CN118750648B - A porous artificial metacarpal bone made of carbon fiber composite material and a preparation method thereof - Google Patents
A porous artificial metacarpal bone made of carbon fiber composite material and a preparation method thereof Download PDFInfo
- Publication number
- CN118750648B CN118750648B CN202411256313.3A CN202411256313A CN118750648B CN 118750648 B CN118750648 B CN 118750648B CN 202411256313 A CN202411256313 A CN 202411256313A CN 118750648 B CN118750648 B CN 118750648B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- fiber composite
- composite material
- porous
- resin
- 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 155
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 147
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 147
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 210000000236 metacarpal bone Anatomy 0.000 title claims description 67
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000004744 fabric Substances 0.000 claims abstract description 19
- 238000005336 cracking Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 26
- 239000000919 ceramic Substances 0.000 claims description 20
- 238000001723 curing Methods 0.000 claims description 20
- 229910052715 tantalum Inorganic materials 0.000 claims description 15
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000003754 machining Methods 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000009719 polyimide resin Substances 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000003345 natural gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 3
- 238000000465 moulding Methods 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 abstract description 39
- 230000009286 beneficial effect Effects 0.000 abstract description 8
- 238000009941 weaving Methods 0.000 abstract description 6
- 238000009958 sewing Methods 0.000 abstract description 5
- 230000008467 tissue growth Effects 0.000 abstract description 4
- 239000012567 medical material Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 27
- 229910000831 Steel Inorganic materials 0.000 description 19
- 239000010959 steel Substances 0.000 description 19
- 230000012010 growth Effects 0.000 description 14
- 239000011148 porous material Substances 0.000 description 13
- 230000002980 postoperative effect Effects 0.000 description 13
- 238000011084 recovery Methods 0.000 description 11
- 238000005452 bending Methods 0.000 description 10
- 230000007547 defect Effects 0.000 description 7
- 230000002349 favourable effect Effects 0.000 description 7
- 210000001519 tissue Anatomy 0.000 description 7
- 229910001069 Ti alloy Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 238000009954 braiding Methods 0.000 description 3
- 230000010261 cell growth Effects 0.000 description 3
- 238000002513 implantation Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000008468 bone growth Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 208000020084 Bone disease Diseases 0.000 description 1
- 208000011092 Hand injury Diseases 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 230000024245 cell differentiation Effects 0.000 description 1
- 230000004663 cell proliferation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
Classifications
-
- 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
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
-
- 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
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Transplantation (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Prostheses (AREA)
Abstract
The invention discloses a porous artificial metacarpal made of a carbon fiber composite material and a preparation method thereof, and belongs to the technical field of medical materials. The preparation method of the porous artificial metacarpal of the carbon fiber composite material comprises the following steps: 1) Weaving a two-dimensional orthogonal carbon fiber fabric; 2) Fixing a die, sewing carbon fiber tows, heating, solidifying and performing thermal decomposition treatment to obtain a three-dimensional orthogonal carbon fiber fabric porous blank; 3) The matrix carbon is produced by chemical vapor deposition or dip-cracking. The porous artificial metacarpal has good biocompatibility, no shielding to X-ray, no artifact problem, and porous structure, and is beneficial to bone tissue growth.
Description
Technical Field
The invention relates to an artificial metacarpal, in particular to a porous artificial metacarpal made of a carbon fiber composite material, and a preparation method thereof, belonging to the technical field of medical materials.
Background
In daily life, the main function of metacarpal bones is to support hand movements and maintain normal morphology of hands, and metacarpal bone defects due to squeezing, striking or bone diseases are a very serious hand injury. Chinese patent CN216090946U discloses a handle-type customized artificial metacarpal prepared from titanium alloy material, which has the advantages of rapid assembly, firm fixation, difficult loosening, contribution to bone ingrowth due to surface coating, etc., but titanium alloy material has certain disadvantages, such as higher density, easy occurrence of artifacts, influence on postoperative diagnosis of patients, etc., and the artificial metacarpal is handle-type customized, long in manufacturing period, high in cost, and incapable of mass production. In addition, the existing artificial metacarpal bone has the problems of slow bone growth, inconvenient fixation, unstable fixation, easy displacement, loosening, dislocation and the like after long-time use, needs secondary operation for revision, and brings double physical and economic pressure to patients. Chinese patent (CN 112190756A) discloses a preparation method of a carbon fiber composite profiling artificial bone, which is characterized in that an artificial rib is prepared by two-dimensional weaving carbon fiber fabric, and meanwhile, an internal pore is constructed by a method of combining presoaked resin with pyrolysis, but the obtained artificial bone still has the technical problems of insufficient internal macropores, low porosity, poor tissue ingrowth and the like, and meanwhile, the mechanical property of the two-dimensional weaving carbon fiber fabric is difficult to meet the application requirements of metacarpal bones.
