Superstructural glassy carbon, preparation method therefor and use thereof

Abstract

A superstructural glassy carbon, a preparation method therefor and a use thereof. Firstly, provided is a superstructural glassy carbon having a stable structure with uniformly distributed anisotropic stress. Secondly, also provided are a preparation method and a use of the superstructural glassy carbon, and a bone repair material obtained on the basis of the superstructural glassy carbon.

Description

Superstructured glassy carbon, its preparation methods and applications

[0001] Priority application

[0002] This application claims priority to Chinese invention patent application No. CN202411029816.7, filed on July 30, 2024, entitled “A superstructured glassy carbon and its preparation method”, and Chinese invention patent application No. CN202411479935.2, filed on October 22, 2024, entitled “A superstructured glassy carbon and its preparation method and application”, both of which are incorporated herein by reference in their entirety. Technical Field

[0003] This invention belongs to the field of materials preparation technology, specifically relating to a superstructured glassy carbon, its preparation method, and its applications. Background Technology

[0004] Glassy carbon is an amorphous carbon that combines some properties of glass, ceramics, and graphite, including high hardness, low density, low electrical resistance, high temperature resistance, and corrosion resistance. It also exhibits good biocompatibility and does not produce masking artifacts in imaging examinations, demonstrating great potential in fields such as energy, aerospace, and biomedicine. Currently, glassy carbon scaffolds are typically prepared by high-temperature pyrolysis of polymer precursors under vacuum or inert gas conditions. However, due to significant volume shrinkage during the preparation process, problems such as severe deformation, structural inhomogeneity, and microscopic defects are frequently encountered, affecting mechanical properties and hindering the precise fabrication of high-strength glassy carbon scaffolds. This severely limits the development and application of glassy carbon scaffolds in various fields.

[0005] Patent CN116143519A discloses a method for preparing large-size medical-grade glassy carbon bulk materials. However, this process requires nanodiamonds as raw material, which are expensive, and the process is complex, requiring high temperature and high pressure conditions. Patent CN116495720A discloses a network-like glassy carbon and its preparation method. However, the three-dimensional network structure glassy carbon prepared by this method has insufficient mechanical properties, making it difficult to meet the needs of many practical applications.

[0006] Existing glassy carbon scaffolds suffer from low mechanical properties, difficulty in precisely controlling their shape and dimensions, and insufficient functionality. Therefore, it is necessary to propose new methods to address these issues in existing technologies, enabling the precise fabrication of high-strength functional glassy carbon scaffolds, thereby promoting the application of glassy carbon scaffold materials in multiple fields. Summary of the Invention

[0007] The purpose of this invention is to provide a superstructured glassy carbon, its preparation method and application, which partially solves or alleviates the above-mentioned deficiencies in the prior art. The specific technical solution adopted by this invention is as follows.

[0008] A first aspect of the present invention is to provide a superstructured glassy carbon.

[0009] A superstructured glassy carbon has a stable structure with uniform stress distribution in all directions; the superstructured glassy carbon uses a unit cell with a three-period minimal surface as the smallest repeating unit; the unit cell with the three-period minimal surface includes a diamond or diamond-like structure; the superstructured glassy carbon is obtained by pyrolyzing a polymer scaffold with the same structural unit and then proportionally reducing its size and carbonizing it.

[0010] Furthermore, the three-period minimum surface includes features satisfying the following digital model:

[0011] (1)Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0, (2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0012] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0013] Or (4)2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3.

[0014] Furthermore, the average surface curvature of the three-period minimal surface structure ranges from -0.135 to 0.137.

[0015] In some preferred embodiments, the average surface curvature of the three-period minimal surface structure is 0.

[0016] Furthermore, the pyrolysis conditions include vacuum high-temperature pyrolysis or high-temperature atmospheric pressure pyrolysis under an inert atmosphere.

[0017] In some preferred embodiments, the inert gas comprises one or more gases selected from the group consisting of nitrogen, argon, helium, and neon.

[0018] In some preferred embodiments, the pyrolysis includes vacuum high-temperature pyrolysis or high-temperature atmospheric pressure pyrolysis. The operation can be carried out by first raising the temperature from room temperature to 250°C, then raising it to 350°C, holding it at that temperature for a period of time, and then raising the temperature by 1 degree Celsius every 2 minutes to 700-3000°C, and then allowing it to cool naturally.

[0019] Furthermore, the polymer includes polymers with high carbon content.

[0020] Preferably, the high-carbon content polymer comprises, from the following: furan resin, furfuryl alcohol resin, furfuryl ketone resin, phenolic resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyetheretherketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylethersulfone, polyethylene naphthalate, polyphenylene oxide ... The material selected from the group consisting of amines, polyacetylene, poly(p-phenylene), polyphthalimide, poly(phenyleneacetylene), polylactide, polychloroprene, cyanopolyacrylate, polynaphthaleneacetylene, poly(p-xylene), polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinylacetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polychlorotrifluoroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly(p-phenylene sulfone), polyphenylene oxide, polybenzoxazole, polypiperidine, polyvinyl alcohol acetal, polybenzothiazole and polyvinylpyrrolidone.

[0021] A second aspect of the present invention is to provide the application of the above-described superstructured glassy carbon.

[0022] The above-mentioned application of superstructured glassy carbon in the preparation of large-size materials, wherein the dimensions of the large-size materials range from millimeters to decimeters. Preferably, the dimensions of the large-size materials include millimeter, centimeter, or decimeter scales.

[0023] In some preferred embodiments, the size of the large-size glassy carbon is greater than 5 cm, but this is not a limitation.

[0024] The above-mentioned application of superstructured glassy carbon in the preparation of microscopically complex structural materials, wherein the dimensions of the microscopically complex structural materials range from nanometer to millimeter. Preferably, the dimensions of the microscopically complex structural materials include nanometer, micrometer, or millimeter scales.

[0025] Furthermore, the precision of the microscopic complex structure material is from the nanometer to the micrometer level. The "precision" refers to the minimum linewidth of the scaffold structure printed using 3D printing methods.

[0026] Furthermore, the large-size material includes large-size glassy carbon material and composite materials made by splicing large-size glassy carbon with other materials; the other materials include metal materials, polymer materials, ceramic materials, glass materials or semiconductor materials.

[0027] The above-mentioned superstructured glassy carbon has applications in the preparation of energy materials or aerospace materials.

[0028] A third aspect of the present invention is to provide a novel bone-inducing material.

[0029] A bone-inducing material is prepared from a surface-modified glassy carbon material; the glassy carbon material has a stable structure with uniform anisotropic stress distribution; the superstructured glassy carbon uses a three-period minimal surface unit cell as the smallest repeating unit; the three-period minimal surface unit cell includes a diamond or diamond-like structure; the glassy carbon material is obtained by pyrolyzing a polymer scaffold with the same structure and then proportionally scaling it down and carbonizing it; the surface-modified glassy carbon material has a coral-like or coral-like morphology, the coral-like or coral-like morphology including straight lines, arcs, branched structures, rings or quasi-ring structures and / or beaded morphologies formed by the self-assembly of nanoparticles; the coral-like or coral-like morphology also includes a non-uniform porous structure.

[0030] Furthermore, the means of altering the surface morphology include solvent treatment, molten salt etching, CO2 etching, or plasma treatment.

[0031] Furthermore, the means of altering surface properties also include introducing functional groups, proteins, peptides, and / or small molecule drugs onto the surface; preferably, the functional groups include carbonyl, hydroxyl, carboxyl, epoxy, vinyl, alkoxy, mercapto, amino, azide, and / or alkyne; but are not limited thereto.

