CN115957374A - Metal artificial bone implant with core-shell structure and preparation method thereof - Google Patents
Metal artificial bone implant with core-shell structure and preparation method thereof Download PDFInfo
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- 239000007943 implant Substances 0.000 title claims abstract description 38
- 239000011258 core-shell material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention discloses a metal artificial bone implant with a core-shell structure and a preparation method thereof, belongs to the technical field of additive manufacturing, and prepares a degradable Fe-HA metal artificial bone implant with the core-shell structure by adopting an additive manufacturing technology based on a slurry direct writing technology. The method comprises the following steps: providing mixed slurry prepared by a binder, pure iron powder and hydroxyapatite powder according to a proportion, respectively placing the mixed slurry into a charging barrel connected with a shell needle tube and a charging barrel connected with an inner core, fixing the mixed slurry on a three-dimensional platform, moving the mixed slurry along a preset path under the driving of the platform, extruding the two kinds of slurry into lines by coaxial needle tubes, and forming a multi-layer ordered porous structure on the platform; and sequentially pre-burning and sintering the three-dimensional porous structure to obtain the Fe-HA metal artificial bone implant.
Description
Technical Field
The invention belongs to the technical field of additive manufacturing, and particularly relates to a metal artificial bone implant with a core-shell structure and a preparation method thereof.
Background
In the modern society, as more and more people face the problem of bone health, the problem of incurable severe bone trauma such as severe bone defect and bone diseases by implanting the degradable metal artificial bone implant becomes an excellent choice.
The high-quality degradable metal artificial bone implant can provide enough mechanical support to meet the daily behavior movement of a patient after being implanted into the body of the patient, provides a bracket for bone cells and bone tissues to grow and attach in the generation and growth processes of new bones of the human body, and simultaneously gradually degrades along with the growth of the new bones, and gradually transfers the borne mechanical stress to the new bones. When the new bone grows completely, the implant is degraded and metabolized completely, the treatment course of bone trauma is finished, and the patient is cured.
The preparation of the high-quality degradable metal artificial bone needs attention to the following four aspects:
1) Highly customized complex junctions. As an alternative to human bone, it is desirable that artificial bone implants have a geometry and size that conforms to the patient's wound. In addition, the artificial bone implant also needs to have certain porosity (> 30% -70%), pore size (100-500 μm) and three through pore canals to meet the requirements of nutrient delivery, metabolite discharge and cell growth;
2) Excellent biological property. When the metal artificial bone implant is implanted into a body, no systemic or local toxic reaction, no blood coagulation, stimulation and other adverse reactions occur, and meanwhile, osteoinductivity is required, so that new bones can be formed under the induction of biomolecule signals;
3) Sufficient mechanical properties. When the metal artificial bone implant is implanted into a body, the metal artificial bone implant can provide enough mechanical support for the daily behavior movement of a patient, and has proper mechanical properties such as elastic modulus and the like so as to avoid the stress shielding phenomenon from influencing the surrounding primary bone;
4) An adapted degradation rate. After the metal artificial bone implant is implanted into a body, along with the regeneration and reconstruction of bone tissues, the artificial bone implant is gradually degraded and replaced by new bone, and finally the repair of bone defects is realized. Thus, it is desirable that the rate of degradation of the artificial bone implant be matched to the rate of regeneration and reconstruction of bone tissue. At the same time, the degradation products of the implant must not be toxic.
Currently, the primary means for preparing artificial bone implants is additive manufacturing, i.e., 3D printing. The 3D printing forming capability is strong, the forming is restrained little, and the artificial bone implant which meets the implantation requirement and has a shape structure can be manufactured easily. The invention provides a method for preparing a degradable metal artificial bone implant with a core-shell structure based on 3D printing, which aims to solve the problem that the conventional artificial bone implant cannot perform cooperative regulation and control on the porosity and the degradation rate of the structure.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a metal artificial bone implant with a core-shell structure and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a metallic artificial bone implant, comprising the following raw materials: iron powder and hydroxyapatite;
the shell material of the metal artificial bone implant comprises iron and hydroxyapatite, the core material comprises iron, and the shell and the core form a core-shell structure.