Disclosure of Invention
Aiming at the defects existing in the prior art, the first aim of the invention is to provide a porous artificial metacarpal made of a carbon fiber composite material, which takes the carbon fiber composite material as a matrix material, has good biocompatibility, no shielding to X rays, no artifact problem, long-term implantation, good bone growth and stability, and has the density similar to that of primary bones, the weight of the porous artificial metacarpal is reduced by 60 percent compared with the prior titanium alloy material, a porous structure is constructed, the growth of bone tissues is facilitated, and the technical problems of the prior carbon fiber composite material such as insufficient macropores, low porosity, poor tissue growth and the like are overcome.
The second aim of the invention is to provide a preparation method of the porous artificial metacarpal of the carbon fiber composite material, which is simple to operate and low in cost, and can realize standardized production.
In order to achieve the technical aim, the invention provides a preparation method of a porous artificial metacarpal of a carbon fiber composite material, which comprises the following steps:
1) Fixing a reserved rod along the Z-axis direction, weaving carbon fiber tows of pre-impregnated resin around the reserved rod in an X-Y plane in a staggered manner to form a two-dimensional carbon fiber fabric, and overlapping the two-dimensional carbon fiber fabric layer by layer along the vertical direction of the reserved rod to form a plurality of layers of two-dimensional orthogonal carbon fiber fabrics;
2) Fixing a plurality of layers of two-dimensional orthogonal carbon fiber fabrics through a die, heating and curing, removing part of reserved rods, penetrating carbon fiber tows of prepreg resin into reserved holes formed by the reserved rods, stitching, heating and curing, and removing the die to perform thermal decomposition treatment to obtain a three-dimensional orthogonal carbon fiber fabric porous blank;
3) Firstly, preparing a three-dimensional orthogonal carbon fiber fabric porous blank body by chemical vapor deposition matrix carbon or dipping-cracking to obtain matrix carbon, removing all reserved bars and machining to obtain a carbon fiber composite material porous artificial metacarpal bone; the machining comprises the working procedures of cutting and polishing to realize the shaping of the porous artificial metacarpal of the carbon fiber composite material; the carbon fiber composite material porous artificial metacarpal bone is of an integrated structure, the middle section of the carbon fiber composite material porous artificial metacarpal bone is a cylinder, and the two ends of the carbon fiber composite material porous artificial metacarpal bone are polyhedrons or cylinders with certain taper; more than two groups of grooves which are symmetrically distributed in the axis direction are uniformly distributed on the surface of the cylinder along the axis direction, wherein one group of grooves is a main groove, and more than two vertical through holes are uniformly distributed in the main groove; the cylindrical surface with a certain taper of the polyhedron or the end part is provided with a vertical through hole which is parallel to the vertical through hole in the main groove.
According to the preparation method of the artificial metacarpal bone made of the carbon fiber composite material, the carbon fiber tows of the pre-impregnated resin are used for constructing the uniformly distributed porous structure through three-dimensional orthogonal weaving and the pyrolytic resin, so that the growth of bone tissues in the later period of a patient is facilitated, and a good foundation is laid for postoperative recovery of the patient.
The preparation method of the artificial metacarpal of the carbon fiber composite material utilizes the reserved rod as a template to form the reserved hole, so that not only can mechanical punching be avoided to reduce the mechanical strength of the carbon fiber composite material, but also through holes can be formed to be matched with a microporous hole structure constructed by resin pyrolysis to form a developed hole structure, thereby being beneficial to bone tissue growth and well solving the technical problems of insufficient macropores, low through hole rate, poor tissue ingrowth and the like of the carbon fiber composite material.
The preparation method of the artificial metacarpal bone made of the carbon fiber composite material adopts three-dimensional orthogonal weaving, has uniformity of material structure, avoids layering phenomenon, has better mechanical strength, has stronger process designability compared with a planar fabric, can be molded at one time, and is suitable for special-shaped workpieces.
Compared with the existing biological materials such as titanium alloy, high polymer, ceramic and the like, the carbon fiber composite porous artificial metacarpal bone provided by the invention has the advantages of light weight, similar bone modulus, good biocompatibility, no artifact, good strength and the like.
As a preferable scheme, the reserved rod is a ceramic rod, a metal rod or a carbon rod. The preformed hole is formed on the preformed rod, the pore size is controllable, the pore size is uniform, and the damage of the carbon fiber caused by subsequent machining of the macropores can be avoided, so that the mechanical property of the carbon fiber composite material is reduced. As a more preferable scheme, the diameter of the reserved rod is 0.5-1.2 mm.
As a preferable scheme, the mass content of the surface resin of the carbon fiber tows of the pre-impregnated resin is 5-10%; the resin is at least one of epoxy resin, phenolic resin, polyimide resin, vinyl ester resin and bismaleimide resin. The resin is used as a binder and also used as a pore-forming agent, and plays a role in binding in the heating and curing process, so that the carbon fibers are solidified into a whole, the mechanical strength of the carbon fibers is improved, the resin is pyrolyzed and volatilized in the pyrolysis process, and a uniformly distributed pore structure is formed in the carbon fiber fabric. The content of the resin influences the pore structure, if the content of the resin is too low, the carbon fibers are too dense, the porosity is low, the density is higher, and if the content of the resin is too high, the carbon fibers are low in proportion, and the mechanical properties are influenced.
