CN116553930B - Preparation method of super-structure glassy carbon material, super-structure glassy carbon material and application - Google Patents
Preparation method of super-structure glassy carbon material, super-structure glassy carbon material and application Download PDFInfo
- Publication number
- CN116553930B CN116553930B CN202310474006.1A CN202310474006A CN116553930B CN 116553930 B CN116553930 B CN 116553930B CN 202310474006 A CN202310474006 A CN 202310474006A CN 116553930 B CN116553930 B CN 116553930B
- Authority
- CN
- China
- Prior art keywords
- super
- carbon
- carbon material
- printing
- glassy carbon
- 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
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 97
- 229910021397 glassy carbon Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 56
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 56
- 239000011521 glass Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 25
- 238000010146 3D printing Methods 0.000 claims description 22
- 238000007639 printing Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 11
- 238000000016 photochemical curing Methods 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000017 hydrogel Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000002079 double walled nanotube Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 230000017423 tissue regeneration Effects 0.000 claims description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 1
- 230000003014 reinforcing effect Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000003111 delayed effect Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000002002 slurry Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000002153 silicon-carbon composite material Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 206010052428 Wound Diseases 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005289 physical deposition Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 230000008467 tissue growth Effects 0.000 description 1
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
- C04B35/515—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
- C04B35/52—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 carbon, e.g. 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
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/42—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix
- A61L27/422—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having an inorganic matrix of carbon
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- 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
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
-
- 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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63448—Polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63452—Polyepoxides
-
- 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
-
- 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
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dermatology (AREA)
- Epidemiology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Medicinal Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a super-structure glassy carbon material, the super-structure glassy carbon material and application thereof. According to the invention, the carbon nano tube is added into the preparation raw material of the super-structure glass carbon material, the high polymer material is used as the main body of the carbon-based material, the carbon nano tube is used as the reinforcing phase, the mechanical property of the carbon-based material is reinforced by utilizing the second phase reinforcing principle of the carbon nano tube, and the surface biocompatibility of the carbon-based material is not influenced; the excellent reinforcing performance of the carbon nano tube is utilized to reinforce the performance of the super-structure glassy carbon material, the carbon nano tube is dispersed in the carbon-based material matrix to play a stable second phase reinforcing role, the dislocation development of the super-structure glassy carbon material can be effectively delayed, the strength and toughness of the porous carbon-based material are greatly improved, and the production process is simple and easy to realize mass production.
Description
Technical Field
The invention relates to the technical field of porous materials, in particular to a preparation method of a super-structure glassy carbon material, the super-structure glassy carbon material and application of the super-structure glassy carbon material.
Background
Carbon-based materials are widely applied to various products in modern life in various forms such as carbon fiber, activated carbon, graphene, glassy carbon and the like due to stable chemical properties, wide sources and high mechanical properties. The glassy carbon is often obtained by carbonizing phenolic resin, furan resin, sucrose, cellulose, polyvinylidene chloride and the like. The fracture morphology and structural characteristics of the glass carbon are similar to those of glass, and the glass carbon has the characteristics of air impermeability, low specific surface area, various identity and the like, has good biocompatibility, and is widely applied to the fields of new energy and biomedical materials; the glassy carbon has high strength but poor toughness, and in particular, the porous glassy carbon has poor impact resistance.
The structure of porous materials may exceed the properties, texture, and exhibit unique properties, such unique structure being referred to as a superstructure. At present, the super-structure material is mostly prepared by adopting 3D printing, the 3D printing technology belongs to a top-down preparation strategy, and compared with a foaming method, a space occupation method, a nano self-assembly method and the like, the super-structure material has the advantages of controllable structure, mass production, high repeatability, wide material use and the like. The 3D printing super-structure glass carbon material has good development prospect in the field of tissue repair and the field of new energy. However, the existing glass carbon material prepared by 3D printing has the disadvantages of high mechanical property, large brittleness, poor toughness, easy breaking under the impact of external force, failure and fracture in the movement process of a patient after being implanted as a bone tissue repair material, secondary wound and the like.
