CN116275117A - Preparation method of porous artificial bone with adjustable pore structure and porous artificial bone - Google Patents
Preparation method of porous artificial bone with adjustable pore structure and porous artificial bone Download PDFInfo
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- CN116275117A CN116275117A CN202310329957.XA CN202310329957A CN116275117A CN 116275117 A CN116275117 A CN 116275117A CN 202310329957 A CN202310329957 A CN 202310329957A CN 116275117 A CN116275117 A CN 116275117A
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 43
- 239000011148 porous material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 19
- 229920005596 polymer binder Polymers 0.000 claims abstract description 17
- 239000002491 polymer binding agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000007639 printing Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims description 18
- 238000005238 degreasing Methods 0.000 claims description 13
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 10
- 239000004626 polylactic acid Substances 0.000 claims description 10
- 229910000883 Ti6Al4V Inorganic materials 0.000 claims description 9
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 4
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 26
- 239000000654 additive Substances 0.000 abstract description 3
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010146 3D printing Methods 0.000 abstract description 2
- 238000000498 ball milling Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 3
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- 238000001704 evaporation Methods 0.000 description 3
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- 238000002513 implantation Methods 0.000 description 1
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B22F10/38—Process control to achieve specific product aspects, e.g. surface smoothness, density, porosity or hollow structures
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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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
- A61L27/56—Porous materials, e.g. foams or sponges
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B22—CASTING; POWDER METALLURGY
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
- B22F10/16—Formation of a green body by embedding the binder within the powder bed
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B22F10/64—Treatment of workpieces or articles after build-up by thermal means
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- 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
- B33Y10/00—Processes of additive manufacturing
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- B33Y70/00—Materials specially adapted for additive manufacturing
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- A61L2430/00—Materials or treatment for tissue regeneration
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Abstract
The invention discloses a porous artificial bone preparation method with an adjustable pore structure and a porous artificial bone, belonging to the field of metal 3D printing in the field of additive manufacturing, comprising the preparation of a polymer binder, the preparation of metal slurry, the printing of sample prototypes with different internal pore structures and the heat treatment of the samples; compared with the prior art, the method for preparing the metal slurry by mixing the polymer binder and the metal powder is simple and low in cost. Because no laser and other equipment is needed, the manufactured stent sample lines have no residual powder, the surfaces of the struts are smooth, the connectivity of the pores in the stent is good, and higher resolution and printing precision can be achieved. Through designing the support structure and comprehensively adjusting different internal pore structures, the permeability and the mechanical property can be simultaneously adjusted, the requirements of the human skeleton on the permeability and the mechanical property can be simultaneously met, and the bone tissue engineering support can be used for customizing bone tissue engineering supports of different people or different parts of the human body.
Description
Technical Field
The invention relates to the field of metal 3D printing in the field of additive manufacturing, in particular to a porous artificial bone preparation method with an adjustable pore structure and a porous artificial bone.
Background
As an additive manufacturing method, slurry direct writing (Direct ink writing, DIW) has been attracting attention in the field of artificial bones in recent years. The polymer solvent or particles are mixed to form a flowable slurry of uniform nature, the viscosity of which ensures extrusion of the strands in a nozzle of a certain internal diameter, and which maintains a certain shape after extrusion, ensuring its forming ability. The extruded lines are moved according to a path designed by slicing software to form a certain shape in the horizontal plane of the substrate, the substrate is sunk one layer, printing of a second layer is carried out, and the process is repeated until the whole three-dimensional structural member is processed and molded. The ideal artificial bone penetration performance and mechanical performance must be kept similar to the host bone tissue to generate good biological reaction with the host bone in vivo, thereby ensuring normal function after implantation. However, regardless of the processing method of the metal artificial bone, the permeability is greatly related to the mechanical properties, and the permeability tends to be linearly increased with the increase of the porosity, while the mechanical properties tend to be linearly reduced. The two characteristics of the permeability and the mechanical property are synchronously regulated, the mechanical property of the bracket cannot be reduced on the premise of ensuring the permeability of the artificial bone, the linear rule is difficult to break through, and a new parameter regulating mode is difficult to find. Therefore, it is difficult to match both the penetration performance and the mechanical performance to the bone tissue of the human body at the same time. Therefore, a preparation method of the porous artificial bone with an adjustable pore structure and the porous artificial bone are provided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a porous artificial bone with an adjustable pore structure and the porous artificial bone, and the performance of the porous artificial bone is changed by adjusting the pore structure.