As a preferable embodiment, the conditions for the heat curing are: the temperature is 200-350 ℃, the time is 3-10 h, and the heating rate is 5-10 ℃/min.
As a preferable embodiment, the conditions of the thermal decomposition treatment are as follows: p is less than 5kPa, the temperature is 500-1000 ℃, the time is 1-5 h, and the heating rate is 3-10 ℃/min. The thermal decomposition is required to be carried out under negative pressure, so that organic micromolecules formed by resin pyrolysis can volatilize in time, and a porous structure is formed.
As a preferred embodiment, the conditions for chemical vapor deposition of the base carbon are: methane and/or natural gas are used as carbon sources, hydrogen and/or nitrogen are used as diluent gases, the flow ratio of the carbon sources to the diluent gases is 1:1-3, and the deposition is carried out for 20-200 h at the temperature of 850-1300 ℃.
As a preferred embodiment, the conditions for the impregnation-cleavage to form the matrix carbon are: the impregnating resin is at least one of epoxy resin, phenolic resin, polyimide resin, vinyl ester resin and bismaleimide resin, the impregnating pressure is 1.0-5.0 MPa, the impregnating time is 3-12 h, the curing temperature is 200-350 ℃, the curing time is 3-10 h, the cracking temperature is 900-1100 ℃, and the cracking time is 2-20 h.
As a further preferable scheme, the middle section of the porous artificial metacarpal of the carbon fiber composite material is a cylinder, and the two ends of the porous artificial metacarpal are polyhedrons (cuboid with a certain taper at the end part); three groups of semicircular grooves which are symmetrically distributed in the axis direction are uniformly distributed on the surface of the cylinder along the axis direction, wherein one group of semicircular grooves with relatively large radius is a main groove, and the other two groups of semicircular grooves with relatively small radius are auxiliary grooves; three vertical through holes are uniformly distributed in the main groove; the surface of the cuboid with the end part having a certain taper is provided with a vertical through hole, and the vertical through hole is parallel to the three vertical through holes in the main groove. The radius of the main groove is twice that of the auxiliary groove. The two ends of the carbon fiber composite material porous artificial metacarpal bone are cuboid with a certain taper, so that the carbon fiber composite material porous artificial metacarpal bone is conveniently embedded into the autologous bone for fixation, and a round vertical through hole in the cuboid is used for fixation between a steel wire or suture and the autologous bone. The main body part cylinder in the middle of the artificial metacarpal plays a main supporting role on surrounding soft tissues, the semicircular grooves on the surface of the cylinder are convenient for the growth and attachment of bone tissues of a patient, wherein two main grooves are axially symmetrically distributed, vertical through holes on the main grooves are parallel to vertical through holes on cuboids at two ends, the direction can be conveniently identified by medical staff in operation, and three circular vertical through holes on the main grooves are used for fixing the prosthesis and accommodating steel wires or sutures. Circular vertical through holes can be arranged on the side surface of the main groove of the cylinder, are positioned between two adjacent vertical through holes in the main groove and are perpendicular to three circular vertical through holes in the main groove, and are mainly used for tissue growth and prosthesis fixation.
As a preferable scheme, the side surface of the main groove is provided with at least one vertical through hole, and the side surface of the main groove is positioned at the middle position of two adjacent vertical through holes in the main groove and is vertical to the vertical through holes in the main groove.
The design of the porous artificial metacarpal bone structure made of the carbon fiber composite material can realize multiple fixation so as to solve the problems that the prosthesis is easy to loosen and shift in the later period of a patient, avoid secondary operation of the patient and relieve the pain of the patient. The first heavy fixation is the embedded fixation of cuboid and autogenous bone at prosthesis both ends, the second heavy fixation is the steel wire or suture fixation of autogenous bone and artificial metacarpal bone main part, and the third heavy fixation is the attachment fixation of patient bone tissue on the preformed hole, semicircular groove and through hole of the prosthesis, thereby multiple fixation provides the guarantee for the long-term implantation of artificial metacarpal bone.
As a preferable scheme, the surface of the porous artificial metacarpal of the carbon fiber composite material is plated with a tantalum coating by physical vapor deposition under the following conditions: ar gas flow is 60-90 sccm, vacuum degree is 1.0X10 -1Pa~4.0×10-1 Pa, tantalum target power is 0.5-3 kW, ion source power is 0.9-1.2 kW, workpiece negative bias voltage is 100-800V, and deposition time is 60-180 min. Plating a tantalum coating on the surface of the porous artificial metacarpal bone made of the carbon fiber composite material is beneficial to cell adhesion, proliferation and differentiation, can further improve the growth of bone tissues around the prosthesis, and meanwhile, the tantalum coating also improves the visibility of the prosthesis in a human body, thereby being convenient for postoperative review.