The chinese patent publication No. CN110649236a discloses a porous silicon-carbon composite material and a method for preparing the same, the porous silicon-carbon composite material is formed by bonding a silicon-based material and a carbon-based material, wherein the silicon-based material comprises silicon, silicon oxide and silicate, the silicate is dispersed in a silicon oxide substrate, the carbon-based material comprises a carbon material and an amorphous carbon coating material, the carbon material and the silicon-based material are contacted with each other and bonded together to form a porous structure, and the amorphous carbon coating material coats the surface of the porous structure; provided that the mass percentage of silicate is 5-30 percent based on the total mass of the porous silicon-carbon composite material of 1-00 percent. The porous silicon-carbon composite material has high specific capacity, high first coulombic efficiency, and excellent cycle performance and rate capability. In addition, the preparation method is simple, and the method is suitable for industrialized mass production of the silicon-carbon composite material for the lithium ion battery.
The chinese patent publication No. CN115403390a discloses a method for preparing a porous carbon skeleton by photo-curing 3D printing using a high-solid content/low-transmittance carbon-based slurry, the physical deposition and low transmittance of particles in the high-solid content slurry limit the application of photo-curing 3D printing in the preparation of carbon-based materials, the invention uses a high-solid content/low-transmittance carbon-based slurry, according to the characteristics of the slurry, the invention provides a photocuring 3D printing preparation method and device for the slurry, the slurry is stirred through an automatic filler system to avoid physical deposition of particles in the slurry in a long-time printing process, and then rotary scrapers are added on two sides of a slurry tank to avoid deposition and adhesion of the slurry and a release film in the printing process, and meanwhile, the light transmittance between the slurry of the current curing layer and a UV LED light source is improved. In addition, the method can improve the light intensity of the UVLED light source and prolong the optimal technological parameters of the exposure time by reducing the curing thickness of each layer, can also improve the problem of the reduction of the transmittance of the slurry, and finally achieves the aim of preparing the carbon-based skeleton with controllable structure.
The Chinese patent document with the publication number of CN113998681A discloses a preparation method for preparing a carbon nano tube-carbon composite foam material by 3D printing and application thereof, relates to the technical field of nano materials, and in particular relates to a preparation method for preparing a carbon nano tube-carbon composite foam material by 3D printing and application thereof. And carbonizing the 3D printed foam structure serving as a template at high temperature under the protection of inert gas to form a loose and porous carbon skeleton, and depositing carbon nano tubes on the carbon skeleton by using a chemical vapor deposition method to form the carbon nano tube-carbon composite porous foam material. The invention prepares a composite foam structure with a porous carbon skeleton coated by carbon nano tubes by a 3D printing and chemical vapor deposition method, and the three-dimensional carbon nano tube material has a unique cross-linked structure and high porosity, so that the composite material has good elasticity and adsorption performance.
In the technical solutions disclosed in the above patents, although a carbon-based material having high density and small carbonization shrinkage deformation can be obtained, a significant improvement effect is not achieved in improving the strength and toughness of the carbon-based material.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the preparation method of the super-structure glass carbon material can prepare the super-structure glass carbon material with high strength and high toughness.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a super-structure glass carbon material comprises the steps of adding carbon nano tubes into a preparation raw material of a porous carbon-based material, and printing the super-structure glass carbon material by a 3D printing technology.
Further is: the method comprises the following steps:
Step one, designing and constructing a three-dimensional digital model of the super-structure glass carbon material;
Step two, taking a high molecular polymer containing carbon nano tubes as a printing material to perform 3D printing to obtain the super-structure bracket;
and thirdly, heating the super-structure support to 400-3000 ℃ in an anaerobic or low-oxygen environment to obtain the super-structure glass carbon material.
Further is: in the second step, the high molecular polymer is a mixture of acrylic-based photosensitive resin, epoxy-based photosensitive resin, photo-curing hydrogel and carbon nano tubes.
Further is: in the second step, the content of the carbon nano tube is 0.01-10% of the total weight of the high molecular polymer.
Further is: the carbon nanotube is at least one of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube.
Further is: the carbon nanotubes are hydroxylated carbon nanotubes and carboxylated carbon nanotubes, or are modified by silane coupling agent or titanate.
Further is: in the second step, the method further comprises a surfactant or a dispersing agent added in the high-molecular polymer.
Further is: the super-structure glassy carbon material is of a porous structure, the pore wall thickness of the porous structure is less than 1mm, and the porosity is greater than 50%.