A method of making a metallic artificial bone implant, comprising the steps of:
weighing absolute ethyl alcohol serving as a solvent and polyvinylpyrrolidone serving as a polymer, and dissolving the polymer and the solvent in a container to prepare a slurry binder;
respectively drying iron powder and hydroxyapatite powder, and then grinding to obtain powder;
weighing iron powder and hydroxyapatite powder to obtain mixed powder, and grinding the slurry binder and the mixed powder to obtain shell slurry;
mixing and grinding the slurry binder and iron powder to obtain the core slurry,
printing slurry, namely respectively putting the shell slurry and the core slurry into a printing mechanism, and stacking the printed mixed slurry wires to form a three-dimensional structure to obtain a metal bracket;
and carrying out heat treatment on the metal bracket.
The invention has the beneficial effects that:
the invention has the advantages that: the volume ratio of the mixed powder in the metal bracket can reach 80 percent, and the shrinkage degree after sintering can be sufficiently reduced, so that the deviation of the obtained dimension and the designed dimension is reduced to the minimum; the method does not need to use laser, electron beam and other methods for repairing, reduces equipment and processing cost, is safer and more reliable, and the whole processed part is sintered and molded simultaneously without local residual stress;
in addition, the design of the core-shell structure improves the performance of the artificial bone sample piece, has the advantages of biological ceramic materials, biological metal materials and common biological ceramic-biological metal mixed structure materials, and improves the defects of the two materials:
(1) The iron structure of the core ensures the overall mechanical property of the sample piece, and improves the elastic modulus, compressive strength, yield strength, toughness and the like;
(2) The iron-hydroxyapatite structure of the shell improves the biological properties such as biocompatibility, biological inductivity and the like of the exterior of the sample piece after the sample piece is contacted with the internal environment of a living body;
(3) The same iron materials of the core and the shell ensure that the core and the shell of the printing line are not easy to delaminate and disjunction, thereby ensuring the structural effectiveness of the sample piece;
(4) The preparation of the degradable artificial bone can be realized by adopting the metal material mainly containing iron, the artificial bone is gradually degraded along with the growth of new bone, the mechanical load is gradually transferred to the new bone, and the secondary operation of taking out the artificial bone is avoided;
(5) The addition of the hydroxyapatite can accelerate the degradation rate of the iron, so that the degradation rate of the iron-hydroxyapatite metal artificial bone implant can be adjusted on the basis of not changing the structural pores;
(6) The iron-hydroxyapatite structure of the shell has a higher degradation rate, the iron structure of the core has a relatively low degradation rate, and after being implanted into a body, the shell structure is degraded at a higher rate first to provide a bone growth space while the core structure maintains the second lower degradation rate to provide sufficient mechanical properties.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a flow chart for preparing an Fe-HA metallic artificial bone implant with a core-shell structure;
FIG. 2 is a schematic diagram of the principle of pneumatically extruded coaxial printing employed in the present invention;
FIG. 3 is a schematic view of the internal structure of a coaxial needle used in the present invention;
FIG. 4 is a table showing the change in compressive strength before and after 21 days of degradation for metallic artificial scaffolds with different porosities and different HA contents;
FIG. 5 is a table of the change in yield strength before and after 21 days degradation for metallic artificial scaffolds containing different amounts of HA for different porosities.