Compared with the prior art, the technical scheme of the invention has the advantages that:
1. The carbon fiber composite material porous artificial metacarpal bone adopts a carbon fiber composite material, has the advantages of light weight, similar bone modulus, good biocompatibility, no artifact, good strength and the like compared with materials such as titanium alloy, high polymer, ceramic and the like, and the carbon fiber composite material porous artificial metacarpal bone material is formed into a porous structure through three-dimensional orthogonalization, thereby being beneficial to the growth of bone tissues in the later period of a patient and laying a good foundation for postoperative recovery of the patient.
2. The porous artificial metacarpal bone made of the carbon fiber composite material has triple fixation, solves the problems of loosening and shifting of the prosthesis in the later period of the patient, avoids the secondary operation of the patient, and relieves the pain of the patient. The first fixation is mosaic fixation of the two ends of the prosthesis and the autologous bone, the second fixation is fixation of the autologous bone and the steel wire or suture of the main body part of the prosthesis, and the third fixation is adhesion fixation of the bone tissue of the patient on the preformed hole, the groove and the through hole of the prosthesis. Thus, triple fixation provides a guarantee for long-term implantation of artificial metacarpals.
3. The main groove through holes of the porous artificial metacarpal made of the carbon fiber composite material are consistent with the directions of the through holes at the two ends, so that the main groove through holes are used for identifying directions in operation by medical staff, the medical staff can quickly complete the assembly and fixation of the prosthesis, the operation time is shortened, the operation risk is reduced, and the pain of a patient is relieved.
4. The appearance form of the porous artificial metacarpal of the carbon fiber composite material is standardized, batch production can be carried out, the porous artificial metacarpal can be processed and adjusted according to the actual defect length of a patient, the operation is simple, the requirements of most patients can be timely met, the customized metacarpal is long in manufacturing period, the illness state of the patient can be delayed, and the pain of the patient is increased.
5. The porous artificial metacarpal of the carbon fiber composite material has a porous structure, the apparent porosity is more than or equal to 22%, the circulation of bone tissue fluid in the later period of a patient is facilitated, the postoperative recovery is promoted, the porous artificial metacarpal has good mechanical properties, such as bending strength is more than or equal to 180MPa, bending modulus is more than or equal to 15GPa, meanwhile, the tantalum coating improves the surface hydrophilicity of the prosthesis, the contact angle is 50-55 degrees, and the adhesion and growth of tissue cells around the prosthesis are facilitated.
Therefore, the invention can provide a carbon fiber composite porous artificial metacarpal bone which can be implanted for a long time, has good biocompatibility, good bone ingrowth and stability, can maintain the shape of the hand after operation and provides hand movement support for patients.
Drawings
FIG. 1 is a schematic illustration of a process for preparing a multi-layer two-dimensional orthogonal carbon fiber fabric.
Fig. 2 is an elevation view of a carbon fiber composite porous artificial metacarpal.
Fig. 3 is a top view of two ends of a porous artificial metacarpal of carbon fiber composite.
Fig. 4 is a side view of a carbon fiber composite porous artificial metacarpal.
Wherein 1 is a cuboid with a certain taper at the end part, 2 is a cylinder, 3 is a through hole with a cuboid surface with a certain taper at the end part, 4 is a semicircular groove (main groove), 5 is a semicircular groove, 6 is a through hole in the main groove, and 7 is a through hole on the side surface of the main groove.
Detailed Description
The present invention will be described in further detail with reference to the drawings, but the following specific examples do not limit the scope of the present invention.
Example 1
1.1 Constructing a carbon fiber composite porous artificial metacarpal bone material by a three-dimensional orthogonal method, specifically fixing a ceramic rod with the diameter of 0.6mm on an X-Y plane with the length of 10 multiplied by 10cm every 4mm, and forming a 10mm multilayer two-dimensional orthogonal carbon fiber porous pre-fixing material by stacking and adding carbon fiber tows pre-impregnated with epoxy resin in a mass ratio of 10:90 layer by staggering in the horizontal direction and the vertical direction.
1.2, Fixing a plurality of layers of two-dimensional orthogonal carbon fiber porous pre-fixing materials through a metal mold, then heating and solidifying, removing a ceramic rod every 8mm, penetrating and sewing carbon fiber tows of the pre-impregnated resin into reserved holes of the ceramic rod, and then heating and solidifying to obtain the carbon fiber porous pre-fixing materials. Wherein the curing temperature is 250 ℃, the curing time is 6 hours, and the heating rate is 5 ℃/min.
1.3 Removing the metal mold, and carrying out thermal decomposition treatment on the carbon fiber porous prefabricated material to obtain a carbon fiber porous material blank, wherein the specific condition is that P is 3kPa, the temperature is 600 ℃, the decomposition time is 4 hours, and the heating rate is 10 ℃/min.
1.4, Performing chemical vapor deposition on the carbon fiber porous material blank to generate matrix carbon, removing residual ceramic rods, and finally obtaining the carbon fiber composite material porous artificial metacarpal bone material, wherein methane is used as a carbon source, hydrogen is used as diluent gas, the gas flow ratio is 1:1, and the deposition is performed for 60 hours at 1100 ℃.
1.5, Processing to obtain a metacarpal bone blank.
