CN111632200A - Microporous composite biological ceramic bone repair support and preparation method and device thereof - Google Patents
Microporous composite biological ceramic bone repair support and preparation method and device thereof Download PDFInfo
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- CN111632200A CN111632200A CN202010491131.XA CN202010491131A CN111632200A CN 111632200 A CN111632200 A CN 111632200A CN 202010491131 A CN202010491131 A CN 202010491131A CN 111632200 A CN111632200 A CN 111632200A
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- 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
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- 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
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a micropore composite biological ceramic bone repair bracket and a preparation method and a device thereof, which comprises a repair bracket body made of composite materials, wherein the repair bracket body comprises a plurality of overlapped bracket layers, each bracket layer is provided with a plurality of micron-sized micropores, a plurality of polyhedrons are formed by a plurality of micropores between each layer, and the composite materials comprise the following components in percentage by weight: 1% -5% of graphene, 50% -60% of zirconia, 20% -40% of hydroxyapatite and beta-tricalcium phosphate, polyhedrons are connected through micropores, the physical properties of the new material, such as compressive strength, elastic modulus, fracture toughness and other indexes, are closer to those of natural bone tissues by utilizing the conductivity and high toughness of the graphene material, the high strength and wear resistance of the zirconia and the good bone induction activity of the hydroxyapatite and the beta-tricalcium phosphate, the new material can bear larger stress to deform without fracture, the abrasion condition of the material and adjacent tissues is reduced, and meanwhile, the new material has higher bone induction activity.
Description
Technical Field
The invention relates to the field of repair of defects of oral, maxillofacial bones, in particular to a microporous composite biological ceramic bone repair support and a preparation method and a device thereof.
Background
The current bone defect repair techniques are as follows:
the method for repairing the jaw bone defect comprises the following steps: as shown in FIG. 8, trauma, tumor, congenital deformity and infection of the maxillofacial area often result in partial or even total loss of the maxillofacial bone tissue. At present, a series of difficult problems exist in the treatment of patients with oral cavity, jaw and facial bone tissue defects, particularly patients with large-scale bone defects, and the problems of bone tissue defect repair are solved firstly, and the upper jaw and the lower jaw are morphologically irregular bones, and the bone tissue defects are often accompanied with the problems of facial tissue displacement, malformation and deformation, poor bone healing, bone nonunion, bone exposure and the like. In the current clinical medicine, as shown in fig. 9 (a) and (b) and fig. 10, the large defects of the bone tissue of the maxillofacial region are usually repaired by skin flaps or bone tissues transferred to other parts of the body, which increases the complexity of the operation and the trauma of the patient, and can not repair the appearance of the maxilla and the mandible individually, and the repair effect is not satisfactory.
Repair material for bone defects: among the bone defect repair materials, bioceramic materials are currently the most bioactive and most applicable materials. The ceramic material which can be applied to 3D printing and manufacturing mostly comprises a single component and mainly comprises a material with osteoinduction activity. However, the single-component ceramic materials are greatly different from the natural bones of human bodies in terms of biomechanical properties and osteogenic properties (as shown in table 1), and are prone to fracture particularly at the parts with discontinuous bones, large defect areas, large occlusion stress and stress concentration, and cannot well meet clinical requirements. Therefore, the research of the composite material is carried out. However, the existing 3D printing process for ceramic composite materials is complex, has high requirements for the properties of raw materials and printing conditions, and still has a lot of technical difficulties, especially in the aspect of 3D printing of porous (microporous) structures with complex spatial structures.
Table 1: difference in physical properties between bone tissue and ceramic material
As can be seen from Table 1, the current single-component ceramic materials are greatly different from natural bones of human bodies in terms of biomechanical properties, such as the indexes of elastic modulus, fracture toughness, compressive strength and tensile strength in the table.
Disclosure of Invention
The invention aims to overcome the defects and provides a microporous composite biological ceramic bone repair support and a preparation method and a device thereof.
In order to achieve the purpose, the technical solution of the invention is as follows: the utility model provides a micropore composite biological ceramic bone repair support, includes the repair support body of making by combined material, and the repair support body includes a plurality of layers of support layer of superpose mutually, and each support layer all is equipped with a plurality of micron order micropore, and a plurality of polyhedron is constituteed to a plurality of micropore between each layer.