The reference numbers in the figures illustrate:
1. a gas supply device; 2. a push rod; 3. an inner core barrel; 4. a plug; 5. a clamp; 6. a conduit; 7. a carriage; 8. a coaxial needle; 9. an inner cavity; 10. an outer cavity.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, a metallic artificial bone implant with a core-shell structure and a method for preparing the same,
example 1:
(1) Preparing a binder, wherein the mass ratio of the solvent absolute ethyl alcohol to the polymer polyvinylpyrrolidone is weighed to be 0.9:1, dissolving a polymer and a solvent in a sealed container with an anti-corrosion function for 30 minutes at a drying environment of 80-90 ℃ to prepare a slurry binder with uniform property, fluidity and certain viscosity;
(2) Powder treatment, iron powder (D) 90 =43.4 μm) and hydroxyapatite powder (D) 90 =9.72 μm), respectively placing in a drying oven, drying at a constant temperature of 60 ℃ for 8h, then respectively placing in a ball mill to ball mill for 50 minutes at a rotating speed of 300 r/min, and obtaining dry powder without obvious agglomeration;
(3) Preparing shell slurry, weighing iron powder and hydroxyapatite according to a mass ratio of 39:1, placing the mixture into a ball mill according to a mass ratio of 5;
(4) Preparing core slurry, putting a slurry binder and iron powder into a ball mill according to the powder mass ratio of 1;
(5) Printing the slurry, putting the inner core slurry into the material barrel 3, putting the shell slurry into the material barrel 4, clamping by the clamp 6, connecting the inner cavity 9 of the coaxial needle 8 to the material barrel 3 and simultaneously connecting the material barrel 4 with the outer cavity 10 of the coaxial needle 8 by using the conduit 7. After the device is connected, 0.2-0.4MPa of stable air pressure is introduced through the air supply device 1, the air pressure pushes the push rod 2 to move forward to push the plug 5 in the charging barrel, so that pressure is formed on mixed slurry, the core slurry is extruded at a constant speed through the inner cavity 9 of the coaxial needle 8 below the charging barrel 3, and the shell slurry is conveyed to the outer cavity 10 of the coaxial needle 8 through the guide pipe 7 below the charging barrel 4 and extruded at a constant speed. The extruded mixed slurry is in a filiform shape, a circular inner core, an annular shell and an obvious two-phase interface are observed from the cross section, a polymer wraps metal powder for solidification and shaping due to the evaporation of a binder solvent in the slurry after extrusion, and mixed slurry wires printed in a mixed mode are stacked at the speed of 15mm/s to form a three-dimensional structure under the drive of a three-dimensional motion platform controlled by a slicing software program to obtain a metal support;
(6) And heat treating the stent, comprising:
1) Cleaning air and vacuumizing: and putting the metal support to be sintered into a vacuum sintering furnace, vacuumizing to reach an air pressure environment below 3Pa, filling inert gas (argon) to a room pressure state, and vacuumizing. The steps are repeated for 3 times to more effectively clean the original air in the furnace and reduce the influence of oxygen at high temperature on the metal bracket;
2) And pyrolysis of the binder: heating the vacuum sintering furnace to 300 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 1h to realize the complete pyrolysis of the binder;
3) And iron powder fusion: heating the vacuum sintering furnace to 1120 ℃ at the heating rate of 6 ℃/min, keeping the temperature for 3 hours, and sintering and fusing metal powder particles in the bracket under the condition of ensuring that the hydroxyapatite does not have phase change;
4) And cooling: after the metal support is fully sintered, inert gas (argon) is introduced to enable the sintering furnace to be separated from a vacuum state so as to enhance convective heat transfer and heat conduction and accelerate the cooling of the metal support. Argon gas was introduced and the sample was taken out after cooling for 1 hour.
The inner diameter of the inner core of the spray head is 0.26mm (25G), and the inner diameter of the outer shell of the spray head is 0.84mm (18G).