1.6, Preparing a tantalum coating from the metacarpal bone blank by physical vapor deposition, wherein the conditions are as follows: ar gas flow is 70sccm, vacuum degree is 3.5X10 -1 Pa, tantalum target power is 2kW, ion source power is 1kW, workpiece negative bias voltage is 200V, deposition time is 100min, and finally the porous artificial metacarpal of the carbon fiber composite material is obtained.
2.1 The porous artificial metacarpal of carbon fiber composite material of this embodiment is as an organic whole structure, and both ends are the cuboid structure that has certain tapering, are convenient for embed in the autologous bone fixed. The length of cuboid is 4mm, and wide is 3mm, and is high to be 5mm, have a diameter in the cuboid structure and be 2mm and run through circular hole for the fixed of steel wire and autologous bone.
2.2 The main part of the porous artifical metacarpal of carbon fiber composite is the cylinder structure, and its diameter is 8mm, and length is 26mm, and the cylinder surface has four 1 mm's semicircle grooves and two 2 mm's main tank, and the growth of patient's bone tissue is attached of being convenient for, and wherein, two main tanks symmetric distribution is on the cylinder, is unanimous with the through-hole direction at both ends, and the medical staff of being convenient for discern the direction in the operation, and has three diameter to be 2mm circular through-holes on the main tank for the fixed of prosthesis and the accomodate of steel wire. The two circular through holes on the side surface of the cylinder are positioned among the three circular through holes of the main groove, and the diameter is 2mm, thereby being beneficial to the growth of tissues and the fixation of the prosthesis.
2.3 Specifically, medical staff can process the product to a proper length according to the length of the metacarpal defect of the patient. The fixing method is to make a through hole at the top end and the bottom end of the primary metacarpal bone of the patient respectively, and embed the two ends of the prosthesis into the primary metacarpal bone marrow cavity correspondingly respectively to realize the first re-fixing. Then the steel wire passes through the primary metacarpal bone, the two ends of the prosthesis and the through holes of the main body part, and is fixed around the circle, and the steel wire knot can be accommodated in the through holes in the main groove, so that the second fixation is realized. As the patient's post-operative recovery time increases, bone tissue adheres and grows in the semicircular grooves and through-holes of the body portion, providing a third re-fixation.
2.4 The porous artificial metacarpal bone of the carbon fiber composite material has a porosity of 30%, the porous structure is favorable for postoperative recovery, the bending strength is 180MPa, the bending modulus is 16GPa, the contact angle is 52 degrees, and the porous artificial metacarpal bone has good hydrophilicity and is favorable for adhesion and growth of cells in later period.
Example 2
1.1 Constructing a carbon fiber composite porous artificial metacarpal bone material by a three-dimensional orthogonal method, specifically fixing a ceramic rod with the diameter of 0.6mm on an X-Y plane with the length of 8 multiplied by 8cm every 4mm, and forming a 10mm multilayer two-dimensional orthogonal carbon fiber porous pre-fixing material by stacking and adding the carbon fiber tows with the mass ratio of epoxy resin to carbon fiber of 5:95 layer by staggering and braiding the carbon fiber tows with the pre-resin in the horizontal direction and the vertical direction.
1.2, Fixing a plurality of layers of two-dimensional orthogonal carbon fiber porous pre-fixing materials through a metal mold, then heating and solidifying, removing a ceramic rod every 8mm, penetrating and sewing carbon fiber tows of the pre-impregnated resin into reserved holes of the ceramic rod, and then heating and solidifying to obtain the carbon fiber porous pre-fixing materials. Wherein the curing temperature is 300 ℃, the curing time is 4h, and the heating rate is 10 ℃/min.
1.3 Removing the metal grinding tool, and carrying out thermal decomposition treatment on the carbon fiber porous prefabricated material to obtain a carbon fiber porous material blank, wherein the specific condition is that P is 3 kPa, the temperature is 800 ℃, the decomposition time is 4 h, and the heating rate is 10 ℃/min.
1.4, Performing chemical vapor deposition on the carbon fiber porous material blank to generate matrix carbon, removing residual ceramic rods, and finally obtaining the carbon fiber composite material porous artificial metacarpal bone material, wherein methane is used as a carbon source, hydrogen is used as diluent gas, the gas flow ratio is 1:1, and the deposition is performed for 80 hours at 1200 ℃.
1.5, Processing to obtain a metacarpal bone blank.
1.6, Preparing a tantalum coating from the metacarpal bone blank by physical vapor deposition, wherein the conditions are as follows: ar gas flow is 90sccm, vacuum degree is 4×10 -1 Pa, tantalum target power is 2kW, ion source power is 1.2kW, workpiece negative bias voltage is 200V, deposition time is 80min, and the porous artificial metacarpal of the carbon fiber composite material is obtained.
2.1 The porous artificial metacarpal of carbon fiber composite material of this embodiment is as an organic whole structure, and both ends are the cuboid structure that has certain tapering, are convenient for embed in the autologous bone fixed. The length of cuboid is 4mm, and wide is 3mm, and is high to be 5mm, have a diameter in the cuboid structure and be 2mm and run through circular hole for the fixed of steel wire and autologous bone.