The invention also discloses the super-structure glass carbon material prepared by the preparation method of the super-structure glass carbon material.
The invention also discloses application of the super-structure glassy carbon material in the field of tissue repair and the field of new energy.
The beneficial effects of the invention are as follows:
1. According to the invention, the carbon nano tube is added into the preparation raw material of the super-structure glass carbon material, the excellent reinforcing performance of the carbon nano tube is utilized to reinforce the performance of the super-structure glass carbon material, and the carbon nano tube is dispersed in the porous carbon-based material matrix to play a stable second phase reinforcing role, so that the dislocation development of the super-structure glass carbon material can be effectively delayed, and the strength and toughness of the super-structure glass carbon material can be greatly improved;
2. According to the invention, through the characteristic that the carbon nano tube has a structure similar to that of a polymer material serving as a raw material for preparing the carbon-based material, the carbon nano tube reinforcing phase is dispersed in the carbon-based material, so that the carbon nano tube and the carbon-based material are combined with each other more efficiently to form a porous structure, the volume expansion of the carbon-based material can be effectively buffered while the strength of the carbon-based material is improved, and the stability of the carbon-based material is improved;
3. the invention uses the macromolecule material as the main body of the carbon-based material, and simultaneously uses the carbon nano tube as the reinforcing phase, and uses the second phase reinforcing principle of the carbon nano tube to strengthen the mechanical property of the carbon-based material, and meanwhile, the biocompatibility of the surface of the carbon-based material is not affected;
4. according to the invention, the process parameters for preparing the carbon-based material by 3D printing are optimized, and the heating range of the high-molecular polymer template is limited according to different types of the high-molecular polymer, so that elements such as hydrogen, nitrogen, oxygen and the like in the high-molecular polymer are cracked into small molecules or gas to escape, only pure carbon or carbon-based material taking carbon as a matrix is left, the purity of the carbon-based material is effectively improved, and the mechanical property of the carbon-based material is ensured;
5. The invention adopts the existing 3D printing technology, does not change the preparation process of the super-structure glassy carbon material excessively, and realizes the enhancement of the strength and toughness of the super-structure glassy carbon material by improving the 3D printing material and the 3D printing process parameters on the original preparation process of the super-structure glassy carbon material, and the production process is simple and easy to realize mass production;
6. the super-structure glass carbon material prepared by the invention has excellent mechanical properties, can be well applied in the biomedical field, can be used for repairing bones of patients, is low in brittleness, high in strength and strong in toughness after being implanted as a bone tissue repairing material, can not fail and break even if the stress of the patients is increased in the movement process, can effectively avoid secondary wounds of the patients caused by movement, and is beneficial to recovery of the patients;
7. The super-structure glassy carbon material prepared by the invention has controllable pores and good pore connectivity, and can effectively promote tissue growth and shorten the recovery period of patients when applied to the biomedical field.
Detailed Description
In order that the invention may be readily understood, a further description of the invention will be provided with reference to the following examples.
The invention discloses a preparation method of a super-structure glassy carbon material, which is characterized in that a carbon nano tube is added into a preparation raw material of a porous carbon-based material, and the super-structure glassy carbon material is printed by a 3D printing technology, wherein the specific preparation process comprises the following steps:
step one, a porous structure model is established by adopting 3D modeling software or a three-dimensional digital model of the super-structure glassy carbon material is established by reverse engineering of imaging data, wherein the type of a porous structure in the super-structure glassy carbon material is an open pore structure, a closed pore structure or a mixture of the open pore structure and the closed pore structure, the pore wall thickness of the porous structure is less than 1mm, the porosity is more than 50%, and the preferable porosity is 50% -90%.
Printing the super-structure bracket by using a high polymer containing carbon nano tubes as a printing material through a 3D printing technology, wherein the high polymer in the step is a mixture of acrylic photosensitive resin, epoxy photosensitive resin, photo-curing hydrogel and carbon nano tubes, and the 3D printing technology adopted in the step comprises a photo-curing 3D printing technology such as LCD/DLP/TPP or the derivative preparation technology thereof;
the content of the carbon nano tube adopted in the step is 0.01-10% of the total weight of the high molecular polymer, and the carbon nano tube is used as a reinforcing phase, if the content is lower than 0.01%, the problem that the reinforcing effect cannot be achieved possibly occurs, and if the content is higher than 10%, the problem that the carbon nano tube cannot be dispersed occurs possibly, so the content of the carbon nano tube is limited in the range;
the specific structural form of the carbon nanotube is single-wall carbon nanotube, double-wall carbon nanotube or multiwall carbon nanotube, the enhancement effect that single-wall carbon nanotube and double-wall carbon nanotube can play is better, but its cost is also higher too, can choose according to the actual demand;
The carbon nanotubes may preferably be modified carbon nanotubes, or preferably hydroxylated carbon nanotubes, carboxylated carbon nanotubes, or preferably carbon nanotubes modified with a silane coupling agent or titanate; the hydroxylated carbon nano tube and the carboxylated carbon nano tube have good dispersibility, and the carbon nano tube modified by the silane coupling agent or the titanate can reduce the surface tension of the material and improve the dispersibility of the carbon nano tube;
In this step, a surfactant or a dispersant may be added to the printing material, and the surface tension can be reduced and the dispersibility of the carbon nanotubes can be improved by the above additives.
And thirdly, heating the printed super-structure support to 400-3000 ℃ in an anaerobic or low-oxygen environment by adopting an oven, a muffle furnace or a tube furnace, wherein the super-structure glass carbon material is prepared by adopting the super-structure support.
Example 1
According to the preparation steps of the invention, the mixture of acrylic-based photosensitive resin, epoxy-based photosensitive resin, photo-curing hydrogel and carbon nano tubes is used as the raw material for preparing the super-structure glassy carbon material, the content of the carbon nano tubes in the printing material accounts for 0.1% of the total weight of the printing material, the mechanical properties of the finally obtained super-structure glassy carbon material are detected, and the strength of the super-structure glassy carbon material is measured to be 33.54+/-0.34 MPa.
Example 2
According to the preparation steps of the invention, the mixture of acrylic-based photosensitive resin, epoxy-based photosensitive resin, photo-curing hydrogel and carbon nano tubes is adopted as the raw material for preparing the super-structure glassy carbon material, and the surfactant is added into the printing material, wherein the content of the carbon nano tubes in the printing material accounts for 0.5% of the total weight of the printing material, the mechanical properties of the finally obtained super-structure glassy carbon material are detected, and the strength of the super-structure glassy carbon material is 54.43 +/-1.32 MPa.
Example 3
According to the preparation steps of the invention, the mixture of acrylic-based photosensitive resin, epoxy-based photosensitive resin, photo-curing hydrogel and carbon nano tubes is used as a raw material for preparing the super-structure glassy carbon material, a dispersing agent is added into a printing material, the content of the carbon nano tubes in the printing material accounts for 1% of the total weight of the printing material, the mechanical properties of the finally obtained super-structure glassy carbon material are detected, and the strength of the super-structure glassy carbon material is 66.43 +/-1.35 MPa.
Comparative example
According to the preparation steps of the invention, acrylic-based photosensitive resin and epoxy-based photosensitive resin are adopted as raw materials for preparing the super-structure glassy carbon material, no carbon nano tube is added in the raw materials, and the mechanical properties of the finally obtained super-structure glassy carbon material are detected, so that the strength of the super-structure glassy carbon material is 22.15+/-0.13 MPa.
By comparing the data of the above examples 1 to 3 with the data of the comparative example, it can be obviously demonstrated that the addition of the carbon nanotubes in the preparation of the super-structure glassy carbon material has a significant effect on the strength of the super-structure glassy carbon material, and the improvement range of the super-structure glassy carbon material is in a direct proportion relation with the content of the added carbon nanotubes in the range of 0.01-10% of the content of the carbon nanotubes, so that the mechanical properties of the super-structure glassy carbon material can be effectively improved by adding the carbon nanotubes.
Claims (8)
1. The preparation method of the super-structure glass carbon material is characterized by comprising the following steps of: printing a super-structure glass carbon material by using a high molecular polymer containing carbon nano tubes as a printing material and a 3D printing technology; the high molecular polymer is a mixture of acrylic acid-based photosensitive resin, epoxy-based photosensitive resin, photo-curing hydrogel and carbon nano tubes, and the content of the carbon nano tubes is 0.01-10% of the total weight of the high molecular polymer.
