08 |
Family
ID=73316141
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010159572.XA Active CN111925227B (zh) | 2020-01-19 | 2020-03-10 | 一种碳纤维复合材料人工气管支架及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111925227B (zh) |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2010274A1 (en) * | 1988-11-10 | 1991-08-16 | Martti Talja | Biodegradable surgical implants and devices |
CN104070687A (zh) * | 2014-06-06 | 2014-10-01 | 中航复合材料有限责任公司 | 一种气囊加压辅助树脂膜转移成型复合材料管型件的方法 |
CN204428211U (zh) * | 2015-01-09 | 2015-07-01 | 中南大学湘雅三医院 | 一种人工肋骨 |
CN105055060A (zh) * | 2015-08-04 | 2015-11-18 | 上海交通大学医学院附属上海儿童医学中心 | 一种气管支架及其应用 |
CN205019206U (zh) * | 2015-08-04 | 2016-02-10 | 上海交通大学医学院附属上海儿童医学中心 | 一种气管支架和组织工程气管 |
CN106957180A (zh) * | 2017-03-10 | 2017-07-18 | 湘潭大学 | 一种Cf/C‑SiC复合材料及其制备方法和应用 |
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 |
CN107854195A (zh) * | 2017-12-12 | 2018-03-30 | 上海交通大学医学院附属上海儿童医学中心 | 一种3d打印非完全性气管环可嵌入双层plla组织工程气管支架及其应用 |
CN108754741A (zh) * | 2018-05-29 | 2018-11-06 | 东华大学 | 组织工程用仿生型气管支架 |
CN109701080A (zh) * | 2018-07-27 | 2019-05-03 | 东华大学 | 一种4轴3d打印管状医用支架及其制备方法 |
CN209173023U (zh) * | 2017-08-23 | 2019-07-30 | 湖南碳康生物科技有限公司 | 一种碳/碳复合材料人工肋骨 |
CN110585491A (zh) * | 2019-09-27 | 2019-12-20 | 长沙晟天新材料有限公司 | 一种碳纤维复合材料接骨板及其制备方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6742855B2 (ja) * | 2016-08-10 | 2020-08-19 | 大阪ガスケミカル株式会社 | 成形断熱材及びその製造方法 |
-
2020
- 2020-03-10 CN CN202010159572.XA patent/CN111925227B/zh active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2010274A1 (en) * | 1988-11-10 | 1991-08-16 | Martti Talja | Biodegradable surgical implants and devices |
CN104070687A (zh) * | 2014-06-06 | 2014-10-01 | 中航复合材料有限责任公司 | 一种气囊加压辅助树脂膜转移成型复合材料管型件的方法 |
CN204428211U (zh) * | 2015-01-09 | 2015-07-01 | 中南大学湘雅三医院 | 一种人工肋骨 |
CN105055060A (zh) * | 2015-08-04 | 2015-11-18 | 上海交通大学医学院附属上海儿童医学中心 | 一种气管支架及其应用 |
CN205019206U (zh) * | 2015-08-04 | 2016-02-10 | 上海交通大学医学院附属上海儿童医学中心 | 一种气管支架和组织工程气管 |
CN106957180A (zh) * | 2017-03-10 | 2017-07-18 | 湘潭大学 | 一种Cf/C‑SiC复合材料及其制备方法和应用 |
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 |
CN209173023U (zh) * | 2017-08-23 | 2019-07-30 | 湖南碳康生物科技有限公司 | 一种碳/碳复合材料人工肋骨 |
CN107854195A (zh) * | 2017-12-12 | 2018-03-30 | 上海交通大学医学院附属上海儿童医学中心 | 一种3d打印非完全性气管环可嵌入双层plla组织工程气管支架及其应用 |
CN108754741A (zh) * | 2018-05-29 | 2018-11-06 | 东华大学 | 组织工程用仿生型气管支架 |
CN109701080A (zh) * | 2018-07-27 | 2019-05-03 | 东华大学 | 一种4轴3d打印管状医用支架及其制备方法 |
CN110585491A (zh) * | 2019-09-27 | 2019-12-20 | 长沙晟天新材料有限公司 | 一种碳纤维复合材料接骨板及其制备方法 |
Non-Patent Citations (4)
Title |
---|
A New Improved Biodegradable Tracheal Prosthesis Using Hydroxy Apatite and Carbon Fiber;TAKAHAMA TATSUHIKO 等;《ASAIO Transactions》;19890731;第35卷(第3期);第291-293页 * |
生物材料在骨科临床中的应用;赵兴伟 等;《中国骨伤》;20041031;第17卷(第10期);第636-637页 * |
碳纤维人工气管的设计及实验研究;戚良晨 等;《生物医学工程学杂志》;19981130;第15卷(第4期);第328-334页 * |
高分子聚合物材料人工气管移植的实验研究;史宏灿 等;《中华外科杂志》;20040831;第42卷(第16期);第972-975页 * |
Also Published As
Publication number | Publication date |
---|---|
CN111925227A (zh) | 2020-11-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11980548B2 (en) | Carbon fiber composite artificial bone and preparation method thereof | |
KR20060065660A (ko) | 다공성 탄소계 성형체의 제조 방법, 및 세포 배양 캐리어시스템과 배양 시스템으로서의 이의 용도 | |
US4613473A (en) | Method for forming composite articles of complex shapes | |
CN101830703B (zh) | 一种炭纤维增强碳化硼复合材料及其制备方法 | |
JP2008531448A (ja) | セラミックマトリックス複合部材の製造方法、および当該方法により得られる部品 | |
KR20050042194A (ko) | 내화성 섬유의 삼차원 섬유구조물, 그것의 제조방법, 및 열구조적 복합물 재료로의 적용 | |
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 | |
US9604886B2 (en) | Ceramic matrix composite material part | |
CN107536659A (zh) | 一种一体化碳纤维复合材料人工骨及其制备方法 | |
CN111925227B (zh) | 一种碳纤维复合材料人工气管支架及其制备方法 | |
CN111548177A (zh) | 一种碳纤维增强陶瓷基复合材料及热解碳界面层制备方法 | |
CN111908935B (zh) | 一种碳基复合材料接骨螺钉及其制备方法 | |
Kim et al. | Effect of a SiC whisker formation on the densification of Tyranno SA/SiC composites fabricated by the CVI process | |
CN112206355B (zh) | 一种仿形人工骨及其制备方法 | |
CN213883677U (zh) | 一种碳纤维复合材料人工气管支架 | |
CN111925226B (zh) | 一种碳纤维复合材料颅骨补片及其制备方法 | |
CN115259882A (zh) | 一种复材纤维丝缠绕碳碳复合材料的生产工艺 | |
CN112190761A (zh) | 一种碳基复合材料人工骨修补材料及其制备方法 | |
CN213883678U (zh) | 一种碳纤维/碳复合材料c形人工气管支架 | |
CN213884404U (zh) | 一种碳纤维绳织复合材料接骨板 | |
CN209136979U (zh) | 一种碳/碳复合材料人工气管支架 | |
JP5572426B2 (ja) | 炭素繊維強化炭化ケイ素系複合材料の製造方法 | |
CN110526731B (zh) | 一种胸腔填充心脏托杯及其制备方法 | |
CN209136980U (zh) | 一种碳/碳复合材料人工气管 | |
CN115153952A (zh) | 一种人工血管接头及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |