CN113579227A - Preparation method of porous artificial bone capable of adjusting degradation rate based on slurry direct writing - Google Patents
Preparation method of porous artificial bone capable of adjusting degradation rate based on slurry direct writing Download PDFInfo
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- CN113579227A CN113579227A CN202110878940.0A CN202110878940A CN113579227A CN 113579227 A CN113579227 A CN 113579227A CN 202110878940 A CN202110878940 A CN 202110878940A CN 113579227 A CN113579227 A CN 113579227A
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- 238000006731 degradation reaction Methods 0.000 title claims abstract description 42
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
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- 238000005245 sintering Methods 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 27
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 22
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 11
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 11
- 239000011812 mixed powder Substances 0.000 claims abstract description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 33
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- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 claims description 3
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- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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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
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- 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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- 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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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/10—Formation of a green body
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- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
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- A—HUMAN NECESSITIES
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
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Abstract
The invention relates to a preparation method of a porous artificial bone capable of adjusting degradation rate based on slurry direct writing, and belongs to the field of additive manufacturing. The method comprises the steps of preparing mixed slurry from a binder prepared from dichloromethane and polylactic acid, pure iron powder and hydroxyapatite powder according to a proportion, putting the mixed slurry into a forming charging barrel, fixing the forming charging barrel on a platform, moving along a preset path under the driving of the platform to form a multi-layer ordered porous structure, and sequentially pre-burning and sintering the three-dimensional porous structure. The volume ratio of the mixed powder in the metal bracket can reach 80%, the shrinkage degree after sintering can be fully reduced, methods such as laser, electron beams and the like are not needed for repairing, the method is safer and more reliable, the whole part to be processed is sintered and molded at the same time, and local residual stress does not exist; due to the good biological activity and biocompatibility of the hydroxyapatite, the degradation rate of the porous artificial bone can be adjusted by adjusting the proportion of the hydroxyapatite, and meanwhile, the biological activity of the artificial bone is increased.
Description
Technical Field
The invention belongs to the field of additive manufacturing, and particularly relates to a preparation method of a metal artificial bone, which is capable of processing a customized metal artificial bone with a complex geometric shape and capable of synchronously adjusting the porosity and the degradation rate of the structure, based on 3D printing of a metal artificial bone prepared by slurry direct writing.
Background
Direct writing of slurry (DIW) employs a technique of depositing and molding an extruded slurry, which is to mix polymer solvents or particles to form a flowable slurry with uniform properties, wherein the viscosity of the slurry can ensure that lines are extruded in a nozzle with a certain inner diameter, and the viscosity of the slurry can maintain a certain shape after extrusion, thereby ensuring the molding capability of the slurry. The extruded lines move according to a path designed by slicing software to form a certain shape in the horizontal plane of the substrate, then the substrate sinks for one layer, the second layer is printed, and then the process is continuously repeated until the whole three-dimensional structural part is machined and molded. The technology is already used for processing metal parts, when slurry is prepared, viscous adhesive and metal particles are uniformly mixed, the flowability and the extrudability of the slurry are ensured, and then the slurry is piled and formed. However, the molded article is a polymer-bonded metal powder, does not have the strength of metal, and is not a true metal member. In a subsequent sintering process, the polymer binder is removed by sintering and the metal powder particles are gradually fused at high temperature to form a structural member having metal strength. 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; overall performance is guaranteed, etc.
In addition, for manufacturing the metal artificial bone by the existing additive manufacturing method, the following three aspects are mainly noted:
1) has better biocompatibility, does not have systemic or local toxic reaction, blood coagulation, stimulation and other adverse reactions after the metal artificial bone implant is internally implanted, and simultaneously needs to have osteoinductivity, so that new bones can be formed under the induction of biomolecule signals.
2) Has certain in vivo degradation capability, and after the metal artificial bone implant is implanted in a body, the metal artificial bone is gradually degraded and replaced by new bone along with the regeneration and reconstruction of bone tissues, thereby finally realizing the repair of bone defect. Therefore, it is required that the degradation rate of the artificial bone matches the regeneration and reconstruction rate of the bone tissue. Meanwhile, the degradation products of the artificial bone must not be toxic.
3) Has proper pore diameter (100-500 mu m) and high porosity (more than 40% -60%), and has a three-dimensional through pore structure inside, so that the nutrient can be normally conveyed, the metabolite can be normally discharged, and the new bone can grow in conveniently.
The artificial bone prepared by the existing additive manufacturing technology has the following problems:
1) the metal artificial bone with proper pore diameter and porosity is printed, but the degradation speed of the metal artificial bone can be controlled only by adjusting the porosity to match the regeneration and reconstruction speed of human bone tissues (the higher the porosity, the higher the degradation speed).
2) The metal artificial bone which can match the regeneration and reconstruction speed of human bone tissues is printed by changing materials, but the artificial bone does not meet the requirements of proper pore diameter and porosity.
Both have the problem that the required degradation rate cannot be met with a pore size and porosity that meet the required accuracy and vice versa.
Disclosure of Invention
The invention provides a preparation method of a porous artificial bone capable of adjusting a degradation rate based on slurry direct writing, and aims to solve the problem that the porosity and the degradation rate of a structure cannot be simultaneously adjusted to be matched with the original skeleton of a human body when a metal artificial bone support is processed by an existing metal 3D printing method.
The technical scheme adopted by the invention is that the method comprises the following steps:
(1) weighing a solvent and a polymer in a mass ratio of 3-5: 1 before mixing and mixing the slurry, and dissolving the polymer and the solvent in a sealed container with an anti-corrosion function at normal temperature for 24-36h or at constant temperature of 37 ℃ for 12h to prepare a slurry binder with uniform property, flowability and certain viscosity;
(2) iron powder D9043.4 μm and hydroxyapatite powder D90Respectively putting the powder with the particle size of 9.72 mu m into a drying box, drying the powder for 6 to 12 hours at the constant temperature of between 50 and 80 ℃, and then respectively putting the dried powder into a ball mill to ball mill for 40 to 60 minutes at the rotating speed of 300 and 400r/min to obtain dried powder without obvious agglomeration;
(3) weighing iron powder and hydroxyapatite powder according to the mass ratio of 12-39:1, putting the iron powder and hydroxyapatite powder into a ball mill according to the mass ratio of 1: 3-4 of the slurry binder and the mixed powder, and carrying out ball milling and mixing for 60-100 minutes at the rotating speed of 600r/min under the sealing condition to obtain uniformly mixed slurry; uniformly mixing the slurry into a viscous state without flaky crystals and particles;
(4) placing the mixed slurry into a charging barrel of a printing head, introducing 0.2-0.4MPa of stable air pressure after clamping by a clamp, pushing a push rod to advance by the air pressure to push a plug inside the charging barrel so as to form pressure on the mixed slurry, extruding the mixed slurry at a constant speed by a nozzle below the charging barrel, enabling the extruded mixed slurry to be filamentous, enabling a polymer to wrap metal powder for shaping due to the evaporation of a binder solvent in the slurry after extrusion, and stacking the mixed slurry wires subjected to mixed printing at the speed of 8-15mm/s to form a three-dimensional structure under the driving of a three-dimensional motion platform controlled by a slicing software program so as to obtain a metal support;
(5) and carrying out heat treatment on the metal bracket, wherein the heat treatment comprises the following steps:
1) cleaning air and vacuumizing: putting a metal support to be sintered into a vacuum sintering furnace, vacuumizing to reach an air pressure environment below 3Pa, filling inert gas (argon) into the furnace until the pressure is in a room pressure state, and vacuumizing; repeating the steps for 3 times to 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 5-10 ℃/min, and keeping the temperature for 0.5-1 h to realize the complete pyrolysis of the binder;
3) and iron powder fusion: heating the vacuum sintering furnace to 1120 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for 2-4 h, so that the metal powder particles in the bracket are sintered and fused under the condition of ensuring that the hydroxyapatite is not subjected to phase change;
4) and cooling: and after the metal support is fully sintered, introducing inert gas (argon) 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, and taking out the sample after introducing argon for cooling for 1 hour.
In step (1) of the present invention, the weight ratio of the solvent to the polymer is 4: 1.
The polymer in the step (1) of the invention adopts polylactic acid PLA.
The solvent in step (1) of the invention adopts dichloromethane DCM.
The printing head in the step (4) of the invention is a pneumatic extrusion type printing head, and comprises: the device comprises an air supply device, a push rod, a clamp, a charging barrel, a plug and a spray head, wherein the plug is placed in the charging barrel, the charging barrel is placed in the clamp, the spray head is connected below the charging barrel, the air supply device is connected with the push rod, and the plug in the charging barrel is pushed by the push rod to extrude mixed slurry.
The inner diameter of the spray head in the step (4) is 0.2-0.3 mm.
In the step (5), the inert gas is argon.
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;
the molecular formula of the hydroxyapatite is Ca10(PO4)6(OH)2The calcium-phosphorus atom molar mass ratio of the calcium-phosphorus composite material is 1.667 which is the same as that of human bone, the calcium-phosphorus composite material is an important composition component in human bone, has good biocompatibility with human hard tissue, bone tissue, muscle tissue and the like, can form good bone bonding with bone tissue after being implanted into a body, and is applied to clinical bone defect at present. Under simulation experiments and living body experiments of the mixed metal scaffold of hydroxyapatite and iron, the metal scaffold has better biological activity, which mainly embodies that the compression strength of the metal scaffold is closer to the compression strength of human bones while a milder inflammatory effect, more macrophages are generated and the like are included.
Drawings
FIG. 1 is a schematic diagram of a pneumatically-extruded printhead employed in the present invention;
fig. 2 is a scanning electron microscope photograph of a metal three-dimensional structure at different magnifications after printing and sintering a mixture of metal iron powder and hydroxyapatite powder (the mass ratio of hydroxyapatite is 0%, 2.5%, 5%, and 7.5% in sequence from left to right), wherein the first row: 75 times magnification, second row: multiplying power of 300 times; third row: the multiplying power is 2000 times;
fig. 3 is an electron microscope photograph of different magnifications after printing a mixture of iron powder and hydroxyapatite powder (hydroxyapatite mass ratio is 0%, 2.5%, 5%, 7.5% from left to right in sequence), printing, sintering and performing a 7-day soaking experiment, the first row: 75 times magnification, second row: multiplying power of 300 times; third row: the multiplying power is 2000 times;
fig. 4 is a graph of the weight loss of a printed stent after a 7-day soak test in accordance with ASTM G31.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the accompanying 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 invention, and not all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without creative efforts based on the embodiments of the present invention belong to the protection scope of the present invention.
In the following examples, iron powder was used as the printing metal powder, dichloromethane DCM was used as the binder solvent, and polylactic acid PLA was used as the polymer;
example 1
Comprises the following steps:
(1) and before mixing the mixed slurry, weighing the mass ratio of the solvent to the polymer to be 3: 1, dissolving a polymer and a solvent in a sealed container with an anti-corrosion function for 24 hours at normal temperature to prepare a slurry binder with uniform property, fluidity and certain viscosity;
(2) iron powder D9043.4 μm and hydroxyapatite powder D90Putting the powder with the particle size of 9.72 mu m into a drying box respectively, drying the powder for 12h at the constant temperature of 50 ℃, then putting the dried powder into a ball mill respectively, and carrying out ball milling for 40 min at the rotating speed of 300r/min to obtain dry powder without obvious agglomeration;
(3) weighing iron powder and hydroxyapatite powder according to the mass ratio of 12:1, putting the iron powder and hydroxyapatite powder into a ball mill according to the mass ratio of 1:3 of a slurry binder to mixed powder, and carrying out ball milling and mixing for 60 minutes at the rotating speed of 500r/min under a good sealing condition to obtain uniformly mixed slurry, wherein the uniformly mixed slurry is sticky and has no flaky crystal and obvious particles;
(4) putting the mixed slurry into a charging barrel 3, clamping the mixed slurry by a clamp 5, introducing 0.2MPa stable air pressure, pushing a push rod 2 to advance by the air pressure to push an inner plug 4 of the charging barrel 3, forming pressure on the metal slurry, extruding the metal slurry by a spray head 6 below the charging barrel, enabling the extruded mixed slurry to be filamentous, enabling a polymer to wrap metal powder for shaping due to the evaporation of a binder solvent in the slurry after extrusion, and stacking the mixed slurry wires which are subjected to mixed printing at the speed of 8-15mm/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 bracket;
(5) and carrying out heat treatment on the metal bracket, wherein the heat treatment comprises the following steps:
1) cleaning air and vacuumizing: placing a 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, vacuumizing, and repeating the steps for 3 times to effectively clean the original air in the furnace and reduce the influence of oxygen on the metal support at high temperature;
2) and pyrolysis of the binder: heating the vacuum sintering furnace to 300 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 0.5h 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 5 ℃/min, keeping the temperature for 2 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: and after the metal support is fully sintered, introducing inert gas argon to enable the sintering furnace to be separated from a vacuum state so as to enhance convective heat transfer and heat conduction, accelerating the cooling of the metal support, and taking out a sample after introducing argon for cooling for 1 hour.