2. The method for preparing the super-structure glassy carbon material of claim 1, wherein the method comprises the following steps: the method comprises the following steps:
Step one, designing and constructing a three-dimensional digital model of the super-structure glass carbon material;
Step two, taking a high molecular polymer containing carbon nano tubes as a printing material to perform 3D printing to obtain the super-structure bracket;
and thirdly, heating the super-structure support to 400-3000 ℃ in an anaerobic or low-oxygen environment to obtain the super-structure glass carbon material.
3. The method for preparing the super-structure glassy carbon material according to claim 2, wherein the method comprises the following steps: the carbon nanotube is at least one of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube.
4. The method for preparing the super-structure glassy carbon material according to claim 2, wherein the method comprises the following steps: the carbon nanotubes are hydroxylated carbon nanotubes or carboxylated carbon nanotubes.
5. The method for preparing the super-structure glassy carbon material according to claim 2, wherein the method comprises the following steps: in the second step, the method further comprises a surfactant or a dispersing agent added in the high-molecular polymer.
6. The method for preparing the super-structure glassy carbon material according to claim 2, wherein the method comprises the following steps: the super-structure glassy carbon material is of a porous structure, the pore wall thickness of the porous structure is less than 1mm, and the porosity is greater than 50%.
7. A super-structure vitreous carbon material produced by the method for producing a super-structure vitreous carbon material according to any one of claims 1 to 6.
8. The use of the super structure glass carbon material as defined in claim 7 in the field of tissue repair and in the field of new energy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310474006.1A CN116553930B (en) | 2023-04-28 | 2023-04-28 | Preparation method of super-structure glassy carbon material, super-structure glassy carbon material and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310474006.1A CN116553930B (en) | 2023-04-28 | 2023-04-28 | Preparation method of super-structure glassy carbon material, super-structure glassy carbon material and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116553930A CN116553930A (en) | 2023-08-08 |
| CN116553930B true CN116553930B (en) | 2024-11-19 |
Family
ID=87495787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310474006.1A Active CN116553930B (en) | 2023-04-28 | 2023-04-28 | Preparation method of super-structure glassy carbon material, super-structure glassy carbon material and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116553930B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119591086A (en) * | 2024-10-22 | 2025-03-11 | 四川大学华西医院 | Super-structure glassy carbon material and application thereof |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3780912T2 (en) * | 1986-11-10 | 1993-03-18 | Kao Corp | COMPOSITE MATERIAL FROM GLASS-LIKE CARBON AND METHOD FOR THE PRODUCTION THEREOF. |
| US5431821A (en) * | 1992-02-07 | 1995-07-11 | The Ohio State University | Glassy carbon in separation processes |
| WO2005028174A2 (en) * | 2003-06-16 | 2005-03-31 | William Marsh Rice University | Fabrication of carbon nanotube reinforced epoxy polymer composites using functionalized carbon nanotubes |
| KR20050087376A (en) * | 2004-02-26 | 2005-08-31 | 삼성에스디아이 주식회사 | Emitter composition of flat panel display and carbon emitter using the same |
| JP4642392B2 (en) * | 2004-06-30 | 2011-03-02 | 株式会社山本製作所 | Method for producing porous carbon material, porous carbon material, and sliding component using the porous carbon material |
| WO2006121155A1 (en) * | 2005-05-12 | 2006-11-16 | Japan Science And Technology Agency | Carbon nanotube composition, process for producing the same, array and electronic device |
| KR101034346B1 (en) * | 2006-12-22 | 2011-05-16 | 주식회사 엘지화학 | Photosensitive resin composition of heat resistance improvement through carbon nanotube |
| CN101798076B (en) * | 2010-04-02 | 2012-02-29 | 上海交通大学 | Preparation method of composite sheet based on glassy carbon and carbon nanotubes |
| EP3186054B1 (en) * | 2014-08-27 | 2020-08-12 | The Exone Company | Process for making carbon articles by three dimensional printing |