Preferably, the composite material comprises the following components in percentage by weight: 1-5% of graphene, 50-60% of zirconia, 20-40% of hydroxyapatite and beta-tricalcium phosphate.
Preferably, the shape of the micro-pores is any one or more of a triangle or a quadrangle.
Preferably, the polyhedrons are connected through the micropores, and both the polyhedrons and the micropores can be used for flowing and attaching human bone tissues and cells.
A preparation method of the microporous composite biological ceramic bone repair scaffold comprises the following steps:
s1, collecting the CT image data of jaw bone segment defect;
s2: converting the acquired CT image data into a digital image model;
s3: designing a virtual bone repair support with a micron-sized porous structure according to a digital model;
s4: according to the designed virtual repair support, 3D printing manufacturing is carried out on the microporous bone repair support by combining graphene and a biological ceramic material;
s5: and sintering and forming the micropore bone repairing support after the 3D printing is finished.
Preferably, S4 includes:
s41: printing materials are prepared according to the following weight percentage: 1-5% of graphene, 50-60% of zirconia, 20-40% of hydroxyapatite and beta-tricalcium phosphate.
And S42, finishing spraying of the dissolving pulp according to the prepared material by a 3D printer, and carrying out photosensitive curing.
Preferably, the proportion of the printing ink in the printing of the hydroxyapatite and the beta-tricalcium phosphate is as follows by weight percentage: 20 to 40 percent of hydroxyapatite, 20 to 40 percent of beta-tricalcium phosphate powder, 5 to 15 percent of dilute citric acid and potassium dihydrogen phosphate, 5 to 15 percent of silicon dioxide and zinc oxide and 5 to 15 percent of paraffin wax microsphere.
Preferably, the proportion of the printing ink in the zirconia printing process is as follows by weight percent: 5-10% of graphene, 60-80% of zirconia, 5-10% of absolute ethyl alcohol, 5-10% of polyacrylic acid and ammonium polyacrylate, 5-10% of polyethylene glycol and polyvinylpyrrolidone, and 5-10% of citric acid and oleic acid.
Preferably, in S42, the spray nozzle has a spray hole size of 140 μm-160 μm and a traveling speed of 90mm/min-110 mm/min.
Preferably, in S4, the prosthetic scaffold layers of the microporous bone prosthetic scaffold are all spaced at intervals of 100 μm to 400 μm on the X, Y, Z axis of the 3D printer.
Preferably, in S4, 3D printing is performed using paste direct writing molding or micro stereolithography.
Preferably, in S2: and denoising the digital image model, and quantitatively comparing the denoised reconstructed image with the original image by taking the mean square error and the peak signal-to-noise ratio as measurement indexes.
A preparation device for the microporous composite biological ceramic bone repair scaffold comprises:
a data acquisition component: collecting the CT image data of the jaw bone segment defect;
a data conversion section: converting the acquired CT image data into a digital image model;
bone repair scaffold design component: designing a virtual bone repair support with a micron-sized porous structure according to a digital model;
bone repair support printing component: according to the designed virtual repair support, 3D printing manufacturing is carried out on the microporous bone repair support by combining graphene and a biological ceramic material;
sintering the molded part: and sintering and forming the micropore bone repairing support after the 3D printing is finished.
Preferably, the data acquisition component, the data conversion component, the bone repair scaffold design component, the bone repair scaffold printing component and the sintering molding component are in any one or more of wired electric connection and wireless induction connection.
Preferably, the graphene is high-purity graphene or graphene oxide.
By adopting the technical scheme, the invention has the beneficial effects that:
1. by adjusting the proportion of each component of the graphene and the biological ceramic material, the conductivity and the high toughness of the graphene material, the high strength and the wear resistance of the zirconia, and the good bone induction activity of the hydroxyapatite and the beta-tricalcium phosphate, the physical properties of the new material, such as the compressive strength, the elastic modulus, the fracture toughness and other indexes, are closer to those of natural bone tissues, the material can bear larger stress to deform without fracture, and the abrasion condition of the material and adjacent tissues is reduced.
2. Due to the addition of the graphene material, the conductivity of the composite ceramic material is improved, and the differentiation and osteogenesis efficiency of osteoblasts can be greatly improved by an auxiliary means of applying micro-current stimulation, so that the aim of remarkably shortening the clinical healing time is fulfilled.
3. Adopt high accuracy 3D printing technique and equipment, make the microstructure of printing material more and more accurate, use the porous microstructure printing technique of receiving the nanometer scale as the representative, greatly improved the spatial structure and the biological performance of material, it includes a plurality of layers of support layers of superpose mutually to restore the support body, each support layer all is equipped with a plurality of micron order micropore, a plurality of micropore between each layer constitute a plurality of polyhedrons, make the polyhedron that the micropore constitutes can make the biomaterial of printing more be favorable to the adhesion growth of cell tissue with histiocyte full contact.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a microporous composite biological ceramic bone repair scaffold according to the present invention;
FIG. 2 is a schematic flow chart of the preparation method S4 of the microporous composite biological ceramic bone repair scaffold of the present invention;
FIG. 3 is a schematic structural diagram of a microporous composite bioceramic bone repair scaffold manufacturing apparatus according to the present invention;
FIG. 4 is a schematic structural view of the microporous composite bioceramic bone repair scaffold of the present invention;
FIG. 5 is a schematic view of the adaptation of the microporous composite bioceramic bone repair scaffold of the present invention to the mandible;
FIG. 6 is a schematic view of the scaffold layer connection structure of the microporous composite bioceramic bone repair scaffold of the present invention;
FIG. 7 is a schematic view of a polyhedron of the present invention;
FIG. 8 is a schematic view of a segmental bone defect of the chin of the mandible;
FIG. 9 is a schematic view of a process of repairing a mandible using a peroneal skin flap of a lower limb according to a conventional method;
FIG. 10 is a schematic view of a lower limb gastrocnemius flap repairing a mandibular defect using a conventional method;
FIG. 11 is a simulation diagram of the repairing jaw bone defect of the microporous composite biological ceramic bone repairing scaffold of the present invention;
FIG. 12 is a schematic 3D printing view of a microporous composite bioceramic bone repair scaffold according to the present invention;
FIG. 13 is a schematic diagram of the principle of surface projection micro-stereolithography according to the present invention.
Description of the main reference numerals: the method comprises the following steps of 1, a preparation device, 11 a data acquisition part, 12 a data conversion part, 13 a bone repair support design part, 14 a bone repair support printing part and 15 a sintering molding part.
Detailed Description
The invention is further described below with reference to the figures and the specific embodiments.
Aiming at the disadvantages of the repair method and the repair material for the jaw bone defect in the prior art: firstly, in the repair method in the prior art, the larger defects of the bone tissues of the maxillofacial part are usually repaired by skin flaps or bone tissues transferred to other parts of the body, so that the complexity of the operation is increased, the wound of a patient is increased, the appearance of the maxilla and the mandible cannot be repaired individually, and the repair effect is not satisfactory; secondly, in the repair material in the prior art, the ceramic material with single component has larger difference with the natural bone of human body no matter from the aspects of biomechanical property and osteogenic property, and is easy to fracture particularly at the parts with discontinuous bone, larger defect area, larger occlusion stress and concentrated stress, and can not well meet the clinical requirement.
[ microporous composite bioceramic bone repair scaffold according to embodiments of the present invention ]
Structure of repair stent
As shown in fig. 4, including the restoration support body of making by combined material, as shown in fig. 6, the restoration support body includes a plurality of layers of support layer of superpose mutually, each support layer all is equipped with a plurality of micron order micropore, a plurality of micropore between each layer constitutes a plurality of polyhedron, link through the micropore between the polyhedron, and polyhedron and micropore all can supply human bone tissue, cell circulation and attached, greatly improved the spatial structure and the biological performance of material, make combined material more be favorable to the adhesion growth of cell tissue. For example, 2 stent layers, even thousands of stent layers, can be made as needed, as long as the size requirements for repairing the stent body can be met. Each support layer all is equipped with a plurality of micropore, and micropore quantity is unrestricted, as long as can extend in order to satisfy the size demand in the space can.
Further, as shown in fig. 7, the shape of the micro-holes is any one or more of a triangle or a quadrangle, the triangle micro-holes can improve the stability of the polyhedron, and the quadrangle micro-holes facilitate the circulation of the human bone tissue and the cells, however, the present invention is not limited thereto, and the shape of the micro-holes is not limited thereto, and may be a polygon such as a hexagon, as long as the shape can facilitate the circulation of the human bone tissue and the cells. Specifically, the corresponding pore size (e.g., pore size in the micron range (100 microns and 400 microns)) and porosity of the bone repair scaffold can be designed as desired.
Composite material for repairing stent
The composite material comprises the following components in percentage by weight: 1-5% of graphene, 50-60% of zirconia, 20-40% of hydroxyapatite and beta-tricalcium phosphate; due to the addition of the graphene material, the conductivity of the composite ceramic material is improved, and the differentiation and osteogenesis efficiency of osteoblasts can be greatly improved by an auxiliary means of applying micro-current stimulation, so that the aim of remarkably shortening the clinical healing time is fulfilled.
[ preparation method of microporous composite bioceramic bone repair scaffold according to embodiment of the present invention ]
As shown in fig. 1, the preparation method comprises:
s1, collecting the CT image data of jaw bone segment defect; the data can be spiral CT or CBCT imaging data, the scanning layer thickness is 0.2-0.625mm, and clear CT influence data can be obtained conveniently.
S2: converting the acquired CT image data into a digital image model; the method adopts the conventional commercial image processing software to establish a digital three-dimensional image model of the jaw bone defect area, respectively displays the indexes of the form, the thickness and the like of soft and hard tissues of the bone defect area, and is convenient for carrying out data analysis on the digital image model through the indexes of the form, the thickness and the like of the soft and hard tissues.
S3: designing a virtual bone repair support with a micron-sized porous structure according to a digital model; meanwhile, the virtual bone repair support with the adaptive pore size and porosity is designed according to the precision degree of the matched 3D printing equipment, so that the 3D printing equipment can print conveniently.
S4: according to the designed virtual repair support, the microporous bone repair support is subjected to 3D printing manufacturing by combining graphene and a biological ceramic material, further, the graphene can be high-purity graphene or graphene oxide, oxygen-containing functional groups on the graphene oxide are increased, so that the property is more active, and the property can be improved through various reactions with the oxygen-containing functional groups.
S5: and sintering and forming the micropore bone repairing support after the 3D printing is finished.
Further, as shown in fig. 2, S4 includes:
s41: mixing the printing materials according to the following ratio: printing materials are prepared according to the following weight percentage: 1-5% of graphene, 50-60% of zirconia, 20-40% of hydroxyapatite and beta-tricalcium phosphate;
the printing ink comprises the following components in percentage by weight: 20 to 40 percent of hydroxyapatite, 20 to 40 percent of beta-tricalcium phosphate powder, 5 to 15 percent of dilute citric acid and potassium dihydrogen phosphate, 5 to 15 percent of silicon dioxide and zinc oxide and 5 to 15 percent of paraffin wax microsphere.
Wherein the proportion of printing ink in zirconia printing is as follows by weight percent: 5-10% of graphene, 60-80% of zirconia, 5-10% of absolute ethyl alcohol, 5-10% of polyacrylic acid and ammonium polyacrylate, 5-10% of polyethylene glycol and polyvinylpyrrolidone, and 5-10% of citric acid and oleic acid.
And S42, finishing spraying of the solution slurry by a 3D printer according to the prepared material and the printing ink, and carrying out photosensitive curing.
Further, in S44, the size of the spray orifice of the spray head is 140 μm-160 μm and the walking speed is 90mm/min-110mm/min during spraying.
Furthermore, the intervals between the repair scaffold layers of the microporous bone repair scaffold on the X, Y, Z axis of the 3D printer are all 100-400 μm.
Further, in S4, as shown in fig. 12, 3D printing is performed by using paste direct writing molding or micro stereolithography, and preferably, as shown in fig. 13, 3D printing is performed by using micro stereolithography in this embodiment, which uses a smaller laser spot (several micrometers), and the resin can undergo a photo-curing reaction in a very small area.
Furthermore, in S2, denoising is performed on the digitized image model, and the denoised reconstructed image and the original image are quantitatively compared with each other by taking the mean square error and the peak signal-to-noise ratio as measurement indexes, so as to determine the optimization degree of the processed CT reconstructed image, adjust the operating software, and feed back and adjust the photographing parameters, so as to obtain a clearer and more accurate CT image.
With the gradual application of the 3D printing technology (Additive manufacturing, AM) in the medical field, the digital imaging technology is combined with medical image data to simulate and reconstruct a three-dimensional image of local tissues of a human body, and an individualized prosthesis is designed according to the specific condition of tissue defect, so that the design and manufacturing process of the prosthesis is simplified, the repairing effect of the body appearance and function is greatly improved, the operation difficulty is reduced, the operation time is shortened, the effect of shape repair is improved, and the pain and the wound born by a patient are relieved.
[ preparation apparatus 1 for a microporous composite bioceramic bone repair scaffold according to an embodiment of the present invention ]
A device 1 for preparing a microporous composite biological ceramic bone repair scaffold, as shown in figure 3, comprises
The data acquisition section 11: collecting the CT image data of the jaw bone segment defect; the data can be spiral CT or CBCT imaging data, the scanning layer thickness is 0.2mm-0.625mm, and clear CT influence data can be obtained conveniently.
The data conversion section 12: converting the acquired CT image data into a digital image model; the method adopts the conventional commercial image processing software to establish a digital three-dimensional image model of the jaw bone defect area, respectively displays the indexes of the form, the thickness and the like of soft and hard tissues of the bone defect area, and is convenient for carrying out data analysis on the digital image model through the indexes of the form, the thickness and the like of the soft and hard tissues.
Bone repair scaffold design part 13: designing a virtual bone repair support with a micron-sized porous structure according to a digital model; meanwhile, the virtual bone repair support with the adaptive pore size and porosity is designed according to the precision degree of the matched 3D printing equipment, so that the 3D printing equipment can print conveniently.
Bone repair scaffold printing component 14: according to the designed virtual repair support, the micropore bone repair support is subjected to 3D printing manufacturing by combining graphene and a biological ceramic material.
Sintering the molded component 15: and sintering and forming the micropore bone repairing support after the 3D printing is finished.
Further, the data acquisition component 11, the data conversion component 12, the bone repair scaffold design component 13, the bone repair scaffold printing component 14, and the sintering molding component 15 are electrically connected by any one or more of a wired connection and a wireless induction connection.
Further, the graphene is high-purity graphene or graphene oxide; the graphene oxide has more active properties due to the increase of oxygen-containing functional groups, and can improve the properties thereof through various reactions with the oxygen-containing functional groups.
Example 1
Digital design of the microporous bone repair scaffold: the data acquisition part 11 is used for acquiring the spiral CT or CBCT image data of jaw segment defect, the scanning layer thickness is 0.425mm, clear image data can be obtained, the integration of data conversion and image processing software is convenient, a digital three-dimensional image model of the jaw defect area is established by adopting the data conversion part 12 (commercial image processing software), the indexes of the shape, thickness and the like of soft and hard tissues of the bone defect area are respectively displayed, meanwhile, the drying treatment is carried out by mean value filtering aiming at the problem of image distortion or noise interference after the digital three-dimensional imaging, two image quality evaluation standards of signal Mean Square Error (MSE) and peak signal-to-noise ratio (PSNR) are applied, the reconstructed image after the noise removal and the original image are quantitatively compared by taking the Mean Square Error (MSE) and the peak signal-to-noise ratio (PSNR) as the measurement indexes, so as to determine the optimization degree of the processed CT reconstructed image, adjusting the operating software, and feeding back and adjusting photographing parameters to obtain a clearer and more accurate CT image; the virtual prosthesis of the bone defect area is designed into a precise and uniform micron-sized porous structure, and the corresponding pore size and porosity of the bone repair support are designed to be 300 mu m through the bone repair support design component 13 according to the precision degree of matched 3D printing equipment.
When the microporous bone repair scaffold is manufactured by printing the bone repair scaffold printing part 143D, a mode of combining graphene oxide with a biological ceramic material (zirconium oxide, hydroxyapatite, beta-tricalcium phosphate) is adopted, oxygen-containing functional groups on the graphene oxide are increased, so that the property is more active, the property can be improved through various reactions with the oxygen-containing functional groups, and the proportioning data is as follows (in weight ratio): 3% of graphene, 58% of zirconium oxide, 39% of hydroxyapatite and 39% of beta-tricalcium phosphate, adopting a micro-stereolithography 3D printing method, designing a microporous bone repair bracket mode according to three-dimensional modeling, and dividing micro-stereolithography into a scanning micro-stereolithography technology and a surface projection micro-stereolithography technology according to different layer forming and curing modes, wherein the surface projection micro-stereolithography technology is adopted in the embodiment, as shown in figure 13, layering and slicing are carried out on a three-dimensional CAD digital model according to a certain thickness by using layering software, each layer of slices is converted into a bitmap file, each bitmap file is input into a dynamic mask, and the resin liquid level is cured one layer at a time according to a graph displayed on the dynamic mask.
The microporous composite bioceramic bone repair scaffold prepared by the preparation method of the microporous composite bioceramic bone repair scaffold comprises a repair scaffold body matched with the defect form of a jaw segment as shown in fig. 4 and 5, and the repair scaffold body comprises overlapping bodies as shown in fig. 6The scaffold comprises a plurality of added scaffold layers, wherein each scaffold layer is provided with a plurality of micron-sized micropores, as shown in figure 7, a plurality of micropores between each layer form a plurality of polyhedrons, the polyhedrons are connected through the micropores, the polyhedrons and the micropores can be used for human bone tissues and cell circulation and attachment, the full contact between a repair scaffold body and tissue cells is facilitated through a polyhedron structure, so that the printed biological material is more favorable for the attachment growth of the cell tissues, and the micropores are quadrilateral; the area of the hole is 0.08mm2A novel porous-structure repairing ceramic scaffold with a fine structure is manufactured by the steps of fully contacting a cell tissue with a repairing scaffold, printing and manufacturing a fine micropore with a shape matched with a bone defect area, and printing a composite material model of graphene, zirconium oxide, hydroxyapatite and β -tricalcium phosphate, preparing β -tricalcium phosphate printing ink by using 35% of hydroxyapatite, 35% of β -tricalcium phosphate powder, 10% of dilute citric acid and potassium dihydrogen phosphate, 10% of silicon dioxide and zinc oxide and 10% of paraffin microspheres according to the weight percentage, preparing zirconium oxide printing ink by using 6% of graphene, 76% of zirconium oxide, anhydrous ethanol, 6% of polyacrylic acid and ammonium polyacrylate, 6% of polyethylene glycol and polyvinylpyrrolidone, 6% of citric acid and oleic acid according to the weight percentage, selecting a 150-micron nozzle with the walking speed of 100mm/min and the interval between layers on the X, Y, Z axis of 100 μm and 400 μm, completing spraying photosensitive curing of dissolving pulp by a 3D printer, sintering and molding the scaffold at a specific temperature, manufacturing the novel porous-structure repairing ceramic scaffold with a fine structure, and manufacturing the porous-structure repairing ceramic scaffold, and being close to the ceramic scaffold with larger bone fracture strength and larger stress bearing standard ceramic scaffold.
Examples 2 to 3
As shown in Table 2, the printing ink composition of the present invention differs from that of example 1 in the weight percentages of the components of the printing material and the weight percentages of the components of the printing ink of hydroxyapatite, β -tricalcium phosphate and zirconia, and the other technical means are the same as those of example 1.
Table 2: EXAMPLES 1-33D, hydroxylapatite, beta-tricalcium phosphate, and zirconia printing inks
In summary, by adjusting the proportions of the components of the graphene and the biological ceramic material, the electrical conductivity and the high toughness of the graphene material, the high strength and the wear resistance of the zirconia, and the good bone induction activity of the hydroxyapatite and the beta-tricalcium phosphate, the physical properties of the new material, such as the compressive strength, the elastic modulus, the fracture toughness and other indexes, are closer to those of natural bone tissues, the material can bear larger stress and deform without fracture, and the abrasion between the material and adjacent tissues is reduced.
Due to the addition of the graphene material, the conductivity of the composite ceramic material is improved, and the differentiation and osteogenesis efficiency of osteoblasts can be greatly improved by an auxiliary means of applying micro-current stimulation, so that the aim of remarkably shortening the clinical healing time is fulfilled.