Example 2:
(1) Preparing a binder, wherein the mass ratio of the solvent absolute ethyl alcohol to the polymer polyvinylpyrrolidone is weighed to be 0.9:1, dissolving a polymer and a solvent in a sealed container with an anti-corrosion function for 30 minutes at a drying environment of 80-90 ℃ to prepare a slurry binder with uniform property, fluidity and certain viscosity;
(2) Powder treatment, iron powder (D) 90 =43.4 μm) and hydroxyapatite powder (D) 90 =9.72 mu m) are respectively placed into a drying box, the drying box is dried for 8 hours at the constant temperature of 60 ℃, and then the drying box is respectively placed into a ball mill to be ball-milled for 50 minutes at the rotating speed of 350 r/min, so that dry powder without obvious agglomeration is obtained;
(3) Preparing shell slurry, weighing iron powder and hydroxyapatite according to a mass ratio of 19 to 1, placing the mixture into a ball mill according to a mass ratio of 5;
(4) Preparing core slurry, putting a slurry binder and iron powder into a ball mill according to the powder mass ratio of 1;
(5) Printing the slurry, putting the inner core slurry into the material barrel 3, putting the shell slurry into the material barrel 4, clamping by the clamp 6, connecting the inner cavity 9 of the coaxial needle 8 to the material barrel 3 and simultaneously connecting the material barrel 4 with the outer cavity 10 of the coaxial needle 8 by using the conduit 7. After the device is connected, 0.2-0.4MPa of stable air pressure is introduced through the air supply device 1, the air pressure pushes the push rod 2 to move forward to push the plug 5 in the charging barrel, so that pressure is formed on mixed slurry, the core slurry is extruded at a constant speed through the inner cavity 9 of the coaxial needle 8 below the charging barrel 3, and the shell slurry is conveyed to the outer cavity 10 of the coaxial needle 8 through the guide pipe 7 below the charging barrel 4 and extruded at a constant speed. The extruded mixed slurry is in a filiform shape, a circular inner core, an annular shell and an obvious two-phase interface are observed from the cross section, a polymer wraps metal powder for solidification and shaping due to the evaporation of a binder solvent in the slurry after extrusion, and mixed slurry wires printed in a mixed mode are stacked at the speed of 12mm/s to form a three-dimensional structure under the drive of a three-dimensional motion platform controlled by a slicing software program to obtain a metal support;
(6) And heat treating the stent, comprising:
1) Cleaning air and vacuumizing: and putting the metal support to be sintered into a vacuum sintering furnace, vacuumizing to reach an air pressure environment below 3Pa, filling inert gas (argon) to a room pressure state, and vacuumizing. The steps are repeated for 3 times to more effectively clean the original air in the furnace and reduce the influence of oxygen at high temperature on the metal bracket;
2) And pyrolysis of the binder: heating the vacuum sintering furnace to 300 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 1h to realize the complete pyrolysis of the binder;
3) And iron powder fusion: heating the vacuum sintering furnace to 1120 ℃ at the heating rate of 6 ℃/min, keeping the temperature for 3 hours, and sintering and fusing metal powder particles in the bracket under the condition of ensuring that the hydroxyapatite does not have phase change;
4) And cooling: after the metal support is fully sintered, inert gas (argon) is introduced to enable the sintering furnace to be separated from a vacuum state so as to enhance convective heat transfer and heat conduction and accelerate the cooling of the metal support. Argon gas is introduced to cool the sample for 1 hour, and then the sample is taken out.
The inner diameter of the inner core of the nozzle tip in this example was 0.26mm (25G) and the inner diameter of the outer shell was 0.84mm (18G).
Example 3:
(1) Preparing a binder, wherein the mass ratio of the solvent absolute ethyl alcohol to the polymer polyvinylpyrrolidone is weighed to be 0.9:1, dissolving a polymer and a solvent in a sealed container with an anti-corrosion function for 30 minutes at a drying environment of 80-90 ℃ to prepare a slurry binder with uniform property, fluidity and certain viscosity;
(2) Powder treatmentMixing iron powder (D) 90 =43.4 μm) and hydroxyapatite powder (D) 90 =9.72 mu m), respectively putting into a drying oven, drying for 8h at a constant temperature of 60 ℃, respectively putting into a ball mill, and ball-milling for 50 min at a rotating speed of 400 r/min to obtain dry powder without obvious agglomeration;
(3) Preparing shell slurry, mixing iron powder and hydroxyapatite according to a mass ratio of 37:3, putting the slurry binder and the mixed powder in a mass ratio of 5;