The aim of the invention can be achieved by the following technical scheme:
the first aspect of the present application provides a method for preparing a porous artificial bone with an adjustable pore structure, comprising:
polylactic acid PLA and dichloromethane DCM were mixed according to 1: (3-5) uniformly mixing the components according to the mass ratio to obtain a polymer binder; uniformly mixing a polymer binder and metal powder according to the mass ratio of 1 (2-4) to obtain slurry;
performing DIW printing by taking the slurry as a raw material to obtain a sample; wherein the sample is of a cylindrical layered structure, each layer of the sample consists of linear uniformly distributed lines, and meshes formed by the lines of adjacent layers are of convex polygon shapes; degreasing and sintering the sample, and cooling to obtain the porous artificial bone.
In some embodiments, the mesh is one of triangular, rectangular, or prismatic in shape.
In some embodiments, the mesh shapes and sizes of adjacent layers are the same; the mesh of the adjacent layer is offset at the n+2 layer relative to the nth layer.
In some embodiments, the mesh shapes of adjacent layers are the same; the size of the mesh hole is reduced or enlarged from top to bottom.
In some embodiments, the degreasing and sintering atmosphere of the sample is 3Pa or less;
degreasing temperature is 300 ℃, degreasing time is 30-60min, and heating rate from room temperature to 300 ℃ is 6-10 ℃/min;
the sintering temperature is 1200 ℃, the sintering time is 90-150min, and the temperature is raised to the sintering temperature at the heating rate of 6-10 ℃/min after degreasing.
In some embodiments, the conical nozzle in DIW printing extrudes the slurry at a pressure of 0.3 to 0.6 MPa; the inner diameter of the conical spray head was 260 microns.
In some embodiments, the metal powder is Ti6Al4V powder.
In some embodiments, each layer of the sample has a layer height of 180 to 240 microns and a print speed of 15mm/s per layer.
In some embodiments, the sample has a post-sintering cooling time of 12 to 24 hours.
A second aspect of the present application provides a porous artificial bone prepared by the method of any one of the first aspects.
The invention has the beneficial effects that:
the invention prepares the metal slurry by mixing the polymer binder with the metal powder, so the method is simple and the cost is lower. And because the metal slurry which is uniformly mixed is extruded by adopting the nozzle, the lines forming the bracket are uniform in thickness and orderly arranged, and higher resolution and printing precision can be achieved. Since no laser or other equipment is needed, the produced stent sample lines have no residual powder inside, the surface of the struts is smooth, no agglomerated particles and particles which are not completely melted are attached, and the connectivity of pores inside the stent is ensured. The entire prototype of the sample was sintered and formed at the same time, so that no local residual stress was present. The penetration and mechanical properties of human bone tissue vary from region to region, and are closely related to the internal pore structure. Different internal pore structures are comprehensively regulated through designing the bracket structure, so that the requirements of the human skeleton on permeability and mechanical properties are met at the same time, and the bracket can be used for customizing bone tissue engineering brackets of different groups or different parts of the human body.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an optical view of a sample of a different structural stent of the present application;
FIG. 2 is a graph of pressure drop and permeability values for upper and lower surfaces of different structural scaffolds of the present application;
fig. 3 is a graph of elastic modulus and yield strength for different structural scaffolds of the present application.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be understood that the terms "open," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like indicate orientation or positional relationships, merely for convenience in describing the present invention and to simplify the description, and do not indicate or imply that the components or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the present invention.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Polylactic acid PLA in the embodiment of the application is 4032D selected from Nature works LLC; dichloromethane DCM is selected from Tianjin far chemical reagent Co., ltd
Example 1
Comprises the following steps:
(1) Preparation of polymeric binders
Polylactic acid PLA was used in an amount of 1: the mass ratio of 3 was dissolved in dichloromethane DCM to prepare a polymer binder, which was left to stand at room temperature for 24 hours until homogenized for preparing a metal paste.