[0032] Furthermore, the three-period minimum surface includes features satisfying the following digital model:

[0033] (1)Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0, (2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0034] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0035] Or (4)2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3.

[0036] Furthermore, the average surface curvature of the three-period minimal surface structure ranges from -0.135 to 0.137.

[0037] Furthermore, the polymeric material includes high-carbon-content polymeric materials; the high-carbon-content polymeric materials comprise materials derived from furan resin, furfuryl alcohol resin, furfuryl ketone resin, phenolic resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyetheretherketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylene sulfone, and polynaphthalene dimethyl ether. The material selected from the group consisting of ethylene glycol formate, polyaniline, polyacetylene, poly(p-phenylene), polyphthalimide, poly(phenyleneacetylene), polylactide, polychloroprene, cyanopolyacrylate, polynaphthaleneacetylene, poly(p-xylene), polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinylacetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polychlorotrifluoroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly(p-phenylene sulfone), polyphenylene oxide, polybenzoxazole, polypiperidine, polyvinyl alcohol acetal, polybenzothiazole and polyvinylpyrrolidone.

[0038] A fourth aspect of the present invention is to provide a method for preparing a superstructured glassy carbon and a novel bone-inducing material.

[0039] A method for preparing superstructured glassy carbon, the method comprising the following steps:

[0040] S01: Design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model including

[0041] (1)Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0,

[0042] (2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0043] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0044] Or (4)2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3;

[0045] S02: Using the three-dimensional digital model designed and constructed in S01 as a template for 3D printing, the materials used in the 3D printing include polymers, to obtain a polymer scaffold.

[0046] S03: The polymer scaffold obtained in S02 is heated to 700-3000℃ under normal pressure in a vacuum or inert gas environment to obtain the superstructured glassy carbon.

[0047] Furthermore, the 3D printing used in S02 includes liquid crystal display printing technology, digital light processing printing technology, two-photon printing technology, extrusion printing technology, or powder laser sintering printing technology.

[0048] Furthermore, the sintering equipment used in the pyrolysis process includes equipment selected from muffle furnaces, tube furnaces, or hot isostatic pressing furnaces.

[0049] In some preferred embodiments, the bond angle of the three-dimensional digital model is 109.5°. The scaffold can be fabricated using direct or indirect 3D printing.

[0050] Direct printing refers to directly printing a specific structure using 3D printing technology.

[0051] Indirect printing involves first printing a mold, and then using a mold guide method to indirectly fabricate a specific structure. The specific operation is as follows:

[0052] S01: Design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model including

[0053] (1)Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0, (2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0054] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0055] Or (4)2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3;

[0056] S02: Construct a solid model with the same length, width, and height as the three-dimensional digital model, subtract the structure of the three-dimensional digital model from the solid model to obtain a guide model, and print the guide model using 3D printing technology;

[0057] S03: Inject polymer material into the guide mold, and then burn the guide mold at high temperature to obtain a scaffold structure made of polymer.

[0058] S04: Further pyrolysis of the scaffold structure yields the superstructured glassy carbon.

[0059] A method for preparing a bone-inducing material includes the following steps:

[0060] S01: Design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model including

[0061] (1)Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0,

[0062] (2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0063] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0064] Or (4)2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3;

[0065] S02: Using the three-dimensional digital model designed and constructed in S01 as a template for 3D printing, the materials used in the 3D printing include polymers, to obtain a polymer scaffold.

[0066] S03: The polymer scaffold is subjected to surface modification treatment, the surface modification treatment method including solvent treatment or molten salt etching treatment; the surface of the polymer scaffold after surface modification has a coral-like or coral-like morphology, the coral-like or coral-like morphology includes straight lines, arcs, branched structures, ring or ring-like structures and / or beaded morphology formed by the self-assembly of nanoparticles; the coral-like or coral-like morphology also includes a non-uniform porous structure;

[0067] S04: The surface-modified polymer scaffold obtained in S03 is pyrolyzed, and the pyrolyzed surface-modified polymer scaffold is proportionally shrunk and carbonized to obtain the osteoinductive material.

[0068] Alternatively, the preparation method of the bone-inducing material may also employ the following steps:

[0069] S01: Design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model including

[0070] (1)Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0,

[0071] (2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0072] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0073] Or (4)2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3;

[0074] S02: Using the three-dimensional digital model designed and constructed in S01 as a template for 3D printing, the materials used in the 3D printing include polymers, to obtain a polymer scaffold.

[0075] S03: The polymer scaffold obtained from S02 is pyrolyzed, and the pyrolyzed polymer scaffold is proportionally reduced and carbonized to obtain glassy carbon material.

[0076] S04: The glassy carbon material is surface modified to obtain the bone-inducing material. The surface modification method includes CO2 etching or plasma treatment. The surface-modified glassy carbon material has a coral-like or coral-like morphology. The coral-like or coral-like morphology includes straight lines, arcs, branched structures, rings or ring-like structures and / or beaded morphologies formed by the self-assembly of nanoparticles. The coral-like or coral-like morphology also includes a non-uniform porous structure.

[0077] In some preferred embodiments, the means of molten salt etching include treatment at high temperatures with one or more of sodium chloride, potassium chloride, magnesium chloride, sodium fluoride, calcium fluoride, lithium chloride and / or calcium chloride, but are not limited thereto.

[0078] In some preferred embodiments, the solvent treatment involves placing the polymer scaffold in a solution at room temperature for self-assembly. When the scaffold, made of an amphiphilic polymer, is immersed in water, the amphiphilic nature of the polymer causes self-assembly to occur on the surface of the scaffold, forming a micelle-like structure deposited on the surface. This is followed by sintering, ultimately forming the coral-like or coral-like morphology.

[0079] Furthermore, the 3D printing used includes liquid crystal display printing technology, digital light processing printing technology, two-photon printing technology, extrusion printing technology, or powder laser sintering printing technology; or, pyrolysis is performed by heating at atmospheric pressure in an inert gas, said inert gas comprising one or more gases selected from the group consisting of nitrogen, argon, helium, and neon.

[0080] Furthermore, methods for altering surface morphology also include introducing functional groups, proteins, peptides, and / or small molecule drugs onto the surface.

[0081] The application of the aforementioned superstructured glassy carbon or the aforementioned osteoinductive materials in the preparation of bone repair materials.

[0082] A fifth aspect of the present invention may also provide a support structure.

[0083] A porous scaffold structure has a stable structure with uniform stress distribution in all directions; the porous scaffold structure uses a unit cell with a three-period minimal surface as the smallest repeating unit; the unit cell with the three-period minimal surface includes a diamond or diamond-like structure; the material constituting the porous scaffold structure is a polymer.

[0084] Furthermore, the three-dimensional digital model includes:

[0085] (1)Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0,

[0086] (2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0087] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0088] Or (4)2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3.

[0089] A superstructured glassy carbon, wherein the superstructured glassy carbon is obtained by proportionally shrinking and carbonizing the above-mentioned porous support structure after pyrolysis; the pyrolysis conditions include vacuum high-temperature pyrolysis or high-temperature atmospheric pressure pyrolysis under an inert atmosphere.

[0090] In some preferred embodiments, the porous support structure or the superstructured glassy carbon has a uniform porous structure with a pore wall thickness of less than 3 mm, but this is not a limitation.

[0091] In some other preferred embodiments, the porous support structure or the superstructured glassy carbon has a non-uniform porous structure.

[0092] Beneficial technical effects:

[0093] This invention aims to resolve the contradiction between the shape, size, and mechanical properties of glassy carbon materials. First, by designing a stress-uniform structure, a superstructured glassy carbon that balances mechanical and shape design is prepared, as detailed below.

[0094] (1) This invention utilizes the excellent behavior of uniform stress distribution during pyrolysis shrinkage of the three-period minimal curved surface superstructure design to prepare large-size, pyrolysis deformation-controllable, structurally uniform, and micro-defect-free superstructure glassy carbon.

[0095] (2) This invention utilizes existing 3D printing technology without significantly altering the existing glassy carbon scaffold preparation and pyrolysis processes, nor requiring any special processes. It achieves this solely through a unique three-period minimal surface lattice design. Therefore, the production process of this superstructured glassy carbon material is simple and easy to mass-produce.

[0096] (3) The superstructured glassy carbon prepared by this invention can be further prepared into large-size products (from millimeter to decimeter) or complex micro-sized products (from nanometer to micrometer). It also has excellent mechanical properties and low density, low resistance, high temperature resistance and corrosion resistance, and can be well applied in energy, aerospace, biomedicine and even art decoration.

[0097] (4) The superstructured glassy carbon prepared by this invention can be modularly divided to realize the assembly design, and can be modularly assembled with other metals, polymers and other materials to form composite materials.

[0098] Furthermore, this invention innovatively proposes that carbon materials can have osteoinductive effects, and proves that osteoinductive materials prepared from glassy carbon materials as a matrix have the ability to accelerate bone tissue repair and regeneration, as detailed below.

[0099] This invention successfully prepared a bone-inducing material by further surface modification of the prepared superstructured glassy carbon or by surface modification of the polymer scaffold before pyrolysis of the superstructured glassy carbon. This bone-inducing material has a unique coral-like or coral-like morphology, which can induce accelerated bone tissue repair and regeneration. Furthermore, this bone-inducing material also possesses excellent mechanical properties, providing good support during bone repair, and can be customized into unique shapes according to actual needs, thus showing broad application prospects in the field of medical devices. Attached Figure Description

[0100] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. In all the drawings, similar elements or parts are generally identified by similar reference numerals. The elements or parts in the drawings are not necessarily drawn to scale. Obviously, the drawings described below are some embodiments of the present invention, and those skilled in the art can obtain other drawings based on these drawings without any creative effort.

[0101] Figure 1 is a model diagram of a three-period minimal surface lattice structure (scaffold structure) provided in one embodiment of the present invention;

[0102] Figure 2 is a schematic diagram of the three-period minimal curved surface lattice structure provided in one embodiment of the present invention in the XYZ directions;

[0103] Figure 3 is a photograph of a centimeter-scale superstructured glassy carbon prepared according to one embodiment of the present invention;

[0104] Figure 4 is a verification diagram of the thermal shrinkage performance of ordinary structured glassy carbon prepared in one of the comparative embodiments of the present invention;

[0105] Figure 5 shows the verification that superstructured carbon of different sizes prepared by the method of the present invention has the ability to shrink proportionally (A is the proportional shrinkage of glassy carbon of different sizes after high-temperature pyrolysis under the same conditions, and B is the shrinkage rate of glassy carbon of different sizes in different directions).

[0106] Figure 6 shows a schematic diagram of large defects and deformations in glassy carbon scaffolds prepared by ordinary methods and ordinary structures (A is glassy carbon of ordinary scaffold structure, B is glassy carbon of ordinary octahedral structure, C is SEM image of defects in glassy carbon of ordinary scaffold structure, and D is SEM image of defects in glassy carbon of ordinary octahedral structure).

[0107] Figure 7 shows scanning electron microscope images of microscopic defects in different glassy carbon materials (A is the superstructured glassy carbon of the present invention, B is the ordinary structured glassy carbon, and the scale bar is 200 μm).

[0108] Figure 8 shows the microstructure and defect analysis of large-size superstructured carbon (A is a high-resolution TEM image of superstructured glassy carbon, scale bar is 5nm and 2nm, B is a cross-sectional SEM image and cross-sectional TEM image of superstructured glassy carbon, scale bar is 50μm and 100nm).

[0109] Figure 9 shows the maximum compressive strength results for different glassy carbon materials;

[0110] Figure 10 shows the excellent mechanical properties of the superstructured glassy carbon of the present invention.

[0111] Figure 11 shows the stress distribution of the three-period minimal surface lattice structure proposed in this invention through finite element analysis.

[0112] Figure 12 shows the finite element analysis of other structures (A is the finite element analysis of a common scaffolding structure, and B is the finite element analysis of a common regular octahedral structure);

[0113] Figure 13 is a schematic diagram of the complex shape of the micro-sized superstructured glassy carbon prepared in this invention (scale bars are 2 μm and 5 μm);

[0114] Figure 14 shows the maximum compressive strength and maximum strain of the micro-sized glassy carbon prepared in this invention (scale bar is 1 μm);

[0115] Figure 15 shows the elasticity test results of the micro-sized glassy carbon prepared in this invention (scale bar is 1 μm);

[0116] Figure 16 shows a TEM image of microscopic superstructured carbon (scale bar: 5 nm).

[0117] Figure 17 is a schematic diagram of the complex structure of the large-size superstructured glassy carbon prepared in this invention (scale bar is 1 cm).

[0118] Figure 18 shows the effect of the modular segmentation design of the superstructured glassy carbon prepared by the present invention;

[0119] Figure 19 is a schematic diagram of the PEEK coating on the surface of the superstructured glassy carbon obtained by the first preparation method;

[0120] Figure 20 is a schematic diagram of the composite of the superstructured glassy carbon surface obtained by the first preparation method and hydroxyapatite.

[0121] Figure 21 is a schematic diagram of the composite of the superstructured glassy carbon surface and hydroxyapatite obtained by the second preparation method.

[0122] Figure 22 is a graphic example of a coral-like or coral-like morphology in one embodiment of the present invention;

[0123] Figure 23 is a scanning electron microscope image of a glassy carbon scaffold with a surface nanostructure obtained after solvent treatment in one embodiment of the present invention (A is the modified glassy carbon prepared by the first preparation method after water immersion, B is the modified glassy carbon prepared by the second preparation method after ethanol immersion, and C is the modified glassy carbon prepared by the second preparation method after water immersion; the scale bars are 20 μm and 1 μm respectively).

[0124] Figure 24 is a scanning electron microscope image of a glassy carbon scaffold with a surface micro-nano morphology obtained by molten salt treatment according to one embodiment of the present invention (first preparation method; scale bar is 1 μm);

[0125] Figure 25 is an electron microscope image of a rough micro / nano morphology obtained by CO2 gas etching in one embodiment of the present invention (first preparation method; scale bar is 40 μm);

[0126] Figure 26 shows the verification of the surface hydrophilicity / hydrophobicity change results after plasma treatment in one embodiment of the present invention (first preparation method; 1 in the figure represents after modification, and 0 represents before modification);

[0127] Figure 27 shows the calcium and phosphorus deposition effect of glassy carbon and surface-treated glassy carbon (first preparation method);

[0128] Figure 28 shows the calcium-phosphorus deposition effect of surface-treated glassy carbon (second preparation method);

[0129] Figure 29 shows the hydrophilicity test of glassy carbon material (first preparation method) after plasma treatment according to one embodiment of the present invention;

[0130] Figure 30 shows the effects of surface-modified glassy carbon materials on bone repair (in a, the left side is superstructured glassy carbon and the right side is a blank control; b and c are the effect images of superstructured glassy carbon used for bone repair from different visual angles).

[0131] Figure 31 shows the bone induction results after surface-modified glassy carbon material was implanted into muscle (green marks in the figure represent increased ct values, and purple marks represent bone tissue cells);

[0132] Figure 32 shows that the glassy carbon material combined with hydroxyapatite (second preparation method) has a more significant bone regeneration promoting ability;

[0133] Figure 33 shows that glassy carbon with surface micro-nano structures (second preparation method) has a more significant and efficient bone regeneration ability compared to titanium alloy;

[0134] Figure 34 shows that glassy carbon with surface micro-nano structures (first preparation method) has a more significant and efficient bone regeneration ability compared to titanium alloy;

[0135] Figure 35 shows the calcium and phosphorus deposition results on the surface of glassy carbon after surface modification in one embodiment of the present invention (A is calcium deposition, B is phosphorus deposition). Detailed Implementation

[0136] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0137] In this document, "and / or" includes any and all combinations of one or more of the listed related items.

[0138] In this article, "multiple" means two or more, that is, it includes two, three, four, five, etc.

[0139] As used in this specification, the term "about" typically means + / -5% of the value, more typically + / -4%, more typically + / -3%, more typically + / -2%, even more typically + / -1%, and even more typically + / -0.5%.

[0140] In this specification, certain embodiments may be disclosed in a range-bound format. It should be understood that this "range-bound" description is merely for convenience and brevity and should not be construed as a rigid limitation on the disclosed range. Therefore, the description of a range should be considered as having specifically disclosed all possible subranges and the individual numerical values ​​within those ranges. For example, a description of the range 1-6 should be considered as having specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and the individual numbers within those ranges, such as 1, 2, 3, 4, 5, and 6. This rule applies regardless of the breadth of the range.

[0141] Definition of noun:

[0142] The "uniform stress distribution in all directions" mentioned in this invention refers to the fact that the static stress analysis results of the three-period minimal surface lattice structure of this invention all show a uniform static stress distribution in the X, Y, and Z directions.

[0143] The "superstructure" described in this invention refers to a structure that simultaneously satisfies the three-period minimum surface and the stable structure of uniform stress in diamond or diamond-like materials as described in this invention.

[0144] The “diamond-like structure” described in this invention refers to a variant having a diamond-like tetrahedral structure, the variant including slight changes in bond angles or side lengths.

[0145] The "proportional reduction" mentioned in this invention means that the three-period minimal surface structure described in this invention has the same or similar shrinkage rate in all directions during the pyrolysis process.

[0146] The "identical structural unit" mentioned in this invention refers to the polymer scaffold also having a stable structure with uniform stress distribution in all directions; it also uses a unit cell with a three-period minimal surface as the smallest repeating unit; the unit cell with the three-period minimal surface includes a diamond or diamond-like structure.

[0147] Example 1

[0148] This embodiment provides a method for preparing a superstructured glassy carbon material. The process is as follows: first, a three-period minimal surface lattice superstructure is designed, and then it is prepared using 3D printing technology.

[0149] The Tri-Periodic Minimal Surface (TPMS) described in this invention is a minimal surface with a crystal structure. It periodically (with periodic variations along the X, Y, and Z axes) constructs a smooth, fully connected porous structure in three-dimensional space with an average curvature range of -0.135 to 0.137 and an optimal average curvature of 0.

[0150] This embodiment provides three-dimensional digital models of four three-period minimal surface lattice structures: D-type, G-type, CY-type, and IWP-type. Among them, the D-type is a diamond structure, while the G-type, CY-type, and IWP-type are non-diamond structures. When the unit cell of the three-period minimal surface of the superstructured glassy carbon is a diamond-like structure, the structural model designed by the D-type equation and the equations of other non-diamond structures can be mixed using Boolean operations and other methods commonly used in the art to obtain a diamond-like structure.

[0151] The specific preparation process includes the following steps.

[0152] Step 1: Use 3D modeling software to design and construct a three-dimensional digital model with a three-period minimal surface lattice structure. The three-dimensional digital model equations involved (hereinafter referred to as "equations") are as follows.

[0153] (1) Type D:

[0154] Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0

[0155] (2) Type G:

[0156] cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0

[0157] (3) CY type:

[0158] sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0159] (4) IWP type:

[0160] 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3

[0161] In this embodiment, the D-type is selected. The three-period minimal surface lattice model (scaffold structure model) designed based on the D-type equation is shown in Figure 1. Furthermore, the structural schematic diagrams of this three-period minimal surface lattice model in the X, Y, and Z directions are shown in Figure 2.

[0162] Step 2: Using carbon-rich polymers as printing materials, this embodiment specifically uses epoxy resin as the material, and prints polymer scaffolds, also known as superstructure scaffolds, through digital light processing printing technology (photocuring printing).

[0163] Step 3: Using equipment such as a muffle furnace, tube furnace, or hot isostatic pressing furnace, the superstructure scaffold prepared in Step 2 is heated at atmospheric pressure under the protection of inert argon gas. Specifically, the temperature is first increased from room temperature to 250°C for 60 minutes, then increased to 350°C for 100 minutes, held at that temperature for 120 minutes, and then increased by 1°C every 2 minutes until reaching 700-3000°C. After natural cooling, the superstructure scaffold is scaled down proportionally to obtain superstructured glassy carbon material. The superstructured glassy carbon prepared in this embodiment has a porous structure with dimensions exceeding 5 cm and pore wall thickness less than 3 mm. The centimeter-sized superstructured glassy carbon prepared in this embodiment is shown in Figure 3.

[0164] It is understood that the present invention may also employ furan resin, furfuryl alcohol resin, furfuryl ketone resin, phenolic resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyetheretherketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylsulfone, polyethylene naphthalate, polyaniline, and other similar resins. One or more of the following materials are used as 3D printing materials: acetylene, poly(p-phenylene), polyphthalimide, poly(phenylene acetylene), polylactide, polychloroprene, cyanopolyacrylate, polynaphthalene acetylene, poly(p-xylene), polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinyl acetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polychlorotrifluoroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly(p-phenylene sulfone), polyphenylene oxide, polybenzoxazole, polypiperidine, polyvinyl alcohol acetal, polybenzothiazole, or polyvinylpyrrolidone.

[0165] It is understood that the present invention can also employ 3D printing technologies such as liquid crystal display printing, two-photon printing, extrusion printing, and powder laser sintering printing.

[0166] It is understood that the present invention may also use inert gases such as nitrogen, helium, or neon, or combinations thereof, as protective gases.

[0167] Example 2

[0168] This provides performance verification of the superstructured glassy carbon material prepared in Example 1.

[0169] 2.1 Shrinkage rate determination

[0170] The shrinkage rate of the superstructured glassy carbon prepared in Example 1 was measured, and the results showed that the superstructured glassy carbon prepared in Example 1 did not exhibit uneven shrinkage or stress concentration.

[0171] Control experiment: The ordinary glassy carbon precursor was first heated from room temperature to 250℃ for 60 minutes, then heated to 350℃ for 100 minutes and held at that temperature for 120 minutes. Then, the temperature was increased to 700-3000℃ in increments of 2 degrees Celsius, and then allowed to cool naturally. The shrinkage rate was then measured, and the results showed obvious uneven shrinkage and stress concentration, as shown in Figure 4.

[0172] 2.2 Verification of proportional shrinkage

[0173] Superstructured glassy carbon of different sizes was prepared using the method in Example 1. Then, a test was conducted to assess the uniform shrinkage of the glassy carbon scaffolds, and the results are shown in Figure 5. Figure 5A shows that after high-temperature pyrolysis under the same conditions, glassy carbon of different sizes shrank proportionally without changing their shape. Figure 5B shows the shrinkage rate of glassy carbon of different sizes in different directions.

[0174] The appearance and microstructure of ordinary glassy carbon prepared according to the control experiment in 2.1 were observed, and the results are shown in Figure 6. As can be seen from Figure 6, the ordinary glassy carbon scaffold prepared by a method other than that of this invention exhibits obvious deformation and large defects after shrinkage.

[0175] 2.3 Microstructure Observation

[0176] The apparent microscopic defects of the superstructured glassy carbon prepared in Example 1 and the ordinary structured glassy carbon prepared in the control experiment of 2.1 were analyzed by scanning electron microscopy, as shown in Figure 7. Obvious surface cracks were observed on the ordinary structured glassy carbon, while no similar defects were found on the superstructured glassy carbon prepared in Example 1, as shown in Figure 8. The figure shows that the superstructured glassy carbon prepared by the present invention has no defects larger than micrometers.

[0177] 2.4 Mechanical property verification

[0178] The superstructured glassy carbon prepared by the scaffold model in Example 1 with a porosity of 50% was subjected to compression tests with the ordinary structured glassy carbon prepared by the control experiment in 2.1. The specific steps are as follows.

[0179] Glassy carbon material samples of 1cm×1cm×1cm were prepared, and the maximum compressive strength of the samples was tested using a universal mechanical compressor. The displacement rate of the compressor beam was set to 1mm / min until the sample failed, and the maximum load was recorded. The ratio of the maximum load to the area of ​​force application was the maximum compressive strength.

[0180] The experimental results are shown in Figure 9. The maximum compressive strength of the superstructured glassy carbon material sample prepared in Example 1 was 186 MPa; the maximum compressive strength of the ordinary structured glassy carbon material sample was only 17.59 MPa.

[0181] Further verification showed that the superstructured glassy carbon material prepared in Example 1 has excellent mechanical properties, and only 0.1g can withstand a weight of 100kg, as shown in Figure 10.

[0182] Example 3

[0183] This embodiment provides several other examples of methods for preparing superstructured glassy carbon materials, as detailed below.

[0184] Example 1

[0185] Step 1: Use 3D modeling software to design and construct a three-dimensional digital model with a three-period minimal surface lattice structure. The three-dimensional digital model equations involved (hereinafter referred to as "equations") are as follows.

[0186] (1) Type D:

[0187] Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0

[0188] (2) Type G:

[0189] cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0

[0190] (3) CY type:

[0191] sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0192] (4) IWP type:

[0193] 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3

[0194] This example selects type D.

[0195] Step 2: Using carbon-rich polymers as printing materials, this example uses furfuryl alcohol resin as the material, and prints a polymer scaffold, also known as a superstructure scaffold, using two-photon printing technology.

[0196] Step 3: Using equipment such as a muffle furnace, tube furnace, or hot isostatic pressing furnace, the superstructure scaffold prepared in Step 2 is heated at atmospheric pressure under the protection of inert argon gas. Specifically, the temperature is first raised from room temperature to 250°C for 70 minutes, then raised to 350°C for 80 minutes, held at that temperature for 100 minutes, and then raised by 1 degree every 3 minutes until the temperature reaches 700-3000°C. Finally, it is allowed to cool naturally to obtain the superstructured glassy carbon material.

[0197] Example 2

[0198] Step 1: Use 3D modeling software to design and construct a three-dimensional digital model with a three-period minimal surface lattice structure. In this example, the D-type is selected.

[0199] Step 2: Using carbon-rich polymers as printing materials, this example uses acrylic resin as the material, and prints a polymer scaffold, also known as a superstructure scaffold, through extrusion printing technology.

[0200] Step 3: Using equipment such as a muffle furnace, tube furnace, or hot isostatic pressing furnace, the superstructure scaffold prepared in Step 2 is heated at atmospheric pressure under the protection of inert argon gas. Specifically, the temperature is first raised from room temperature to 255°C for 100 minutes, then raised to 360°C for 100 minutes, held at that temperature for 80 minutes, and then raised by 1 degree every 5 minutes until the temperature reaches 700-3000°C. Finally, it is allowed to cool naturally to obtain the superstructured glassy carbon material.

[0201] Example 3

[0202] Step 1: Use 3D modeling software to design and construct a three-dimensional digital model with a three-period minimal surface lattice structure. In this example, the D-type is selected.

[0203] Step 2: Using carbon-rich polymers as printing materials, this example uses polyurethane as the material, and a polymer scaffold, also known as a superstructure scaffold, is printed using powder laser sintering printing technology.

[0204] Step 3: Using equipment such as a muffle furnace, tube furnace, or hot isostatic pressing furnace, the superstructure scaffold prepared in Step 2 is heated at atmospheric pressure under the protection of inert argon gas. Specifically, the temperature is first raised from room temperature to 260°C for 90 minutes, then raised to 360°C for 90 minutes, held at that temperature for 120 minutes, and then raised by 1 degree Celsius every minute until it reaches 700-3000°C. Finally, it is allowed to cool naturally to obtain the superstructured glassy carbon material.

[0205] It should be noted that the above implementation methods are merely examples, and the final sintering should be used to obtain a superstructured glassy carbon material, rather than as a limitation.

[0206] Example 4

[0207] Further explanation is provided for the four three-period minimal surface models involved in Example 1.

[0208] The four three-period minimum surface models are all based on the definition of a three-period minimum surface. They all have a structural periodic repetition in three dimensions and an average curvature range of -0.135 to 0.137.

[0209] More intuitively, the average curvature of each point on the surface is 0.

[0210] Furthermore, this is because structures with zero curvature possess isotropic and uniform stress distribution.

[0211] Finite element simulations of the three-period minimal surface structure of the D-type equation were performed using ABAQUS software, as shown in Figure 11. HyperMesh was used for preprocessing during the simulation, and ABAQUS was used for solving. Preprocessing included geometric manipulation and removal of very small features that did not affect the calculation results. A mesh was then generated using a 0.4 mm mesh size and second-order tetrahedral elements. The total number of elements was 400,814, and the number of nodes was 617,725. The material was set as an elasto-plastic material with a density of 1.1 g / cm³, a Young's modulus of 11 GPa, and a Poisson's ratio of 0.4. One end of the structure was completely fixed, and a 5% compressive strain was applied in three different lattice directions (X, Y, Z). The stress distribution under compressive strain in different directions was calculated. The results show that the model exhibits a uniform stress distribution with no stress concentration when strain is applied in each direction. Furthermore, the lower right figure of Figure 11 shows that this three-period minimal surface lattice structure was proportionally shrunk after pyrolysis to form a superstructured glassy carbon.

[0212] As can be seen from the finite element analysis of other structures, stress concentration can occur in other structures, as shown in Figure 12.

[0213] Example 5

[0214] The superstructured glassy carbon proposed in this invention can also be prepared into other materials; this embodiment only shows some examples.

[0215] In some embodiments, the superstructured glassy carbon proposed in this invention can be prepared as a micro-complex structure (micro-size) material, the specifications of which include nanoscale or microscale.

[0216] Specifically:

[0217] S01: Design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model including

[0218] (1)Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0, (2)cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0,

[0219] (3)sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0

[0220] Or (4)2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))–(cos(2x)+cos(2y)+cos(2z))=0.3;

[0221] S02: Using the three-dimensional digital model designed and constructed in S01 as a template, two-photon printing is performed. The materials used include polymers to obtain a polymer scaffold.

[0222] S03: The polymer scaffold obtained in S02 is sintered under vacuum or atmospheric pressure inert gas. The sintering temperature conditions are similar to those in Example 1 to obtain micro-sized superstructured glassy carbon, which is further prepared into a specific shape. An example is shown in Figure 13.

[0223] Further tests were conducted on the mechanical properties and elasticity of this micro-sized superstructured glassy carbon. The results are shown in Figures 14 and 15. The results show that the maximum compressive strength of the micro-sized glassy carbon is 7.23 GPa, the maximum strain is 66%, and it has ultra-high elastic deformation recovery ability, with a maximum elastic recovery strain of 25%.

[0224] Further characterization of this micro-sized superstructured glassy carbon material is shown in Figure 16. Its TEM image reveals a large number of rolled graphene sheet structures, indicating enhanced mechanical properties.

[0225] In some embodiments, the superstructured glassy carbon proposed in this invention can also be prepared into large-size complex structural materials and printed using photopolymerization, as shown in Figure 17.

[0226] In some embodiments, the superstructured glassy carbon proposed in this invention can also be modularly segmented, as shown in Figures 18a and 18b.

[0227] Example 6

[0228] This embodiment provides an example of a surface-modified or surface-modified glassy carbon material.

[0229] First, a glassy carbon material is prepared.

[0230] First preparation method:

[0231] Unless otherwise specified, all superstructured glassy carbons mentioned in the following examples were prepared using the first preparation method.

[0232] Step 1: Use 3D modeling software to design and construct a three-dimensional digital model with a three-period minimal surface lattice structure (scaffold structure). The three-dimensional digital model equations involved are of type D.

[0233] Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0.

[0234] Step 2: Using carbon-rich polymers as printing materials, in this embodiment, epoxy resin is used as the material, and polymer scaffolds, also known as superstructure scaffolds, are obtained by printing with digital light processing printing technology (e.g., photopolymerization printing).

[0235] Step 3: Surface modification of the prepared superstructure scaffold.

[0236] Step 4: Using equipment such as a muffle furnace, tube furnace, or hot isostatic pressing furnace, the surface-modified superstructure scaffold prepared in Step 3 is heated at atmospheric pressure under the protection of inert argon gas. Specifically, the temperature is first raised from room temperature to 250°C for 60 minutes, then raised to 350°C for 100 minutes, held at that temperature for 120 minutes, and then raised by 1 degree Celsius every 2 minutes until the temperature reaches 700-3000°C. Then it is naturally cooled to obtain the surface-modified or surface-modified glassy carbon material, which is the bone-inducing material described in this invention.

[0237] Second preparation method:

[0238] Step 1: Design and construct a three-dimensional digital model with a diamond structure using 3D modeling software; use a carbon-rich polymer as the printing material. In this embodiment, a resin mixture containing polyurethane and carbon nanotubes is used as the material, and a polymer scaffold, also known as a superstructure scaffold, is obtained by photopolymerization printing.

[0239] Step 2: Surface modification of the prepared superstructure scaffold.

[0240] Step 3: Using equipment such as a muffle furnace, tube furnace, or hot isostatic pressing furnace, the surface-modified superstructure scaffold prepared in Step 3 is heated at atmospheric pressure under the protection of inert argon gas. Specifically, the temperature is first raised from room temperature to 250°C for 60 minutes, then raised to 350°C for 100 minutes, held at that temperature for 120 minutes, and then raised by 1 degree Celsius every 2 minutes until the temperature reaches 700-3000°C. Then it is naturally cooled to obtain the surface-modified or surface-modified glassy carbon material, which is the bone-inducing material described in this invention.

[0241] This embodiment can also provide another alternative method.

[0242] First, a superstructure scaffold is fabricated using 3D printing technology. Then, the superstructure scaffold is pyrolyzed into glassy carbon material. Next, the glassy carbon material is surface-modified to obtain the osteoinductive material.

[0243] The following examples illustrate surface modification methods. It is understood that the specific implementation methods described below are merely examples and not limitations.

[0244] (1) Surface solvent treatment: The above-mentioned superstructure scaffolds were post-treated with water solvents, and the immersion temperature was room temperature to obtain bone-inducing materials.

[0245] (2) Surface micro-nano morphology molten salt etching: The above-mentioned superstructure scaffold is subjected to high temperature treatment at 800°C or above by one of the following molten salts or mixed molten salts: sodium chloride, potassium chloride, magnesium chloride, sodium fluoride, calcium fluoride, lithium chloride, and calcium chloride, to obtain bone induction material with rough surface micro-nano morphology.

[0246] (3) Surface CO2 treatment: The glass carbon above is continuously purged with CO2 gas under normal pressure and heated to 800-1200℃, and then cooled to room temperature to obtain a bone-inducing material with surface modification.

[0247] (4) Plasma treatment: The glassy carbon is sputtered with pure O2 or a mixture of Ar and O2 as the gas source using a plasma device. The plasma power is controlled within the range of 50-1000W for 5-60 minutes to obtain a hydrophilic surface.

[0248] Optionally, functional groups, proteins, peptides, and / or small molecule drugs can be further introduced onto the surface. Following conventional techniques in the art, functional groups or other substances can be attached to or introduced onto the surface-modified material as needed.

[0249] The results are shown in Figures 22-28. Figures 22-25 show examples of the microstructure of the modified surface. The modified material surface has a coral-like or coral-like morphology, which includes straight lines, arcs, branched structures, rings or ring-like structures and / or beaded morphologies formed by the self-assembly of nanoparticles (see Figure 22 for a schematic diagram); the coral-like or coral-like morphology also includes a non-uniform porous structure (Figures 23A and 23C; Figure 23A is obtained by the first preparation method, and Figure 23C is obtained by the second preparation method). It can be understood that the beaded morphology is formed by the self-assembly of nanoparticles, and can be a relatively regular morphology or an irregular beaded morphology without obvious boundaries. In some cases, these beads formed by the self-assembly of nanoparticles are even observed to be fused together with the naked eye.

[0250] Figure 27 shows glassy carbon materials prepared by the first method and treated with a solvent method; Figure 28 shows glassy carbon materials prepared by the second method and treated with a solvent method. Both types of glassy carbon materials exhibit more pronounced calcium and phosphorus deposition, thus possessing bone-inducing ability.

[0251] Further hydrophilicity tests were conducted on the surface-modified glassy carbon material after plasma treatment in (4). The surface-modified and unmodified glassy carbon materials were placed in black ink, with a paper towel placed on top. The plasma-treated carbon material quickly absorbed the black ink, and the paper towel on top also quickly absorbed the ink. The results are shown in Figure 27. This demonstrates that the plasma-treated glassy carbon material possesses superior water absorption capacity.

[0252] In some embodiments, the superstructured glassy carbon (first preparation method) proposed in this invention can also be composited with polymer materials. For example, a PEEK coating is applied to the surface of the superstructured glassy carbon, as shown in Figure 19. The figures show coatings prepared with a 1% concentration of PEEK dispersion and coatings prepared with a 2% concentration of PEEK dispersion, respectively. As another example, the superstructured glassy carbon (first preparation method and second preparation method) proposed in this invention can also be composited with hydroxyapatite (ceramic material), so that its surface is loaded with hydroxyapatite, as shown in Figures 20 and 21. Figure 20 shows the composite of superstructured glassy carbon prepared by the first preparation method and hydroxyapatite; Figure 21 shows the composite of superstructured glassy carbon prepared by the second preparation method and hydroxyapatite. These composite materials can be further used in the fields of energy, aerospace, and biomedicine.