(4) Preparing core slurry, putting a slurry binder and iron powder into a ball mill according to the powder mass ratio of 1;
(5) Printing the slurry, putting the inner core slurry into the material barrel 3, putting the shell slurry into the material barrel 4, clamping by the clamp 6, connecting the inner cavity 9 of the coaxial needle 8 to the material barrel 3 and simultaneously connecting the material barrel 4 with the outer cavity 10 of the coaxial needle 8 by using the catheter 7. After the device is connected, 0.2-0.4MPa of stable air pressure is introduced through the air supply device 1, the air pressure pushes the push rod 2 to move forward to push the plug 5 in the charging barrel, so that pressure is formed on mixed slurry, the core slurry is extruded at a constant speed through the inner cavity 9 of the coaxial needle 8 below the charging barrel 3, and the shell slurry is conveyed to the outer cavity 10 of the coaxial needle 8 through the guide pipe 7 below the charging barrel 4 and extruded at a constant speed. The extruded mixed slurry is filamentous, a circular inner core, an annular shell and an obvious two-phase interface are observed from the cross section, a polymer wraps metal powder for solidification and shaping due to the evaporation of a binder solvent in the slurry after extrusion, and mixed slurry wires printed in a mixed mode are stacked at the speed of 10mm/s to form a three-dimensional structure under the drive of a three-dimensional motion platform controlled by a slicing software program to obtain a metal support;
(6) And heat treating the stent, comprising:
1) Cleaning air and vacuumizing: and putting the metal support to be sintered into a vacuum sintering furnace, vacuumizing to reach an air pressure environment below 3Pa, filling inert gas (argon) to a room pressure state, and vacuumizing. The steps are repeated for 3 times to more effectively clean the original air in the furnace and reduce the influence of oxygen at high temperature on the metal bracket;
2) And pyrolysis of the binder: heating the vacuum sintering furnace to 300 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 1h to realize the complete pyrolysis of the binder;
3) And iron powder fusion: heating the vacuum sintering furnace to 1120 ℃ at the heating rate of 6 ℃/min, keeping the temperature for 3 hours, and sintering and fusing metal powder particles in the bracket under the condition of ensuring that the hydroxyapatite does not have phase change;
4) And cooling: after the metal support is fully sintered, inert gas (argon) is introduced to enable the sintering furnace to be separated from a vacuum state so as to enhance convective heat transfer and heat conduction and accelerate the cooling of the metal support. Argon gas is introduced to cool the sample for 1 hour, and then the sample is taken out.
The inner diameter of the inner core of the nozzle tip in this example was 0.26mm (25G) and the inner diameter of the outer shell was 0.84mm (18G).
The inner diameter of the inner core of the spray head is 0.26mm (25G), and the inner diameter of the outer shell is 0.84mm (18G).
As shown in fig. 2-3, the printing mechanism includes an inner core cylinder 3 and an outer core cylinder 4, the inner core cylinder 3 and the outer core cylinder 4 are respectively provided with a clamping fixture 6, the inner core cylinder 3 and the outer core cylinder 4 are respectively provided with a push rod 2, one end of the push rod 2 is fixedly provided with a plug 5, the push rod 2 is connected with an air supply device 1, the bottom end of the inner core cylinder 3 is connected with a coaxial needle 8, the bottom end of the outer core cylinder 4 is connected with the coaxial needle 8 through a conduit 7, as shown in fig. 4, the coaxial needle 8 includes an outer cavity 10 and an inner cavity 9.
As shown in fig. 4, in a table of the changes of compressive strengths of metallic artificial scaffolds with different porosities (30%, 50% and 70%) and different contents of HA (0, 2.5%,5%, 7.5%) before and after 21 days of degradation, in vitro degradation experiments were performed on samples with different mass fractions of HA, and subsequent mechanical property tests and degradation rate tests were performed, and the test results show that the increase of the content of HA can greatly weaken the mechanical properties of the samples, but can improve the degradation rate.
As shown in fig. 5, the table shows the yield strength change of the metal artificial bone scaffold with different porosities (30%, 50% and 70%) and different contents of HA (0, 2.5%,5%, 7.5%) before and after 21 days of degradation, and it can be proved by the table that the inner core Fe scaffold can provide high mechanical properties all the time during the degradation process to ensure the mechanical strength of the artificial bone.