With high accuracy 3D printing technique and equipment, make the microstructure of printing material more and more accurate, porous microstructure printing technique with receiving the nanometer scale as the representative, greatly improved the spatial structure and the biological performance of material, it includes a plurality of layers of support layers of superpose mutually to restore the support body, each support layer all is equipped with a plurality of micron order micropore, a plurality of micropore between each layer constitute a plurality of polyhedrons, make the polyhedron that the micropore constitutes can make the biomaterial of printing more be favorable to the adhesion growth of cell tissue with histiocyte full contact.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the invention, and all equivalent changes and modifications made in the claims of the present invention should be included in the scope of the present invention.
Claims (10)
1. The microporous composite biological ceramic bone repair support is characterized by comprising a repair support body made of composite materials, wherein the repair support body comprises a plurality of superposed support layers, each support layer is provided with a plurality of micron-sized micropores, and a plurality of micropores between each layer form a plurality of polyhedrons.
2. The microporous composite bioceramic bone repair scaffold according to claim 1, wherein the composite material comprises, in weight percent: 1-5% of graphene, 50-60% of zirconia, 20-40% of hydroxyapatite and beta-tricalcium phosphate.
3. The microporous composite bioceramic bone repair scaffold according to claim 1, wherein the micropores are in the shape of any one or more of a triangle or a quadrilateral.
4. The microporous composite bioceramic bone repair scaffold according to claim 1, wherein the polyhedrons are connected by micropores, and both the polyhedrons and the micropores allow for human bone tissue, cell flow and attachment.
5. A method for preparing a microporous composite bioceramic bone repair scaffold according to any one of claims 1-4, the method comprising:
s1, collecting the CT image data of jaw bone segment defect;
s2: converting the acquired CT image data into a digital image model;
s3: designing a virtual bone repair support with a micron-sized porous structure according to a digital model;
s4: according to the designed virtual repair support, 3D printing manufacturing is carried out on the microporous bone repair support by combining graphene and a biological ceramic material;
s5: and sintering and forming the micropore bone repairing support after the 3D printing is finished.
6. The method for preparing the microporous composite biological ceramic bone repair scaffold according to claim 5, wherein S4 comprises:
s41: printing materials are prepared according to the following weight percentage: 1-5% of graphene, 50-60% of zirconia, 20-40% of hydroxyapatite and beta-tricalcium phosphate.
And S42, finishing spraying of the dissolving pulp according to the prepared material by a 3D printer, and carrying out photosensitive curing.
7. The preparation method of the microporous composite biological ceramic bone repair scaffold according to claim 6, wherein the proportion of printing ink in printing hydroxyapatite and beta-tricalcium phosphate is as follows: 20 to 40 percent of hydroxyapatite, 20 to 40 percent of beta-tricalcium phosphate powder, 5 to 15 percent of dilute citric acid and potassium dihydrogen phosphate, 5 to 15 percent of silicon dioxide and zinc oxide and 5 to 15 percent of paraffin wax microsphere.
8. The preparation method of the microporous composite biological ceramic bone repair scaffold according to claim 6, wherein the proportion of printing ink in the zirconia printing process is as follows by weight percent: 5-10% of graphene, 60-80% of zirconia, 5-10% of absolute ethyl alcohol, 5-10% of polyacrylic acid and ammonium polyacrylate, 5-10% of polyethylene glycol and polyvinylpyrrolidone, and 5-10% of citric acid and oleic acid.
9. The method for preparing a scaffold for bone repair from bio-ceramic having micro pores according to claim 6, wherein in S42, the spraying nozzle has a nozzle size of 140 μm to 160 μm and a traveling speed of 90mm/min to 110 mm/min.
10. A device for preparing a microporous composite bioceramic bone repair scaffold according to any one of claims 1-4, comprising:
a data acquisition component: collecting the CT image data of the jaw bone segment defect;
a data conversion section: converting the acquired CT image data into a digital image model;
bone repair scaffold design component: designing a virtual bone repair support with a micron-sized porous structure according to a digital model;
bone repair support printing component: according to the designed virtual repair support, 3D printing manufacturing is carried out on the microporous bone repair support by combining graphene and a biological ceramic material;
sintering the molded part: and sintering and forming the micropore bone repairing support after the 3D printing is finished.
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