(2) Preparation of metal paste
Mixing the prepared polymer binder with Ti6Al4V powder, wherein the mass ratio of the polymer binder to the metal powder is 1:2, pouring the mixture into a ball milling tank for ball milling and mixing, and mixing for 20 minutes at a rotating speed of 500 r/min;
(3) Printing sample prototypes based on DIW
The mixed slurry was transferred to a conical nozzle with an inner diameter of 260 microns by extrusion at a pressure of 0.3 MPa. The parameters for printing are: the layer height was 180 microns, and the XY movement speed was 10 mm/s. Different structures of the designed bracket are led into slicing software, and the bracket is manufactured layer by layer under the drive of a three-dimensional motion platform controlled by a slicing software program. The printed prototype was left at room temperature for 12 hours, ensuring complete evaporation of dichloromethane DCM, yielding the prototype.
(4) Sample heat treatment
And (3) placing the prototype part into a vacuum sintering furnace, vacuumizing to reach an air pressure environment below 3Pa, and degreasing and sintering by using a tube furnace diffusion pump. The sample is degreased at 300 ℃ for 30min at a heating rate of 6 ℃/min from room temperature to 300 ℃ and then is heated to 1200 ℃ at a heating rate of 6 ℃/min for 90min to sinter Ti6Al4V powder, and finally is cooled with a furnace and is taken out at room temperature.
Example 2
Comprises the following steps:
(1) Preparation of polymeric binders
Polylactic acid PLA was used in an amount of 1: the mass ratio of 4 was dissolved in dichloromethane DCM to prepare a polymer binder, which was left to stand at room temperature for 30 hours until homogenized for preparing a metal paste.
(2) Preparation of metal paste
Mixing the prepared polymer binder with Ti6Al4V powder, wherein the mass ratio of the polymer binder to the metal powder is 1:3, pouring the mixture into a ball milling tank for ball milling and mixing, and mixing for 30 minutes at a rotating speed of 600 r/min;
(3) Printing sample prototypes based on DIW
The mixed slurry was transferred to a conical nozzle with an inner diameter of 260 microns by extrusion at a pressure of 0.4 MPa. The parameters for printing are: the layer height was 210 microns, and the XY movement speed was 12 mm/s. Different structures of the designed bracket are led into slicing software, and the bracket is manufactured layer by layer under the drive of a three-dimensional motion platform controlled by a slicing software program. The printed prototype was left at room temperature for 18 hours, ensuring complete evaporation of dichloromethane DCM, yielding the prototype.
(4) Sample heat treatment
And (3) placing the prototype part into a vacuum sintering furnace, vacuumizing to reach an air pressure environment below 3Pa, and degreasing and sintering by using a tube furnace diffusion pump. The sample is degreased at 300 ℃ under the heating rate of 8 ℃/min from room temperature to 300 ℃ and kept at 1200 ℃ for 120min under the heating rate of 8 ℃/min to sinter Ti6Al4V powder, and finally cooled with a furnace and taken out at room temperature.
Example 3
Comprises the following steps:
(1) Preparation of polymeric binders
Polylactic acid PLA was used in an amount of 1: the polymer binder was prepared by dissolving the mass ratio of 5 in dichloromethane DCM, and the polymer binder was left to stand at room temperature for 36 hours until homogenized for preparing a metal paste.
(2) Preparation of metal paste
Mixing the prepared polymer binder with Ti6Al4V powder, wherein the mass ratio of the polymer binder to the metal powder is 1:4, pouring the mixture into a ball milling tank for ball milling and mixing, and mixing for 40 minutes at a rotating speed of 700 r/min;
(3) Printing sample prototypes based on DIW
The mixed slurry was transferred to a conical nozzle with an inner diameter of 260 microns by extrusion at a pressure of 0.6 MPa. The parameters for printing are: the layer height was 240 microns, and the XY movement speed was 15mm/s. Different structures of the designed bracket are led into slicing software, and the bracket is manufactured layer by layer under the drive of a three-dimensional motion platform controlled by a slicing software program. The printed prototype was left at room temperature for 24 hours, ensuring complete evaporation of dichloromethane DCM, yielding the prototype.