[0253] Example 7

[0254] This embodiment provides a verification of the application of surface-modified glassy carbon material in bone repair.

[0255] Experimental procedure: The prepared osteoinductive material obtained by solvent treatment was implanted into the critical bone defect (5 mm in diameter) of the skull of 6-week-old SD rats. Then, at 2 months, the rat skulls were removed, and the efficacy of the superstructured glassy carbon on bone repair was analyzed by CT.

[0256] Results: See Figure 30, which is a schematic diagram of the surface-modified glassy carbon material (first preparation method) used for bone repair and its therapeutic effect (Figure 30a shows modified glassy carbon on the left and a blank control on the right; bone tissue growth in the superstructured glassy carbon is visible in Figure 30a). Over a two-month period, the pores on the left were observed to be significantly smaller than those on the right, proving that the surface-modified glassy carbon material prepared in this invention has bone repair capabilities. Figures 30b and 30c also provide verification from different perspectives.

[0257] Figure 31 shows the implantation of surface-modified glassy carbon material (second preparation method) into muscle tissue. Bone tissue formation was induced on the surface of the glassy carbon scaffold, demonstrating its ability to induce bone formation (osteoinduction). It is speculated that the unique coral-like or coral-like morphological structure of this surface exerts a mechanical effect on cells. This invention innovatively proposes that carbon materials induce osteoinduction.

[0258] In some other preferred embodiments, bone induction is formed by the self-assembly of nanoscale materials.

[0259] In some other preferred embodiments, the glassy carbon material is surface-processed to form a rough surface, and this uniformly rough surface plays a role in bone growth and bone induction.

[0260] Example 8

[0261] This embodiment provides another application verification of surface-modified glass carbon material in bone repair.

[0262] Experimental Procedure: Modified glassy carbon materials obtained by solvent treatment (first preparation method and second preparation method) were placed in a hydrothermal reactor. Under high temperature and high pressure conditions, a hydroxyapatite coating was formed on the surface of the glassy carbon materials. The glassy carbon materials with the hydroxyapatite coating and the modified glassy carbon materials were then implanted into the femoral condyle. At predetermined time points, specimens from the bone defects in each group were removed for efficacy evaluation.

[0263] Controlled experiment: A titanium alloy scaffold was implanted into the femoral condyle in the same manner. At a predetermined time point, a specimen was removed from the bone defect site for efficacy evaluation.

[0264] The results of the first preparation method are shown in Figure 34; the results of the second preparation method are shown in Figures 32 and 33. Figure 32 shows that the modified glassy carbon material composited with hydroxyapatite has a more significant bone regeneration promoting ability; in the same group, the entire defect area was fully healed at 12 weeks compared to 4 weeks; there were blank areas in the middle of the samples at 4 weeks. Figure 33 shows that the modified glassy carbon material with a nano-bead-like morphology on the surface has a more significant and efficient bone regeneration promoting ability compared to titanium alloy (control) (pink represents the grown bone cells / bone tissue; the pink portion in the superstructured glassy carbon is more abundant than in the titanium alloy). Figure 34 shows that compared to the titanium alloy implantation group, the superstructured glassy carbon implantation group showed more bone tissue growth.

[0265] Example 9

[0266] This embodiment provides another application of glassy carbon material in bone induction.

[0267] When glassy carbon without the scaffold model design in Example 1 is surface-modified using the method shown in Example 6, its surface can also form coral-like or coral-like micro / nano morphologies. Further verification shows that the glassy carbon material of Example 6 exhibits similar or identical calcium and phosphorus deposition phenomena, indicating that the surface modification method provided by this invention and the coral-like or coral-like morphology material formed after modification have osteoinductive effects. The results are shown in Figure 35, where yellow represents calcium and blue represents phosphorus.

[0268] The embodiments of the present invention have been described above with reference to the accompanying drawings. However, the present invention is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of the present invention without departing from the spirit and scope of the claims. All of these forms are within the protection scope of the present invention.

Claims

1. An ultrastuctured glassy carbon, characterized in that, The superstructure glass carbon has a stable structure with uniform distribution of anisotropic stress; the superstructure glass carbon takes a three-period minimal surface cell as a minimum repeating unit; the three-period minimal surface cell includes a diamond or diamond-like structure; and the superstructure glass carbon is obtained by pyrolysis and equal-proportion reduction and carbonization of a high-molecular polymer support with the same structure unit.

2. The ultrastuctured glassy carbon of claim 1, wherein The three-period minimal surface includes the following numerical model characteristics: (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0, (2) cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0, (3) sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0, or (4) 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))-(cos(2x)+cos(2y)+cos(2z))=0.

3. The surface average curvature of the three-period minimal surface structure ranges from -0.135 to 0.

137.

3. The ultrastuctured glassy carbon of claim 1, wherein The pyrolysis conditions include vacuum high-temperature pyrolysis or high-temperature normal-pressure pyrolysis in an inert atmosphere.

4. The ultrastuctured glassy carbon of claim 1 wherein, The high-molecular polymer includes a high-carbon-content high-molecular polymer.

5. The ultrastuctured glassy carbon of claim 1 wherein, The high-carbon-content high-molecular polymer includes one or more materials selected from the group consisting of furan resin, furfuryl alcohol resin, furfural resin, phenol formaldehyde resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyether ether ketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene chloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylsulfone, polyethylene naphthalate, polyaniline, polyacetylene, poly-p-phenylene, polyphthalimide, polyphenylene acetylene, polylactide, polychloroprene, cyano polyacrylate, polynaphthalene acetylene, parylene, polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinyl acetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polytrifluorochloroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly-p-phenylene sulfone, polyphenylene, polybenzoxazole, polypiperidine, polyvinyl acetal, polybenzothiazole, and polyvinyl pyrrolidone.

6. The ultrastuctured glassy carbon of claim 5, wherein ​ 7. Use of the super-structured glassy carbon according to any one of claims 1 to 6 for the production of large-sized materials, characterized in that, The large-size material has a size ranging from millimeter to decimeter; or, the use of the super-structure glassy carbon according to any one of claims 1-6 in the preparation of micro-structure complex material, characterized in that the micro-structure complex material has a size ranging from nanometer to millimeter.

8. Use according to claim 7, wherein the compound is ###0002### The large-size material includes large-size glassy carbon material and large-size glassy carbon composite material spliced with other materials; the other materials include metal material, polymer material, ceramic material, glass material or semiconductor material.

9. The use of the super-structure glassy carbon according to any one of claims 1-6 in the preparation of energy material or aerospace material.

10. A bone inductive material, characterized by, The bone-inductive material is prepared from a surface-modified glassy carbon material; the glassy carbon material has a stable structure with uniformly distributed stress in all directions; the super-structure glassy carbon takes a three-period minimal surface cell as the smallest repeating unit; the three-period minimal surface cell includes diamond or diamond-like structure; the glassy carbon material is obtained by pyrolysis and equal-proportion carbonization of a high-molecular polymer scaffold with the same structure; the surface-modified glassy carbon material has a coral-like or coral-like morphology, which includes straight lines, curved lines, branched structures, circular rings or circular ring-like structures and / or string-bead-like morphology formed by self-assembly of nanoparticles; the coral-like or coral-like morphology further includes inhomogeneous pore structures.

11. The osteoinductive material as described in claim 10, characterized in that, The means for changing the surface morphology include solvent treatment, molten salt etching, CO2 etching or plasma treatment.

