CN113118455B - 3D printing method for preparing metal artificial bone based on slurry direct writing - Google Patents
3D printing method for preparing metal artificial bone based on slurry direct writing Download PDFInfo
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- CN113118455B CN113118455B CN202110445313.8A CN202110445313A CN113118455B CN 113118455 B CN113118455 B CN 113118455B CN 202110445313 A CN202110445313 A CN 202110445313A CN 113118455 B CN113118455 B CN 113118455B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F3/1134—Inorganic fillers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- 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
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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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
Abstract
The invention relates to a 3D printing method for preparing a metal artificial bone based on slurry direct writing, and belongs to a metal 3D printing method in the field of additive manufacturing. After the printing metal powder, the pore-forming agent manganese powder and the binder are uniformly mixed, the mixture is extruded into lines through a pneumatic printing nozzle, and a solvent in the binder volatilizes and becomes a three-dimensional structure with a complex shape along with the movement of a three-dimensional motion platform. In the later sintering process, the polymer in the binder is pyrolyzed at about 300 ℃, the metal material for preparing the artificial bone is fused together in the environment of more than 1000 ℃, and the manganese powder is evaporated under the high vacuum condition of less than 1000 ℃ to form microscopic pores inside the wire. The structural pores between the micro pores and the lines are independent, and the adjustment of the micro pores can be carried out while keeping the structural porosity unchanged, so that the mechanical property of the artificial bone scaffold is adjusted, and the structural porosity and the mechanical property of the artificial bone scaffold can be kept consistent with the original skeleton of a human body.
Description
Technical Field
The invention relates to a 3D printing method for preparing a metal artificial bone based on slurry direct writing in the field of additive manufacturing, in particular to a metal artificial bone processing method which can process customized metal artificial bones with complex geometric shapes and can synchronously adjust the porosity and the mechanical property of the metal artificial bone.
Background
The mainstream metal additive manufacturing technology at present mainly comprises: powder Bed Fusion (PBF) and Direct Energy Deposition (DED). The powder bed melting technology (PBF) which adopts laser as energy occupies more than 90% of the metal 3D printing market, and the technology is that laser sweeping of single-layer metal powder is carried out on a metal powder bed, the powder is melted to form a fixed shape, then powder is continuously paved layer by layer and swept, and the steps are continuously repeated until a sample piece is molded. The Direct Energy Deposition (DED) technique is to send powder under the protection of gas through a powder feeder to an energy beam, the energy beam melts the powder, and then the powder is stacked layer by layer and solidified to form. The two technologies melt metal powder by intensive energy and then stack and form the metal powder, but have the following defects in the processing process:
1. the high precision energy processing system makes the process expensive;
2. certain potential safety hazards exist;
3. the energy sweeping of the single layer enables the temperature difference between the upper layer and the lower layer to exist, and residual stress can be generated to a certain extent, so that the overall performance is influenced;
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 metallic strength. The technology can be used for processing the artificial bone with the micro-structure pore, the cost is low, and the forming sample piece has no internal stress.
When the metal artificial bone is processed, in order to match the mechanical characteristics of the original skeleton of a human body, the mechanical strength, particularly the elastic modulus of the metal is reduced during processing, otherwise, the stress shielding phenomenon is generated, and the problems of the human body skeleton looseness and the like are caused. No matter which method is used for processing the metal artificial bone, the porosity and the mechanical property are greatly related, the mechanical property is in a linear reduction trend along with the increase of the porosity, the linear trend enables two characteristics of the porosity and the mechanical property to be synchronously adjusted, the mechanical strength of the support cannot be reduced while the porosity characteristic of the support structure is kept unchanged, and parameter adjustment outside a linear rule is difficult to achieve. Thus, it is difficult to match both porosity and mechanical strength to human bone.
Disclosure of Invention
The invention provides a 3D printing method for preparing a metal artificial bone based on slurry direct writing, which aims to solve the problem that the porosity and mechanical properties of a metal artificial bone support processed by the existing metal 3D printing method cannot be simultaneously adjusted to be matched with the original skeleton of a human body.
The technical scheme adopted by the invention is that the method comprises the following steps:
(1) Weighing the polymer and the solvent in a mass ratio of 1: 3-5, dissolving the polymer and the solvent in a sealed container for 6-12 hours to prepare a slurry binder which has uniform property, can flow and has certain viscosity;
(2) Weighing printing metal powder with the diameter of 5-100 micrometers and irregular manganese powder serving as a pore-forming agent with the particle size of 5-15 micrometers according to the volume ratio of 1.1-2.4, putting the manganese powder into a ball mill according to the mass ratio of a slurry binder to the total metal powder of 1:3-5, and performing ball milling and mixing for 30-60 minutes at the rotating speed of 200-800r/min to obtain uniformly mixed metal slurry;
(3) Placing metal slurry into a charging barrel, clamping by a clamp, introducing stable air pressure, pushing a push rod by the air pressure so as to push a plug inside the charging barrel, forming pressure on the metal slurry, extruding the metal slurry through a spray head below the charging barrel, enabling the extruded metal powder mixed with a binder to be filamentous, quickly evaporating a solvent in the extruded binder, coating a polymer on the metal powder for solidification, and stacking the metal wires at a speed of 5-20mm/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 an original piece;
(4) And heat treating the prototype part, including:
1) And vacuumizing: placing a prototype to be sintered into a vacuum sintering furnace, and vacuumizing to reach an air pressure environment below 3 Pa;
2) And pyrolysis of the binder: heating the vacuum 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) Manganese powder evaporation and iron powder fusion: heating the vacuum furnace to 1000-1400 ℃ at the heating rate of 5-10 ℃/min until the temperature reaches the metal vapor pressure critical temperature of the manganese powder, continuing to rise, evaporating the manganese powder, and keeping the temperature for 2-5 h to perform sintering fusion between the printed metal powder particles;
4) And cooling: and after the prototype part is fully sintered, automatically cooling the sintering furnace, and taking out the sample.
The printing head of the invention is a pneumatic extrusion type printing head, comprising: the metal slurry extruding device comprises a gas supply device, a push rod, a clamp, a material barrel, a plug and a spray head, wherein the plug is placed in the material barrel, the material barrel is placed in the clamp, the spray head is connected below the material barrel, the gas supply device is connected with the push rod, and the plug in the material barrel is pushed by the push rod to extrude metal slurry.
The inner diameter of the spray head is 0.2-1.0 mm.
The printing metal powder is a metal artificial bone material and comprises iron and titanium alloy.
In the step (1), the polymer comprises polylactic acid (PLA), polyvinyl alcohol (PVA), polyethylene glycol (PEG), chitosan and Polystyrene (PS);
the solution comprises dichloromethane DCM, water and ethanol solution.
The invention has the advantages that: the volume ratio of the metal mixed powder in the prototype can reach 80%, 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; laser, electron beams and the like are not needed, equipment and processing cost is reduced, the method is safer and more reliable, the whole processed part is sintered and molded at the same time, and local residual stress does not exist; the manganese powder is used as a pore-forming agent, can be evaporated into manganese metal steam after the self temperature reaches the critical vapor pressure under the high vacuum condition, the critical temperature is lower than 1000 ℃, the removal temperature of the pore-forming agent is higher, the printed metal powder already begins to form a sintering neck at the moment, the connection strength is realized, the collapse of a sample piece can be avoided, the pore-forming agent is removed before the melting point of the printed metal, the melting of the printed metal material can be avoided, the critical vapor pressure temperature of the metal pore-forming agent is lower than that of the printed metal material, and the printed metal can not be evaporated and dissipated; after the manganese powder is evaporated, at the inside microcosmic hole that forms evenly distributed of iron wire strip, structure hole between the lines is independent mutually, play the effect of adjusting the whole mechanical properties of artificial bone, thereby realize adjusting the target of artificial bone mechanical properties under the unchangeable condition of artifical bone scaffold structure porosity, make the structure porosity and the mechanical properties of artifical bone scaffold can adjust simultaneously to the degree with the original skeleton assorted of human body, can greatly promote the elastic modulus of metal artificial bone to reduce, improve the stress shielding phenomenon that artificial bone implantation leads to.
Drawings
FIG. 1 is a schematic diagram of a pneumatically driven extrusion printhead employed in the present invention;
FIG. 2 is a schematic process diagram of a deployed metal paste;
fig. 3 is a scanning electron microscope photograph of a three-dimensional structure of a metal at different magnifications after printing and sintering of a mixture of a printed metal iron powder and a pore-forming agent manganese powder (volume ratio Fe: mn = 7:3), the first line: printed sample, second line: sintering;
FIG. 4 is a scanning electron micrograph of the metal wire after printing and sintering of pore formers at different ratios, with a scale of 50 μm, first row: printed sample, second row: sintering; the designation Fe9Mn1 stands for Fe: mn =9:1 volume ratio;
FIG. 5 is a photograph of cross-sections of sintered metal wires with different pore formers;
FIG. 6 is a graph showing the mechanical properties of sintered metal artificial bone samples with different pore-forming agents in different proportions and different structural porosities.
Detailed Description
Example 1 printing metal powder was iron powder, binder solvent was dichloromethane DCM, polymer was polylactic acid PLA;
comprises the following steps:
(1) Weighing the mass ratio of the polymer to the solvent to be 1:4, dissolving the polymer and the solvent in a sealed container for 6 hours to prepare a slurry binder with uniform property, fluidity and certain viscosity;
(2) Weighing the printing metal powder with the diameter of 5-45 micrometers and the manganese powder serving as a pore-forming agent with irregular particle size of about 5-8 micrometers according to the volume ratio of 1.1, and putting the mixture into a ball mill according to the mass ratio of the slurry binder to the total metal powder of 1:5 for ball-milling and mixing for 30 minutes at the rotating speed of 500r/min to obtain uniformly mixed metal slurry;
(3) Placing metal slurry into a charging barrel 3, clamping by a clamp 4, introducing stable air pressure, pushing a push rod 2 by the air pressure so as to push a plug 5 in the charging barrel 3, forming pressure on the metal slurry, extruding the metal slurry through a spray head 6 below the charging barrel, enabling the extruded metal powder mixed with a binder to be filamentous, rapidly evaporating a solvent in the extruded binder, coating a polymer on the metal powder for solidification, and stacking the metal wires at the speed of 10mm/s to form a three-dimensional structure under the driving of a three-dimensional motion platform controlled by a slicing software program to obtain an original piece;
(4) And heat treating the prototype part, including:
1) And vacuumizing: placing a prototype to be sintered into a vacuum sintering furnace, and vacuumizing to reach an air pressure environment below 3 Pa;
2) And pyrolysis of the binder: heating the vacuum 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) Manganese powder evaporation and iron powder fusion: heating the vacuum furnace to 1000 ℃ at the heating rate of 5 ℃/min to reach the metal vapor pressure critical temperature of the manganese powder, continuing to rise, evaporating the manganese powder, and keeping the temperature for 3 hours to perform sintering fusion among the printed metal powder particles;
4) And cooling: and after the prototype part is fully sintered, automatically cooling the sintering furnace, and taking out the sample.
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 clamp 4, a plug 5 and a spray head 6, wherein the plug 5 is placed in the charging barrel 3, the charging barrel 3 is placed in the clamp 4, the spray head 6 is connected below the charging barrel, the air supply device 1 is connected with the push rod 2, the plug 5 in the charging barrel 3 is pushed by the push rod 2 to extrude metal slurry, and the overall processing principle is shown in fig. 2;
the inner diameter of the spray head is 0.2mm.
Example 2 printing metal powder was titanium alloy powder, binder solvent was dichloromethane DCM, polymer was polystyrene PS;
comprises the following steps:
(1) Weighing the mass ratio of the polymer to the solvent to be 1:3, dissolving the polymer and the solvent in a sealed container for 12 hours to prepare a slurry binder with uniform property, fluidity and certain viscosity;
(2) Weighing the printing metal powder with the diameter of 30-70 microns and manganese powder serving as a pore-forming agent with irregular particle size of 9-12 microns according to the volume ratio of 1:1, and putting the mixture into a ball mill according to the mass ratio of a slurry binder to the total metal powder of 1:4 for ball-milling and mixing for 45 minutes at the rotating speed of 800r/min to obtain uniformly mixed metal slurry;
(3) Putting metal slurry into a charging barrel 3, clamping by a clamp 4, introducing stable air pressure, pushing a push rod 2 by the air pressure so as to push a plug 5 in the charging barrel 3 to form pressure on the metal slurry, extruding the metal slurry through a spray head 6 below the charging barrel, forming extruded metal powder mixed with a binder into a filament shape, quickly evaporating a solvent in the extruded binder, coating the metal powder with a polymer, solidifying, and stacking the metal wires at a speed of 5mm/s to form a three-dimensional structure under the drive of a three-dimensional motion platform controlled by a slicing software program to obtain an original piece;
(4) And heat treating the prototype part, including:
1) And vacuumizing: placing a prototype to be sintered into a vacuum sintering furnace, and vacuumizing to reach an air pressure environment below 3 Pa;
2) And pyrolysis of the binder: heating the vacuum furnace to 300 ℃ at the heating rate of 10 ℃/min, and keeping the temperature for 0.7h to realize the complete pyrolysis of the binder;
3) Manganese powder evaporation and iron powder fusion: heating the vacuum furnace to 1400 ℃ at the heating rate of 10 ℃/min to reach the metal vapor pressure critical temperature of the manganese powder, continuing to rise, evaporating the manganese powder, and keeping the temperature for 3 hours to perform sintering fusion among the printed metal powder particles;
4) And cooling: and after the original model is fully sintered, automatically cooling the sintering furnace, and taking out the sample.
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 clamp 4, a plug 5 and a spray head 6, wherein the plug 5 is placed in the charging barrel 3, the charging barrel 3 is placed in the clamp 4, the spray head 6 is connected below the charging barrel, the air supply device 1 is connected with the push rod 2, the plug 5 in the charging barrel 3 is pushed by the push rod 2 to extrude metal slurry, and the overall processing principle is shown in fig. 2;
the inner diameter of the spray head is 0.6mm.
Example 3 stainless steel was used for printing metal powder, water was used for binder solvent, and polyvinyl alcohol PVA and polyethylene glycol PEG were used for polymer.
Comprises the following steps:
(1) Before mixing the metal slurry, weighing the mass ratio of the polymer PVA to the PEG of 2:1, wherein the mass ratio of the polymer to the solvent is 1:5, dissolving the polymer and the solvent in a sealed container for 9 hours to prepare a slurry binder with uniform property, fluidity and certain viscosity;
(2) Weighing printing metal powder with the diameter of 70-100 micrometers and manganese powder serving as a pore-forming agent with irregular particle size of about 12-15 micrometers according to the volume ratio of 1;
(3) Placing metal slurry into a charging barrel 3, clamping by a clamp 4, introducing stable air pressure, pushing a push rod 2 by the air pressure so as to push a plug 5 in the charging barrel 3, forming pressure on the metal slurry, extruding the metal slurry through a spray head 6 below the charging barrel, enabling the extruded metal powder mixed with a binder to be filamentous, rapidly evaporating a solvent in the extruded binder, coating a polymer on the metal powder for solidification, and stacking the metal wires at a speed of 20mm/s to form a three-dimensional structure under the driving of a three-dimensional motion platform controlled by a slicing software program to obtain an original piece;
(4) And heat treating the prototype part, including:
1) And vacuumizing: placing a prototype to be sintered into a vacuum sintering furnace, and vacuumizing to reach an air pressure environment below 3 Pa;
2) And pyrolysis of the binder: heating the vacuum furnace to 300 ℃ at the heating rate of 8 ℃/min, and keeping the temperature for 1h to realize the complete pyrolysis of the binder;
3) Manganese powder evaporation and stainless steel powder fusion: heating the vacuum furnace to 1200 ℃ at the heating rate of 8 ℃/min to reach the metal vapor pressure critical temperature of the manganese powder, continuing to rise, evaporating the manganese powder, and keeping the temperature for 3 hours to perform sintering fusion among the printed metal powder particles;
4) And cooling: and after the prototype part is fully sintered, automatically cooling the sintering furnace, and taking out the sample.
The printing head of the invention is a pneumatic extrusion type printing head, comprising: the metal slurry extrusion device comprises an air supply device 1, a push rod 2, a charging barrel 3, a clamp 4, a plug 5 and a spray head 6, wherein the plug 5 is placed in the charging barrel 3, the charging barrel 3 is placed in the clamp 4, the spray head 6 is connected to the lower part of the charging barrel, the air supply device 1 is connected with the push rod 2, the push rod 2 pushes the plug 5 in the charging barrel 3 to extrude metal slurry, and the overall processing principle is shown in fig. 2.
The inner diameter of the spray head is 1.0mm.
The invention is further illustrated by the following performance test experiments.
The mechanical properties of the processed metal artificial bone scaffold are verified, iron powder is used as printing metal, dichloromethane DCM is used as solvent, polylactic acid PLA is used as polymer to prepare adhesive, the volume ratios of the iron powder to the manganese powder are respectively 10, 9:1, 7:3, 5:5 and 3:7, and the metal slurry is prepared and subjected to uniaxial compression test after the structure is processed. Samples printed by metal slurry with the volume ratio of iron powder to manganese powder being 10, 9:1, 7:3, 5:5 and 3:7 are respectively named as Fe, fe9Mn1, fe7Mn3, fe5Mn5 and Fe3Mn7. Comparing the samples before and after sintering, as shown in fig. 3, a-c are printed scanning electron microscope pictures of the metal samples under different multiplying powers, the metal iron and manganese powder are wrapped by polymer PLA to form a bracket, and spherical iron powder and irregular manganese powder particles can be seen in the c picture and are uniformly distributed. In fig. 3, d-f are scanning electron microscope pictures of the sintered metal sample piece at different magnifications, and it can be seen in the f picture that the iron powder is sintered to form sintering necks, which are connected together to form lines, manganese powder particles inside the lines of the support are evaporated and disappear, and the space occupied by the manganese powder particles originally forms pores.
In order to investigate the internal pore conditions of lines formed by different iron powder and manganese powder ratios, sample pieces prepared by slurries with different iron-manganese volume ratios are compared, as shown in fig. 4, a to e are the surfaces of the printed lines with different manganese contents, wherein Fe9Mn1 represents that the volume ratio of iron to manganese is 9:1, and the volume ratio of iron to manganese in the graph with the highest manganese content e reaches 3:7, and it can be seen from the graph that the roughness of the surface of the sample piece increases with the increase of the manganese content, which is caused by the unsmooth extrusion of the lines through the nozzle due to the irregular shape of manganese. In fig. 4, f to j are pictures of the sample after sintering, which correspond to the sintering results of a to e, respectively, and it can be seen that the sintered surface of the pure iron sample in the f picture has slightly small pores, which are caused by volatilization of the binder polymer PLA, and the pores on the surface of the line are increased after the manganese powder is added.