(4) Sample heat treatment
And (3) placing the prototype part into a vacuum sintering furnace, vacuumizing to reach an air pressure environment below 3Pa, and degreasing and sintering by using a tube furnace diffusion pump. The sample is degreased at 300 ℃ under the heating rate of 10 ℃/min from room temperature to 300 ℃ and is then heated to 1200 ℃ under the heating rate of 10 ℃/min for 150min to sinter Ti6Al4V powder, and finally is cooled with a furnace and is taken out after being cooled to room temperature.
The invention is further illustrated by performance test simulations and experiments.
The permeability and mechanical properties of the processed metal artificial bone scaffold are verified, and the scaffold with 12 different internal pore structures including angle rotation, line deflection, gradient, conventional structure and the like is designed and tested by a method combining numerical simulation and experiment. Scaffolds of 12 different internal pore structures were designated as Rotation15, rotation30, rotation45, rotation60, shifted50, shifted100, gradient I, gradient II, porosity40, porosity50, porosity60, porosity70% respectively. Wherein, the porosities of the Rotation 15%, the Rotation 30%, the Rotation 45%, the Rotation 60%, the Shifted50%, the Shifted100%, the Gradient I and the Gradient II are 50%, and the porosities are 50% and 50% of the porosities are the control group.
Wherein the angular Rotation group: the angle of lay between the stent layers varies from layer to layer, the upper layer of the stent always being rotated clockwise by a specific angle (pitch angles γ=15 °, 30 °, 45 °, 60 °) with respect to the next layer, while maintaining a porosity of 50%.
Line offset Shifted groups: the stent is designed in an orthogonal grid pattern (the laying angle of the adjacent layer lines is 0 DEG/90 DEG), unlike conventional stents where the alternating layers are perfectly aligned, the line shifting structure shifts at the n+2 layer relative to the n-th layer lines while maintaining a porosity of 50%.
Gradient structure Gradient group: the stent is designed in an orthogonal grid pattern (the laying angle of the lines of the adjacent layers is 0 DEG/90 DEG), and the gradient structure realizes gradient change of porosity by gradually increasing or decreasing the distance between the lines, unlike the conventional stent in which the alternating layers are completely aligned.
Conventional structured porosities group: all the brackets are in a traditional orthogonal grid pattern (the laying angle of the adjacent layer lines is 0 degree/90 degree), and the porosity of each bracket structure is changed.
As fig. 1 is an optical image of a sintered Ti6Al4V stent sample, we can clearly see the characteristic differences in internal pore structure between stent samples.
Fig. 2 is a graph of permeability values for different structural scaffolds. In terms of permeability, CFD simulation and permeability experiments show that the angular rotation and line offset enable the pressure drop of fluid passing through the stent to be larger, and the permeability of the stent is reduced. Both gradient structures had similar pressure drop and permeability, with reduced permeability compared to the control porosities of 50%. For conventional structures, permeability increases with increasing porosity.
Fig. 3 is a graph of elastic modulus and yield strength curves for different structural scaffolds. In terms of mechanical properties, it was found by FEA simulation and compression experiments that the elastic modulus and yield strength of the scaffold increased with rotation of angle and decreased with increasing porosity. The rotation of the angle reduced the elastic modulus and yield strength of the scaffold compared to the control porosities of 50%. The deflection of the strands reduces the elastic modulus and yield strength, and the gradient structure reduces the elastic modulus and yield strength of the stent.
In terms of permeability, rotation of the angle reduces the permeability by 35.35% -66.29%. The offset of the lines reduced the permeability by 27.63% and 61.67%. The two gradient structures have similar permeability, and compared with the control group, the permeability is reduced by 12.03% and 16.15%. Porosity increased from 40% to 70% and permeability increased by 813.75%. As can be seen from the results, the internal pore structure has a permeability adjustment range of 1.75 to 14.62X10 -9 m 2 Meets the requirements of the literature report on the trabecular permeability of human bones (2.56 multiplied by 10) -11 -7.43×10 -8 m 2 ). The change of the internal pore structure can regulate the porosity, and the bone tissue engineering scaffold meeting the permeability requirements of different parts of the human body is obtained.
In terms of mechanical properties, the elastic modulus and yield strength of the scaffold increases with angular rotation and decreases with increasing porosity. Compared with the control group of porosities of 50%, the elastic modulus of the stent is reduced by 12.78-90.98%, and the yield strength is reduced by 10.66-82.64%. The deflection of the lines reduces the elastic modulus and yield strength by 45.11% -60.90% and 23.99% -29.39%, respectively. The mechanical properties of the two gradient structures are similar, and the elastic modulus and the yield strength of the bracket are reduced by about 66% and about 73%. The elastic modulus and the yield strength of the bracket are reduced along with the increase of the porosity, the porosity is increased from 40% to 70%, and the elastic modulus and the yield strength are increased by about 70%. Through experiments, the range of the elastic modulus of the internal pore structure can be found to be 1.2-17.3GPa, the requirement range (0.1-4.5 GPa) of the trabecula of the human body is met, the range of the yield strength is 24.1-179.8MPa, and the elastic modulus is obviously higher than the requirement range (0.9-7.4 MPa) of the trabecula of the bone, so that stress shielding is avoided, and the bearing function is met.
Simulation and experimental results prove that the requirements of the mechanical property and the permeability of human bones can be met by comprehensively adjusting the internal pore structure.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. A method for preparing a porous artificial bone with an adjustable pore structure, which is characterized by comprising the following steps:
polylactic acid PLA and dichloromethane DCM were mixed according to 1: (3-5) uniformly mixing the components according to the mass ratio to obtain a polymer binder; uniformly mixing a polymer binder and metal powder according to the mass ratio of 1 (2-4) to obtain slurry;
performing DIW printing by taking the slurry as a raw material to obtain a sample; wherein the sample is of a cylindrical layered structure, each layer of the sample consists of linear uniformly distributed lines, and meshes formed by the lines of adjacent layers are of convex polygon shapes; degreasing and sintering the sample, and cooling to obtain the porous artificial bone.
2. The method for preparing a porous artificial bone with an adjustable pore structure according to claim 1, wherein the mesh is one of triangular, rectangular or prismatic.
3. The method for preparing a porous artificial bone with an adjustable pore structure according to claim 2, wherein the mesh shapes and sizes of the adjacent layers are the same; the mesh of the adjacent layer is offset at the n+2 layer relative to the nth layer.
4. The method for preparing a porous artificial bone with an adjustable pore structure according to claim 2, wherein the mesh shapes of adjacent layers are the same; the size of the mesh hole is reduced or enlarged from top to bottom.
5. The method for preparing a porous artificial bone with an adjustable pore structure according to claim 1, wherein the degreasing and sintering air pressure environment of the sample is below 3 Pa;
degreasing temperature is 300 ℃, degreasing time is 30-60min, and heating rate from room temperature to 300 ℃ is 6-10 ℃/min;
the sintering temperature is 1200 ℃, the sintering time is 90-150min, and the temperature is raised to the sintering temperature at the heating rate of 6-10 ℃/min after degreasing.
6. The method for preparing porous artificial bone with adjustable pore structure according to claim 1, wherein the conical nozzle in DIW printing extrudes the slurry at a pressure of 0.3-0.6 MPa; the inner diameter of the conical spray head was 260 microns.
7. The method for preparing a porous artificial bone with an adjustable pore structure according to claim 1, wherein the metal powder is Ti6Al4V powder.
8. The method for preparing a porous artificial bone with an adjustable pore structure according to claim 1, wherein the layer height of each layer of the sample is 180-240 micrometers, and the printing speed of each layer is 15mm/s.
9. The method for preparing a porous artificial bone with an adjustable pore structure according to claim 1, wherein the cooling time after sintering of the sample is 12-24 hours.
10. A porous artificial bone prepared by the preparation method of any one of claims 1 to 9.
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