The mass loss of samples containing different HA mass fractions (0, 2.5%,5% and 7.5%) at 50% porosity after 1 day, 3 days, 7 days and 21 days degradation tests is shown in the following table
From this table, it is understood that the degradation ability of the artificial bone is gradually enhanced as the HA content is increased.
The 3D printing technology adopted by the invention is Direct Ink Writing (DIW), which is a 3D printing mode of extrusion deposition molding: the polymer solvent is mixed with the required metal powder to prepare a uniform flowing slurry, and the slurry is extruded from a customized printing needle head to a substrate layer by layer according to a designated route for printing. In the printing process, the solvent in the printed lines is quickly volatilized, so that the lines are solidified and molded, and the whole sample piece is shaped. And after printing is finished, carrying out high-temperature heat treatment on the sample piece, so that the polymer in the sample piece is sublimated and the metal powder is partially fused with each other to form a real metal sample piece. The technology can be used for processing the artificial bone with the micro-structure pore, the cost is low, and the formed sample piece has no internal stress. Compared with the existing mainstream metal additive manufacturing technology, the slurry direct writing technology has the advantages of lower processing cost; the processing process is safe; the overall performance is guaranteed, and the like. In addition, the invention adopts a coaxial needle head to perform direct-writing printing of the sizing agent, and the coaxial needle head is divided into an inner cavity and an outer cavity which are respectively communicated with different sizing agents. The lines extruded by the coaxial needle head have a core-shell structure, and the advantages of the core-shell structure and the lines can be combined under proper configuration.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential 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, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (10)
1. A metallic artificial bone implant, comprising the following raw materials: iron powder and hydroxyapatite;
the shell material of the metal artificial bone implant comprises iron and hydroxyapatite, the core material comprises iron, and the shell and the core form a core-shell structure.
2. The metallic artificial bone implant according to claim 1, wherein the material further comprises a binder.
3. The shell raw material according to claim 1, wherein the mass ratio of iron to hydroxyapatite in the shell raw material is 37-119: 3.
4. a method of making a metallic artificial bone implant, comprising the steps of:
weighing absolute ethyl alcohol serving as a solvent and polyvinylpyrrolidone serving as a polymer, and dissolving the polymer and the solvent in a container to prepare a slurry binder;
respectively drying iron powder and hydroxyapatite powder, and then grinding to obtain powder;
weighing iron powder and hydroxyapatite powder to obtain mixed powder, and grinding the slurry binder and the mixed powder to obtain shell slurry;
mixing and grinding the slurry binder and iron powder to obtain the core slurry,
printing slurry, namely respectively putting the shell slurry and the core slurry into a printing mechanism, and stacking the printed mixed slurry wires to form a three-dimensional structure to obtain a metal bracket;
and carrying out heat treatment on the metal bracket.
5. The method for preparing a metallic artificial bone implant according to claim 4, wherein the mass ratio of the solvent absolute ethyl alcohol to the polymer polyvinylpyrrolidone is 0.9:1, the mass ratio of iron powder to hydroxyapatite in the mixed powder is 9-39, the mass ratio of the slurry binder to the mixed powder in the shell slurry is 1.
6. The method for preparing a metallic artificial bone implant according to claim 4, wherein the heat treatment of the metallic scaffold comprises the steps of:
and (3) putting the metal support into a vacuum sintering furnace, vacuumizing, heating the vacuum sintering furnace for sintering, and cooling and taking out the sample after the metal support is sintered.
7. The method as claimed in claim 6, wherein the evacuation is performed under a pressure of less than 3Pa, and the evacuation is performed after filling inert gas to a room pressure, and the above steps are repeated 3 times.
8. The method of claim 4, wherein the sintering is performed by introducing an inert gas and cooling.
9. The method for preparing an artificial bone implant according to claim 4, wherein the vacuum sintering furnace is heated to 300 ℃ for sintering for 0.5-1 h, and then the vacuum sintering furnace is heated to 1120 ℃ for sintering for 2-4 h.
10. Use of the method of preparation of a metallic artificial bone implant according to any of claims 4 to 9 for the preparation of a metallic artificial bone implant of core-shell structure.
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