2.2 The main part of the porous artifical metacarpal of carbon fiber composite is the cylinder structure, and its diameter is 8mm, and length is 20mm, and the cylinder surface has four 1 mm's semicircle grooves and two 2 mm's main tank, and the growth of patient's bone tissue is attached of being convenient for, and wherein, two main tanks symmetric distribution is on the cylinder, is unanimous with the through-hole direction at both ends, and the medical staff of being convenient for discern the direction in the operation, and has three diameter to be 3mm circular through-holes on the main tank for the fixed of prosthesis and the accomodate of steel wire. The two circular through holes on the side surface of the cylinder are positioned among the three circular through holes of the main groove, and the diameter is 2mm, thereby being beneficial to the growth of tissues and the fixation of the prosthesis.
2.3 Specifically, medical staff can process the product to a proper length according to the length of the metacarpal defect of the patient. The fixing method is to make a through hole at the top end and the bottom end of the primary metacarpal bone of the patient respectively, and embed the two ends of the prosthesis into the primary metacarpal bone marrow cavity correspondingly respectively to realize the first re-fixing. Then the steel wire passes through the primary metacarpal bone, the two ends of the prosthesis and the through holes of the main body part, and is fixed around the circle, and the steel wire knot can be accommodated in the through holes in the main groove, so that the second fixation is realized. As the patient's post-operative recovery time increases, bone tissue adheres and grows in the semicircular grooves and through-holes of the body portion, providing a third re-fixation.
2.4 The porous artificial metacarpal bone made of the carbon fiber composite material has the apparent porosity of 22%, the porous structure is favorable for postoperative recovery, the bending strength is 201MPa, the bending modulus is 17GPa, the contact angle is 55 degrees, and the porous artificial metacarpal bone has good hydrophilicity and is favorable for adhesion and growth of cells in later period.
Example 3
1.1 Constructing a carbon fiber composite porous artificial metacarpal bone material by a three-dimensional orthogonal method, specifically fixing a ceramic rod with the diameter of 1.0mm on an X-Y plane with the length of 10 multiplied by 10cm every 4mm, and forming a 10mm multilayer two-dimensional orthogonal carbon fiber porous pre-fixing material by stacking and adding the carbon fiber tows with the mass ratio of epoxy resin to carbon fiber of 5:95 layer by staggering and braiding carbon fiber tows with the pre-resin in the horizontal direction and the vertical direction.
1.2, Fixing a plurality of layers of two-dimensional orthogonal carbon fiber porous pre-fixing materials through a metal mold, then heating and solidifying, removing a ceramic rod every 8mm, penetrating and sewing carbon fiber tows of the pre-impregnated resin into reserved holes of the ceramic rod, and then heating and solidifying to obtain the carbon fiber porous pre-fixing materials. Wherein the curing temperature is 200 ℃, the curing time is 6 hours, and the heating rate is 5 ℃/min.
1.3 Removing the metal mold, and carrying out thermal decomposition treatment on the carbon fiber porous prefabricated material to obtain a carbon fiber porous material blank, wherein the specific condition is that P is 4kPa, the temperature is 1000 ℃, the decomposition time is 3 hours, and the heating rate is 10 ℃/min.
1.4, Impregnating and cracking the carbon fiber porous material blank to generate matrix carbon, removing residual ceramic rods, and finally obtaining the carbon fiber composite material porous artificial metacarpal bone material, wherein the blank is impregnated by epoxy resin, the impregnating pressure is 2.5MPa, the impregnating time is 6h, the curing temperature is 250 ℃, the curing time is 6h, the cracking temperature is 1000 ℃, and the cracking time is 10h.
1.5, Processing to obtain a metacarpal bone blank.
1.6, Preparing a tantalum coating from the metacarpal bone blank by physical vapor deposition, wherein the conditions are as follows: ar gas flow is 80sccm, vacuum degree is 4×10 -1 Pa, tantalum target power is 1.5kW, ion source power is 1.2kW, workpiece negative bias voltage is 100V, deposition time is 120min, and the porous artificial metacarpal of the carbon fiber composite material is obtained.
2.1 The porous artificial metacarpal of carbon fiber composite material of this embodiment is as an organic whole structure, and both ends are the cuboid structure that has certain tapering, are convenient for embed in the autologous bone fixed. The length of cuboid is 4mm, and wide is 3mm, and is high to be 5mm, have a diameter in the cuboid structure and be 2mm and run through circular hole for the fixed of steel wire and autologous bone.
2.2 The main part of the porous artifical metacarpal of carbon fiber composite is the cylinder structure, and its diameter is 8mm, and length is 24mm, and the cylinder surface has four 1 mm's semicircle grooves and two 2 mm's main tank, and the growth of patient's bone tissue is attached of being convenient for, and wherein, two main tanks symmetric distribution is on the cylinder, is unanimous with the through-hole direction at both ends, and the medical staff of being convenient for discern the direction in the operation, and has three diameter 2mm circular through-holes on the main tank for the fixed of prosthesis and the accomodate of steel wire. The two circular through holes on the side surface of the cylinder are positioned among the three circular through holes of the main groove, and the diameter is 2mm, thereby being beneficial to the growth of tissues and the fixation of the prosthesis.