12. The osteoinductive material as described in claim 10, characterized in that, The means for changing the surface properties further include introducing functional groups, proteins, polypeptides and / or small molecule drugs on the surface; preferably, the functional groups include carbonyl, hydroxyl, carboxyl, epoxy, vinyl, alkoxy, thiol, amino, azide and / or alkyne.

13. The osteoinductive material as described in claim 10, characterized in that, The three-period minimal surface includes the following numerical model characteristics: (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0, (2) cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0, (3) sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)- cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0 or (4) 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))-(cos(2x)+cos(2y)+cos(2z))=0.

3. The surface average curvature of the three-period minimal surface structure ranges from -0.135 to 0.

137.

14. The osteoinductive material as described in claim 10, characterized in that, ​ 15. The osteoinductive material as described in claim 10, characterized in that, The high molecular polymer includes a high carbon content high molecular polymer; the high carbon content high molecular polymer comprises one or more materials selected from the group consisting of furan resin, furfuryl alcohol resin, furfural resin, phenolic resin, epoxy resin, polyurethane, polyimide, polyethylene glycol, acrylic resin, polylactic acid, polycaprolactone, polyethylene, polyether ether ketone, nylon, polycarbonate, polymethyl methacrylate, polyvinyl butyral, polyethylene terephthalate, polyacrylonitrile, polyvinylidene fluoride, polyvinylidene dichloride, polystyrene, polybutadiene, polyphenylene ether, polyphenylene sulfide, polybutene-1, polybenzimidazole, polyaryletherketone, polyarylsulfone, polyethylene naphthalate, polyaniline, polyacetylene, poly-p-phenylene, polyphthalimide, polyphenylene acetylene, polylactide, polychloroprene, cyano polyacrylate, polynaphthalene acetylene, p-xylene, polymethylphenylsiloxane, liquid crystal polymer, polythiophene, polyvinyl acetylene, polyoxadiazole, polybisphenol A, polyacrylonitrile-butadiene-styrene copolymer, polytrifluorochloroethylene, polyepoxy resin-acrylate copolymer, polybenzoquinone, poly-p-phenylene sulfone, polyphenylene, polybenzoxazole, poly-piperidine, polyvinyl acetal, polybenzothiazole and polyvinyl pyrrolidone.

16. A method of making a super-structured glassy carbon, comprising: The preparation method comprises the following steps: S01: design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model comprising (1) Sin(x)sin(y)sin(z)+sin(x)cos(y)cos(z)+cos(x)sin(y)cos(z)+cos(x)cos(y)sin(z)=0, (2) cos(x)sin(y)+cos(y)sin(z)+sin(x)cos(z)=0, (3) sin(x)sin(y)sin(z)+sin(2x)sin(y)+sin(2y)sin(z)+sin(2z)sin(x)-cos(x)cos(y)cos(z)+sin(2x)cos(z)+cos(x)sin(2y)+cos(y)sin(2z)=0 Or (4) 2(cos(x)cos(y)+cos(y)cos(z)+cos(z)cos(x))-(cos(2x)+cos(2y)+cos(2z))=0.3; S02: using the three-dimensional digital model designed and constructed in S01 as a template for 3D printing, the material used for 3D printing comprising a high molecular polymer, to obtain a high molecular polymer scaffold; S03: heating the high molecular polymer scaffold obtained in S02 to 700-3000 DEG C under normal pressure in a vacuum or inert gas environment, to obtain the superstructure glass carbon. Comprise the following steps:

17. A method of preparing an osteoinductive material, characterized by, S01: design and construct a three-dimensional digital model with a three-period minimal surface lattice structure, the three-dimensional digital model comprising ​ (1) Sin(x)sin(y)sin(z) + sin(x)cos(y)cos(z) + cos(x)sin(y)cos(z) + cos(x)cos(y)sin(z) = 0, (2) cos(x)sin(y) + cos(y)sin(z) + sin(x)cos(z) = 0, (3) sin(x)sin(y)sin(z) + sin(2x)sin(y) + sin(2y)sin(z) + sin(2z)sin(x) - cos(x)cos(y)cos(z) + sin(2x)cos(z) + cos(x)sin(2y) + cos(y)sin(2z) = 0 or (4) 2(cos(x)cos(y) + cos(y)cos(z) + cos(z)cos(x)) - (cos(2x) + cos(2y) + cos(2z)) = 0.3; S02: 3D printing the three-dimensional digital model designed and constructed in S01 as a template, wherein the material used in the 3D printing comprises a high polymer, to obtain a high polymer scaffold; S03: performing surface modification treatment on the high polymer scaffold, wherein the surface modification treatment means comprises solvent treatment or molten salt etching treatment; the surface of the high polymer scaffold after surface modification has a coral-like or coral-like morphology, and the coral-like or coral-like morphology comprises straight lines, curved lines, branched structures, circular rings or circular ring structures and / or string bead-like morphologies formed by self-assembly of nanoparticles; the coral-like or coral-like morphology further comprises a non-uniform pore structure; S04: pyrolyzing the surface-modified high polymer scaffold obtained in S03, and carbonizing the surface-modified high polymer scaffold after pyrolysis to obtain the bone inductive material in a reduced proportion; Alternatively, the bone inductive material can also be prepared by the following steps: S01: designing and constructing a three-dimensional digital model with a three-periodic minimal surface lattice structure, wherein the three-dimensional digital model comprises (1) Sin(x)sin(y)sin(z) + sin(x)cos(y)cos(z) + cos(x)sin(y)cos(z) + cos(x)cos(y)sin(z) = 0, (2) cos(x)sin(y) + cos(y)sin(z) + sin(x)cos(z) = 0, (3) sin(x)sin(y)sin(z) + sin(2x)sin(y) + sin(2y)sin(z) + sin(2z)sin(x) - cos(x)cos(y)cos(z) + sin(2x)cos(z) + cos(x)sin(2y) + cos(y)sin(2z) = 0 or (4) 2(cos(x)cos(y) + cos(y)cos(z) + cos(z)cos(x)) - (cos(2x) + cos(2y) + cos(2z)) = 0.3; ​ Or (4) 2(cos(x)cos(y) + cos(y)cos(z) + cos(z)cos(x)) - (cos(2x) + cos(2y) + cos(2z)) = 0.3; S02: 3D printing the three-dimensional digital model designed in S01 as a template, wherein the material used in the 3D printing comprises a high polymer, to obtain a high polymer scaffold; S03: pyrolyzing the high polymer scaffold obtained in S02, and carbonizing the pyrolyzed high polymer scaffold to obtain a glassy carbon material; S04: performing surface modification treatment on the glassy carbon material to obtain the bone inductive material, wherein the surface modification treatment comprises CO2 etching or plasma treatment; The glassy carbon material after surface modification has a coral-like or coral-like morphology, wherein the coral-like or coral-like morphology comprises straight lines, curved lines, branched structures, circular rings or circular ring structures and / or string bead-like morphologies formed by self-assembly of nanoparticles; the coral-like or coral-like morphology further comprises a non-uniform pore structure.

18. The production method according to claim 17, wherein The 3D printing used comprises liquid crystal display printing technology, digital light processing printing technology, two-photon printing technology, extrusion printing technology or powder laser sintering printing technology; or the pyrolysis is atmospheric pressure heating in an inert gas, wherein the inert gas comprises one or more gases selected from the group consisting of nitrogen, argon, helium and neon.

19. The production method according to claim 17, wherein The means for changing the surface morphology further comprises introducing functional groups, proteins, polypeptides and / or small molecule drugs on the surface.

20. Use of the superstructure glassy carbon of any one of claims 1-6 or the bone inductive material of any one of claims 10-15 in the preparation of a bone repair material.

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