In order to better understand the distribution of the pores inside the lines, the sample is cut to observe the pore distribution of the internal cross section, as shown in fig. 5, wherein, a is a photograph of the sample, and b-f are photographs of the line cross sections of the sample with different iron-manganese ratios, it can be seen that the internal pores also increase with the increase of the content of manganese powder. It can be seen that as the content of manganese powder increases, the internal porosity produced inside the wire increases.
The test results of the artificial bone scaffold prepared by the same slurry formula show that the mechanical property value is reduced along with the increase of the structural porosity, and the mechanical property is reduced along with the increase of the proportion of the pore-forming agent in the slurry under the condition that the structural porosity is kept unchanged, so that the adjustment of the mechanical property of the artificial bone scaffold can be changed while the porosity of the whole structure is kept unchanged (fig. 6).
Claims (5)
1. A3D printing method for preparing a metal artificial bone based on slurry direct writing is characterized by comprising the following steps:
(1) Weighing the mass ratio of the polymer to the solvent to be 1: 3-5, dissolving the polymer and the solvent in a sealed container for 6-12 hours to prepare a slurry binder which has uniform property, can flow and has certain viscosity;
(2) Weighing printing metal powder with the diameter of 5-100 micrometers and irregular manganese powder serving as a pore-forming agent with the particle size of 5-15 micrometers according to the volume ratio of 1.1-2.4, putting the manganese powder into a ball mill according to the mass ratio of a slurry binder to the total metal powder of 1:3-5, and performing ball milling and mixing for 30-60 minutes at the rotating speed of 200-800r/min to obtain uniformly mixed metal slurry;
(3) Placing metal slurry into a charging barrel, clamping by a clamp, introducing stable air pressure, pushing a push rod by the air pressure so as to push a plug inside the charging barrel, forming pressure on the metal slurry, extruding the metal slurry through a spray head below the charging barrel, forming a filiform metal powder mixed with an adhesive by the extruded metal powder, quickly evaporating a solvent in the adhesive after extrusion, solidifying the polymer coated metal powder, and stacking the metal wires at a speed of 5-20mm/s to form a three-dimensional structure under the drive of a three-dimensional motion platform controlled by a slicing software program to obtain an original piece;
(4) And heat treating the prototype part, including:
1) And vacuumizing: placing a prototype to be sintered into a vacuum sintering furnace, and vacuumizing to reach an air pressure environment below 3 Pa;
2) And pyrolysis of the binder: heating the vacuum 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) Manganese powder evaporation and iron powder fusion: heating the vacuum furnace to 1000-1400 ℃ at the heating rate of 5-10 ℃/min until the temperature reaches the metal vapor pressure critical temperature of the manganese powder, continuing to rise, evaporating the manganese powder, and keeping the temperature for 2-5 h to perform sintering fusion between the printed metal powder particles;
4) And cooling: and after the prototype part is fully sintered, automatically cooling the sintering furnace, and taking out the sample.
2. The 3D printing method for preparing the metal artificial bone based on the slurry direct writing is characterized by comprising the following steps of: the printing head adopted is a pneumatic extrusion type printing head and comprises: the metal slurry extruding 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 inside the charging barrel, the charging barrel is placed inside the clamp, the spray head is connected below the charging barrel, the air supply device is connected with the push rod, and the plug inside the charging barrel is pushed by the push rod to extrude metal slurry.
3. The 3D printing method for preparing the metal artificial bone based on the slurry direct writing is characterized by comprising the following steps of: the inner diameter of the spray head is 0.2-1.0 mm.
4. The 3D printing method for preparing the metal artificial bone based on the slurry direct writing is characterized by comprising the following steps of: the printing metal powder is a metal artificial bone material and comprises iron and titanium alloy.
5. The 3D printing method for preparing the metal artificial bone based on the slurry direct writing is characterized by comprising the following steps of: in the step (1), the polymer comprises polylactic acid (PLA), polyvinyl alcohol (PVA), polyethylene glycol (PEG), chitosan and Polystyrene (PS);
the solvent comprises dichloromethane DCM, water and ethanol solution.
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