2.3 Specifically, medical staff can process the product to a proper length according to the length of the metacarpal defect of the patient. The fixing method is to make a through hole at the top end and the bottom end of the primary metacarpal bone of the patient respectively, and embed the two ends of the prosthesis into the primary metacarpal bone marrow cavity correspondingly respectively to realize the first re-fixing. Then the steel wire passes through the primary metacarpal bone, the two ends of the prosthesis and the through holes of the main body part, and is fixed around the circle, and the steel wire knot can be accommodated in the through holes in the main groove, so that the second fixation is realized. As the patient's post-operative recovery time increases, bone tissue adheres and grows in the semicircular grooves and through-holes of the body portion, providing a third re-fixation.
2.4 The porous artificial metacarpal bone of the carbon fiber composite material has a porosity of 26%, the porous structure is favorable for the recovery of postoperative patients, the bending strength is 192MPa, the bending modulus is 16GPa, the contact angle is 50 degrees, and the porous artificial metacarpal bone has good hydrophilicity and is favorable for the adhesion and growth of cells in the later period.
Example 4
1.1 Constructing a carbon fiber composite porous artificial metacarpal bone material by a three-dimensional orthogonal method, specifically fixing a ceramic rod with the diameter of 1.2mm on an X-Y plane with the length of 10 multiplied by 10cm every 4mm, and forming a 10mm multilayer two-dimensional orthogonal carbon fiber porous pre-fixing material by stacking and adding the carbon fiber tows with the mass ratio of epoxy resin to carbon fiber of 5:95 layer by staggering and braiding the carbon fiber tows with the pre-resin in the horizontal direction and the vertical direction.
1.2, Fixing a plurality of layers of two-dimensional orthogonal carbon fiber porous pre-fixing materials through a metal mold, then heating and solidifying, removing a ceramic rod every 8mm, penetrating and sewing carbon fiber tows of the pre-impregnated resin into reserved holes of the ceramic rod, and then heating and solidifying to obtain the carbon fiber porous pre-fixing materials. Wherein the curing temperature is 280 ℃, the curing time is 5 hours, and the heating rate is 5 ℃/min.
1.3 Removing the metal mold, and carrying out thermal decomposition treatment on the carbon fiber porous prefabricated material to obtain a carbon fiber porous material blank, wherein the specific condition is that P is 3kPa, the temperature is 1000 ℃, the decomposition time is 3 hours, and the heating rate is 10 ℃/min.
1.4, Impregnating and cracking the carbon fiber porous material blank to generate matrix carbon, removing residual ceramic rods, and finally obtaining the carbon fiber composite material porous artificial metacarpal bone material, wherein the blank is impregnated by epoxy resin, the impregnating pressure is 2.5MPa, the impregnating time is 6h, the curing temperature is 250 ℃, the curing time is 6h, the cracking temperature is 1000 ℃, and the cracking time is 10h.
And 1.5, processing to obtain the porous artificial metacarpal of the carbon fiber composite material.
2.1 The porous artificial metacarpal of carbon fiber composite material of this embodiment is as an organic whole structure, and both ends are the cuboid structure that has certain tapering, are convenient for embed in the autologous bone fixed. The length of cuboid is 4mm, and wide is 3mm, and is high to be 5mm, have a diameter in the cuboid structure and be 2mm and run through circular hole for stainless steel wire and autologous bone's fixed.
2.2 The main part of the porous artifical metacarpal of carbon fiber composite is the cylinder structure, and its diameter is 8mm, and length is 26mm, and the cylinder surface has four 1 mm's semicircle grooves and two 2 mm's main tank, and the growth of patient's bone tissue is attached of being convenient for, and wherein, two main tanks symmetric distribution is on the cylinder, is unanimous with the through-hole direction at both ends, and the medical staff of being convenient for discern the direction in the operation, and has three diameter 2mm circular through-holes on the main tank for the fixed of prosthesis and the accomodate of steel wire. The two circular through holes on the side surface of the cylinder are positioned among the three circular through holes of the main groove, and the diameter is 2mm, thereby being beneficial to the growth of tissues and the fixation of the prosthesis.
2.3 Specifically, medical staff can process the product to a proper length according to the length of the metacarpal defect of the patient. The fixing method is to make a through hole at the top end and the bottom end of the primary metacarpal bone of the patient respectively, and embed the two ends of the prosthesis into the primary metacarpal bone marrow cavity correspondingly respectively to realize the first re-fixing. Then the steel wire passes through the primary metacarpal bone, the two ends of the prosthesis and the through holes of the main body part, and is fixed around the circle, and the steel wire knot can be accommodated in the through holes in the main groove, so that the second fixation is realized. As the patient's post-operative recovery time increases, bone tissue adheres and grows in the semicircular grooves and through-holes of the body portion, providing a third re-fixation.