Example 2
Comprises the following steps:
(1) weighing a solvent and a polymer according to a mass ratio of 4:1 before mixing and mixing the slurry, and dissolving the polymer and the solvent in a sealed container with an anti-corrosion function at normal temperature for 30 hours to prepare a slurry binder which is uniform in property, flowable and has certain viscosity;
(2) iron powder D9043.4 μm and hydroxyapatite powder D90Putting the powder with the particle size of 9.72 mu m into a drying box respectively, drying the powder for 9h at the constant temperature of 65 ℃, then putting the dried powder into a ball mill respectively, and carrying out ball milling for 50 min at the rotating speed of 350r/min to obtain dry powder without obvious agglomeration;
(3) weighing iron powder and hydroxyapatite powder according to the mass ratio of 25:1, putting the weighed iron powder and hydroxyapatite powder into a ball mill according to the mass ratio of 1:3.5 of the slurry binder to the mixed powder, and carrying out ball milling and mixing for 80 minutes at the rotating speed of 550r/min under the sealing condition to obtain uniformly mixed slurry; uniformly mixing the slurry into a viscous state without flaky crystals and particles;
(4) placing the mixed slurry into a charging barrel of a printing head, introducing 0.3MPa stable air pressure after clamping by a clamp, pushing a push rod to move forward by the air pressure to push a plug inside the charging barrel, so that the mixed slurry is pressurized and extruded at a constant speed by a nozzle below the charging barrel, wherein the extruded mixed slurry is filamentous, and after extrusion, a polymer wraps metal powder for shaping due to evaporation of a binder solvent in the slurry, and mixed slurry wires printed in a mixed mode are stacked at a speed of 12mm/s to form a three-dimensional structure under the driving of a three-dimensional motion platform controlled by a slicing software program to obtain a metal support;
(5) and carrying out heat treatment on the metal bracket, wherein the heat treatment comprises the following steps:
1) cleaning air and vacuumizing: putting a 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; repeating the steps for 3 times to 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 8 ℃/min, and keeping the temperature for 0.8h 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 8 ℃/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: and after the metal support is fully sintered, introducing inert gas argon to enable the sintering furnace to be separated from a vacuum state so as to enhance convective heat transfer and heat conduction, accelerating the cooling of the metal support, and taking out a sample after introducing argon for cooling for 1 hour.
Example 3
Comprises the following steps:
(1) weighing a solvent and a polymer according to a mass ratio of 5:1 before mixing and mixing the slurry, and dissolving the polymer and the solvent in a sealed container with an anti-corrosion function at normal temperature for 36 hours or at constant temperature of 37 ℃ for 12 hours to prepare a slurry binder with uniform property, fluidity and certain viscosity;
(2) iron powder D9043.4 μm and hydroxyapatite powder D90Putting the powder with the particle size of 9.72 mu m into a drying box respectively, drying the powder for 6h at the constant temperature of 80 ℃, and then putting the powder into a ball mill respectively to ball mill for 60 min at the rotating speed of 400r/min to obtain dry powder without obvious agglomeration;
(3) weighing iron powder and hydroxyapatite powder according to the mass ratio of 39:1, putting the weighed iron powder and hydroxyapatite powder into a ball mill according to the mass ratio of 1:4 of the slurry binder to the mixed powder, and carrying out ball milling and mixing for 100 minutes at the rotating speed of 600r/min under the sealing condition to obtain uniformly mixed slurry; uniformly mixing the slurry into a viscous state without flaky crystals and particles;
(4) placing the mixed slurry into a charging barrel of a printing head, introducing 0.4MPa stable air pressure after clamping by a clamp, pushing a push rod to move forward by the air pressure to push a plug inside the charging barrel, so that the mixed slurry is pressurized and extruded at a constant speed by a nozzle below the charging barrel, wherein the extruded mixed slurry is filamentous, and after extrusion, a polymer wraps metal powder for shaping due to evaporation of a binder solvent in the slurry, and mixed slurry wires printed in a mixed mode are stacked at a speed of 15mm/s to form a three-dimensional structure under the driving of a three-dimensional motion platform controlled by a slicing software program to obtain a metal support;
(5) and carrying out heat treatment on the metal bracket, wherein the heat treatment comprises the following steps:
1) cleaning air and vacuumizing: putting a 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; repeating the steps for 3 times to 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 10 ℃/min, keeping the temperature for 4 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: and after the metal support is fully sintered, introducing inert gas argon to enable the sintering furnace to be separated from a vacuum state so as to enhance convective heat transfer and heat conduction, accelerating the cooling of the metal support, and taking out a sample after introducing argon for cooling for 1 hour.
The printing head of the invention is a pneumatic extrusion type printing head, comprising: the device comprises an air supply device 1, a push rod 2, a charging barrel 3, a plug 4, a clamp 5 and a spray head 6, wherein the plug 4 is placed in the charging barrel 3, the charging barrel 3 is placed in the clamp 5, the spray head 6 is connected below the charging barrel, the air supply device 1 is connected with the push rod 2, the plug 4 in the charging barrel 3 is pushed by the push rod 2 to extrude metal slurry, and the principle of the device is shown in figure 1.
The inner diameter of the nozzle of the invention is 0.28 mm.
The effect of the present invention is further illustrated by the soaking experiment below.
Purpose of the experiment: the degradation condition of the metal stent in the human body environment after being implanted into the human body is simulated by soaking the printed metal stent in the environment simulating body fluid, and finally, the speed condition of the degradation rate is indirectly reflected by measuring the weight loss rate.
The experimental contents are as follows:
1) dividing the experiment into three groups of 1 day of degradation, 3 days of degradation and 7 days of degradation;
2) after the metal brackets are manufactured, suspending the three groups of metal brackets in corresponding beakers;
3) selecting Hanks balanced salt solution as simulated body fluid, and pouring the simulated body fluid into a beaker until the simulated body fluid meets the requirements of ASTM G31 standard;
4) manufacturing a simulated in-vivo environment with 37 ℃ and 98% humidity by using a constant temperature box;
5) placing the beaker into a thermostat, and replacing the simulated body fluid every day according to the ASTM G31 standard;
6) taking out the experimental group degraded for 1 day after degrading for 1 day, and performing cleaning and calculating processes (see processes 7) -12));
7) mixing 3.5g of hexamethylenetetramine with 500ml of hydrochloric acid with the specific gravity of 1.19, and adding deionized water to 1000ml to prepare 1L of cleaning solution;
8) placing the experimental group for 1 day of degradation into degradation liquid and ultrasonically cleaning for ten minutes;
9) taking out the degradation liquid from the degradation liquid to degrade the experimental group for one day, and putting the experimental group into distilled water for ultrasonic cleaning for fifteen minutes;
10) taking out the mixture from the distilled water and putting the mixture into a drying box at the temperature of 80-102 ℃ for drying for 60-80 minutes;
11) weighing the cleaned sample piece, and calculating the weight loss and the untreated weight loss rate;
12) eliminating the influence of cleaning errors according to the ASTM G31 standard, and calculating the weight loss rate (see figure 4);
13) taking out the experimental group degraded for 3 days after the degradation for 3 days, and carrying out cleaning and calculating processes (the process is simulated as 7) -12));
14) and taking out the 7-day degradation experimental group after 7 days of degradation, and performing cleaning and calculation processes (the process is similar to 7) -12)).
And (4) experimental conclusion:
1) when the degradation time is short, the degradation condition is unstable, the influence factors caused by environmental interference factors and experimental operation are large, errors are easy to generate due to the fact that the degradation rate is slow, but the degradation condition tends to be stable along with the increase of the degradation time, the influence of the environmental interference factors and the influence factors caused by experimental operation is small, and the degradation rule can be embodied;
2) for metal scaffolds with the same internal structure (the porosity, the pore size and the like are the same), the weight loss rate is increased along with the increase of the proportion of the hydroxyapatite powder, namely the degradation rate is increased;
3) the degradation rate can be improved by improving the proportion of the hydroxyapatite powder, so that the porous artificial bone with adjustable speed can be printed on the premise of meeting the requirements of porosity and pore size.
The size of the metal bracket used in the experiment is a cube with the side length of 6mm, the porosity is 50%, the size of the line is 0.28mm, and the scanning electron microscope photos of the three-dimensional structure before and after degradation are shown in figures 2 and 3. The distribution of iron powder (grey black particles in the figure) and hydroxyapatite powder (white particles and white agglomerates in the figure) after sintering of the metal sample can be seen in fig. 2 and 3. As the ratio of hydroxyapatite powder increases, the accumulation of surface degradation products of the metal scaffold becomes more pronounced in fig. 3, i.e., a more severe degradation process occurs, the faster the degradation rate.