| US9926427B2 (en) * | 2015-12-10 | 2018-03-27 | Nanotek Instruments, Inc. | Chemical-free production of graphene-reinforced polymer matrix composites |
| US10821654B2 (en) * | 2017-10-12 | 2020-11-03 | Clemson University Research Foundation | Carbon and carbide origami |
| CN110903099A (en) * | 2018-09-13 | 2020-03-24 | 中国科学院上海硅酸盐研究所 | Porous body composed of one-dimensional nano materials in oriented arrangement and preparation method thereof |
| KR20230004858A (en) * | 2020-05-01 | 2023-01-06 | 카본 세라믹스 컴퍼니, 엘엘씨 | Glassy Carbon Compositions, Multilayer Laminates, and 3-D Printed Articles |
| CN112209733B (en) * | 2020-10-20 | 2023-10-13 | 南京信息工程大学 | A carbon nanotube-based broadband electromagnetic wave absorbing honeycomb metamaterial and its preparation method |
| CN115403390B (en) * | 2022-09-20 | 2023-03-31 | 吉林大学 | Method for preparing porous carbon skeleton by photocuring 3D printing through high-solid-content/low-transmittance carbon-based slurry |
-
2023
- 2023-04-28 CN CN202310474006.1A patent/CN116553930B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 3D printable resin/carbon nanotube composites for wearable strain sensors: Enhancing mechanical and electrical properties;Poompiew N et al.;JOURNAL OF SCIENCE-ADVANCED MATERIALS AND DEVICES;20230630;第8卷(第2期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116553930A (en) | 2023-08-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Luo et al. | Fabrication of flexible, ultra-strong, and highly conductive bacterial cellulose-based paper by engineering dispersion of graphene nanosheets | |
| US20190077667A1 (en) | High-strength network structured nano-carrier material and preparation method and application thereof | |
| CN108329046B (en) | Preparation method of carbon aerogel heat insulation composite material | |
| Illa et al. | Bacterial cellulose-derived carbon nanofibers as anode for lithium-ion batteries | |
| CN116553930B (en) | Preparation method of super-structure glassy carbon material, super-structure glassy carbon material and application | |
| US20190322826A1 (en) | Method for preparing carbon nanotube/polymer composite | |
| Shi et al. | Synthesis, structure, and applications of lignin-based carbon materials: a review | |
| CN110143591A (en) | A kind of composite carbon airgel with high specific surface area and preparation method thereof | |
| CN113663611A (en) | A kind of high temperature resistant composite nanofiber aerogel material and preparation method thereof | |
| Li et al. | Hydrothermally synthesized N and S co-doped mesoporous carbon microspheres from poplar powder for supercapacitors with enhanced performance | |
| Hasan et al. | Recent advances in aerogel materials from electrospun nanofibers: a review | |
| CN108264038A (en) | A kind of method that simple and direct batch prepares large scale carbon nano tube/graphene hybrid | |
| CN115557800A (en) | A method for preparing silicon carbide-based composite materials by homogeneous ceramicization of porous carbon | |
| CN117117136A (en) | A composite graphite negative electrode material and its preparation method and application | |
| Hao et al. | Ionothermal synthesis of fiber-reinforced carbon aerogel composites from fructose with high mechanical and thermal insulation properties | |
| CN115196988B (en) | A kind of nitride nanobelt modified carbon/carbon composite material and preparation method thereof | |
| CN103626155B (en) | An efficient and environmentally friendly method for preparing carbon nanofibers | |
| CN108083254A (en) | Using lignin/phenol/furfural as carbon aerogels of presoma and preparation method thereof | |
| CN109679295B (en) | Method for enhancing composite performance of carbon fiber and resin matrix | |
| CN116143519A (en) | Preparation method of large-size medical glassy carbon block material | |
| Chen et al. | Inexhaustible natural celluloses in advanced Li–S batteries: a review | |
| CN108863434A (en) | A kind of high-content carbon nanotube enhancing PRECURSOR-DERIVED CERAMICS composite material and preparation method | |
| CN111285349B (en) | A kind of highly graphitized boron-doped carbon nanocapsule and preparation method thereof | |
| CN109103026B (en) | Preparation method of fluorine and nitrogen co-doped bacterial cellulose derived carbon nanofiber membrane | |
| CN109179372B (en) | High-performance biological cellulose carbon aerogel and preparation method and application thereof |
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 |