2.4 The apparent porosity of the porous artificial metacarpal of the carbon fiber composite material is 27%, the porous structure is favorable for the recovery of postoperative patients, the bending strength is 189MPa, the bending modulus is 15GPa, the contact angle is 69 degrees, and the hydrophilicity is relatively low because the surface of the porous artificial metacarpal of the carbon fiber composite material is not plated with a tantalum coating.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411256313.3A CN118750648B (en) | 2024-09-09 | 2024-09-09 | A porous artificial metacarpal bone made of carbon fiber composite material and a preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202411256313.3A CN118750648B (en) | 2024-09-09 | 2024-09-09 | A porous artificial metacarpal bone made of carbon fiber composite material and a preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118750648A CN118750648A (en) | 2024-10-11 |
| CN118750648B true CN118750648B (en) | 2024-11-12 |
Family
ID=92940640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202411256313.3A Active CN118750648B (en) | 2024-09-09 | 2024-09-09 | A porous artificial metacarpal bone made of carbon fiber composite material and a preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118750648B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641522A (en) * | 2012-04-13 | 2012-08-22 | 辽宁工业大学 | Method for preparing medical three-dimensional gradient netlike carbon fiber/ hydroxyapatite (HA)/ medical stone composite material |
| CN112190756A (en) * | 2020-09-28 | 2021-01-08 | 湖南碳康生物科技有限公司 | Preparation method of carbon fiber composite material profiling artificial bone |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI498111B (en) * | 2012-11-07 | 2015-09-01 | Univ Nat Cheng Kung | Artificial implant for carpometacarpal joint |
| WO2017069656A2 (en) * | 2015-09-25 | 2017-04-27 | Олег Викторович БАРЗИНСКИЙ | Composite material for repairing bone defects, method of producing same, and implant made therefrom |
| WO2018038624A1 (en) * | 2016-08-22 | 2018-03-01 | Олег Викторович БАРЗИНСКИЙ | Composite carbon nanomaterial for repairing bone defects, a method for producing same, and an implant made from composite carbon nanomaterial |
| CN213883674U (en) * | 2020-09-28 | 2021-08-06 | 湖南碳康生物科技有限公司 | Carbon fiber/carbon composite material T-shaped artificial rib connecting piece |
-
2024
- 2024-09-09 CN CN202411256313.3A patent/CN118750648B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641522A (en) * | 2012-04-13 | 2012-08-22 | 辽宁工业大学 | Method for preparing medical three-dimensional gradient netlike carbon fiber/ hydroxyapatite (HA)/ medical stone composite material |
| CN112190756A (en) * | 2020-09-28 | 2021-01-08 | 湖南碳康生物科技有限公司 | Preparation method of carbon fiber composite material profiling artificial bone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118750648A (en) | 2024-10-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11980548B2 (en) | Carbon fiber composite artificial bone and preparation method thereof | |
| CA2083484C (en) | Composite orthopedic implant with modulus variations | |
| CN107536659B (en) | A kind of integral carbon fibre composite material artificial bone and preparation method thereof | |
| RU88952U1 (en) | IMPLANT FOR COMPENSATION OF BONE DEFECTS | |
| CN101301230A (en) | Preparation method of artificial joint prosthesis with locally controllable porous structure | |
| WO2012142952A1 (en) | Porous tantalum rod | |
| RU88953U1 (en) | IMPLANT FOR SURGICAL REPAIR TREATMENT OF BONE DEFECTS | |
| CN110606762B (en) | Carbon fiber composite skull repairing piece and preparation method thereof | |
| CN105380731A (en) | Porous tantalum metal bone connector and application thereof | |
| CN118750648B (en) | A porous artificial metacarpal bone made of carbon fiber composite material and a preparation method thereof | |
| CN112190375B (en) | High-bioactivity carbon fiber/carbon composite material C-shaped artificial trachea stent and preparation method thereof | |
| CN103465542A (en) | Degradable iron, zinc and magnesium-based gradient composite material based on biological bone healing and preparation thereof | |
| WO2017063425A1 (en) | Porous tantalum metal bone connector and application thereof | |
| CN206621458U (en) | A kind of acetabular cup prosthesis of porous surface | |
| US8167955B2 (en) | Carbon fiber reinforced carbon foams for repair and reconstruction of bone defects | |
| CN105380732A (en) | Bone repair material with multi-dimensional channel structure | |
| CN101283936A (en) | Partial grid structure artificial joint prosthesis and preparation method thereof | |
| CN110606746B (en) | Skull repairing patch and preparation method thereof | |
| CN205107979U (en) | Porous tantalum metal bone connector | |
| CN107303207B (en) | Porous metal rod | |
| EP3222234B1 (en) | Porous tantalum metal hollow screw | |
| CN112206355B (en) | Profiling artificial bone and preparation method thereof | |
| CN118664923A (en) | Carbon fiber composite material chest rib integrated artificial bone and preparation method thereof | |
| CN118845310A (en) | An artificial skull made of porous carbon fiber composite material and a preparation method thereof | |
| CN101474425A (en) | Artificial metal spongy bone and method for producing the same |
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 |