Claims (7)
1. A preparation method of a porous artificial bone capable of adjusting degradation rate based on slurry direct writing is characterized by comprising the following steps:
(1) weighing a solvent and a polymer in a mass ratio of 3-5: 1 before mixing and mixing the slurry, and dissolving the polymer and the solvent in a sealed container with an anti-corrosion function at normal temperature for 24-36h or at constant temperature of 37 ℃ for 12h to prepare a slurry binder with uniform property, flowability and certain viscosity;
(2) iron powder D9043.4 μm and hydroxyapatite powder D90Respectively putting the powder with the particle size of 9.72 mu m into a drying box, drying the powder for 6 to 12 hours at the constant temperature of between 50 and 80 ℃, and then respectively putting the dried powder into a ball mill to ball mill for 40 to 60 minutes at the rotating speed of 300 and 400r/min to obtain dried powder without obvious agglomeration;
(3) weighing iron powder and hydroxyapatite powder according to the mass ratio of 12-39:1, putting the iron powder and hydroxyapatite powder into a ball mill according to the mass ratio of 1: 3-4 of the slurry binder and the mixed powder, and carrying out ball milling and mixing for 60-100 minutes at the rotating speed of 600r/min under the sealing condition to obtain uniformly mixed slurry; uniformly mixing the slurry into a viscous state without flaky crystals and particles;
(4) placing the mixed slurry into a charging barrel of a printing head, introducing 0.2-0.4MPa of stable air pressure after clamping by a clamp, pushing a push rod to advance by the air pressure to push a plug inside the charging barrel so as to form pressure on the mixed slurry, extruding the mixed slurry at a constant speed by a nozzle below the charging barrel, enabling the extruded mixed slurry to be filamentous, enabling a polymer to wrap metal powder for shaping due to the evaporation of a binder solvent in the slurry after extrusion, and stacking the mixed slurry wires subjected to mixed printing at the speed of 8-15mm/s to form a three-dimensional structure under the driving of a three-dimensional motion platform controlled by a slicing software program so as to obtain a metal support;
(5) and carrying out heat treatment on the metal bracket, wherein the heat treatment comprises the following steps:
1) cleaning air and vacuumizing: putting a metal support to be sintered into a vacuum sintering furnace, vacuumizing to reach an air pressure environment below 3Pa, filling inert gas (argon) into the furnace until the pressure is in a room pressure state, and vacuumizing; repeating the steps for 3 times to 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 5-10 ℃/min, and keeping the temperature for 0.5-1 h to realize the complete pyrolysis of the binder;
3) and iron powder fusion: heating the vacuum sintering furnace to 1120 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for 2-4 h, so that the metal powder particles in the bracket are sintered and fused under the condition of ensuring that the hydroxyapatite is not subjected to phase change;
4) and cooling: and after the metal support is fully sintered, introducing inert gas (argon) 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, and taking out the sample after introducing argon for cooling for 1 hour.
2. The preparation method of the porous artificial bone based on the slurry direct-writing adjustable degradation rate according to claim 1, characterized in that: in the step (1), the mass ratio of the weighed solvent to the weighed polymer is 4: 1.
3. The preparation method of the porous artificial bone based on the slurry direct-writing adjustable degradation rate according to claim 1, characterized in that: the polymer in the step (1) adopts polylactic acid (PLA).
4. The preparation method of the porous artificial bone based on the slurry direct-writing adjustable degradation rate according to claim 1, characterized in that: the solvent in the step (1) adopts dichloromethane DCM.
5. The preparation method of the porous artificial bone based on the slurry direct-writing adjustable degradation rate according to claim 1, characterized in that: the printing head in the step (4) is a pneumatic extrusion type printing head, and comprises: the device comprises an air supply device, a push rod, a clamp, a charging barrel, a plug and a spray head, wherein the plug is placed in the charging barrel, the charging barrel is placed in the clamp, the spray head is connected below the charging barrel, the air supply device is connected with the push rod, and the plug in the charging barrel is pushed by the push rod to extrude mixed slurry.
6. The preparation method of the porous artificial bone based on the slurry direct-writing adjustable degradation rate according to claim 1, characterized in that: the inner diameter of the spray head in the step (4) is 0.2-0.3 mm.
7. The preparation method of the porous artificial bone based on the slurry direct-writing adjustable degradation rate according to claim 1, characterized in that: and (5) selecting argon as the inert gas.
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