CN111761066B - Method for preparing zinc-magnesium alloy product by 3D gel printing - Google Patents

Method for preparing zinc-magnesium alloy product by 3D gel printing Download PDF

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CN111761066B
CN111761066B CN202010517925.9A CN202010517925A CN111761066B CN 111761066 B CN111761066 B CN 111761066B CN 202010517925 A CN202010517925 A CN 202010517925A CN 111761066 B CN111761066 B CN 111761066B
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zinc
printing
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magnesium alloy
magnesium
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CN111761066A (en
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林涛
靳浏平
邵慧萍
李继康
韩宇
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University of Science and Technology Beijing USTB
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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
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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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
    • A61L27/58—Materials at least partially resorbable by the body
    • A—HUMAN NECESSITIES
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    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/146—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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    • B22F3/10—Sintering only
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    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
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    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • C22C18/00—Alloys based on zinc
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Abstract

The invention provides a method for preparing a zinc-magnesium alloy product by 3D gel printing. Pretreating zinc-magnesium alloy powder, mixing with an organic premix, preparing a slurry which is stable, not easy to settle, not easy to agglomerate, high in solid content and has the characteristic of shear thinning, printing by using a 3D gel printer, and drying and sintering a printed blank to obtain a zinc-magnesium alloy product. The preparation of the slurry adopts zinc naphthenate to coat active zinc and magnesium powder, so that the oxidation of the zinc naphthenate in the preparation, printing and drying processes of the slurry is slowed down, and the sintering process can form alloy and is sintered compactly. The method can conveniently solve the problem of additive manufacturing of the active metal zinc-magnesium alloy which is difficult to prepare by a common metal 3D printing method, so that a zinc-magnesium alloy product is easily prepared by 3D printing; the prepared zinc-magnesium alloy has proper degradation rate in body fluid, and the porous support has higher strength and good medical prospect under higher porosity.

Description

Method for preparing zinc-magnesium alloy product by 3D gel printing
Technical Field
The invention relates to a method for preparing a zinc-magnesium alloy product through 3D printing, and belongs to the field of additive manufacturing (3D printing).
Background
The zinc alloy has low melting point, good fluidity and strong plasticity, and can be remelted and recycled. Strong corrosion resistance, and is not easy to oxidize compared with magnesium alloy. Therefore, the zinc alloy plays an important role in the fields of electronic devices, automobile accessories and the like. In addition, zinc is an important macroelement of human body and plays an important role in the aspects of human body functions, cell metabolism and the like. Zinc is a trace element which is most widely distributed in organisms, almost all cells with life activities contain zinc, and the zinc plays important roles in catalyzing the activity of various enzymes, regulating the differentiation and gene expression of cells, maintaining the structural stability of cell membranes, participating in the maturation of immune functions and the like in the organisms. Zinc degrades more slowly than magnesium and more rapidly than iron. Therefore, the zinc alloy has wide prospect in the aspect of degradable materials, has great application potential in medical degradable materials, and is expected to be developed into cardiovascular stents, nasal stents, bone fracture plates for internal fixation, fixation and the like. Magnesium is an essential metal in the human body, is an important activator of various enzyme systems in cell metabolism, activates many important enzymes, and thus a zinc-magnesium alloy is prepared to have a proper corrosion rate in body fluids by adjusting the contents of zinc and magnesium elements.
The zinc alloy is formed by die casting because of good fluidity and low melting point. In the process of die-casting forming, air holes are formed due to poor exhaust of a die, shrinkage cavities are formed in the cooling process, cold shut is caused by cooling in the mold filling process, and mechanical properties of the alloy are reduced due to large uneven stress of the thickness of a casting and the like. And the design of the die is difficult, the energy consumption is large, and the like, so that the production cost is increased.
Three-dimensional rapid prototyping printing is called 3D printing for short, also called Additive Manufacturing (Additive Manufacturing), is a leading-edge technology which needs a plurality of technologies such as material science technology, electromechanical control technology, information technology and the like to be closely matched, relates to a plurality of subjects such as CAD modeling, machinery, laser, materials and the like, and adopts a layer-by-layer stacking mode from bottom to top to form by means of three-dimensional model data. 3D printing technique can realize the accurate control to microstructure through the computer according to the specific spatial structure who designs, is thought to have very big potentiality on making complicated shape article, is known as the core technology of "industrial revolution for the third time". However, 3D printing is still difficult at present due to the problems of low melting point, high activity, easy splashing and volatilization and the like of zinc and magnesium. The 3D gel-printing (3 DGP) technology is a new 3D print forming technology based on the combination of gel injection molding and inkjet printing. The slurry is prepared by mixing organic monomer, organic solvent, metal or ceramic powder and dispersant. The slurry is sprayed to the printing platform from the charging barrel and is stacked layer by layer from bottom to top to form a printed product. And the printing and curing forming are realized during the printing process. The printed product with high density is obtained by the processes of drying, degreasing, sintering and the like.
Patent ZL201810339941.6 provides a method for preparing magnesium alloy by 3D gel printing, and provides a feasible way for 3D printing and forming of magnesium alloy. Because magnesium has high degradation rate and is easy to form bubbles at the initial stage of implantation, magnesium is added on the basis of zinc to prepare alloy to adjust the degradation rate. In terms of medical implant materials, due to patient variability, implant materials can be well customized for different patients by 3D printing.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a novel method for manufacturing a zinc-magnesium alloy product by 3D gel printing.
The invention provides a method for preparing a zinc alloy product by 3D gel printing, which comprises the following steps:
(1) the zinc-magnesium alloy comprises the following components: mg15.5-48.5 wt.%, and Zn in balance, uniformly mixing zinc powder and magnesium powder in proportion, dissolving zinc naphthenate accounting for 0.5-2.5 wt.% of the powder mass in an organic solvent A, adding the uniformly mixed zinc powder and magnesium powder, stirring and dispersing, and performing vacuum drying at 40-50 ℃ to obtain zinc-magnesium mixed powder;
(2) uniformly mixing an organic monomer and an organic solvent B according to the volume ratio of 1:5-5:1 to prepare a premixed liquid with the concentration of the organic monomer of 16.6-83.3 vol.%, mixing and stirring the zinc-magnesium mixed powder obtained in the step (1) and the premixed liquid according to the volume ratio of (1-4):1, adding 0.3-4.5 wt.% of a dispersing agent, and uniformly mixing to obtain slurry with the solid content of 50-80 vol.% and the viscosity of 1200-3600 Pa.s;
(3) filling the slurry obtained in the step (2) into a charging barrel of a 3D gel printer, introducing the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.1-1.0mm, the viscosity of the slurry passing through the nozzle is 14-32Pa.s, the printing layer height is 0.08-0.8mm, and the extrusion rate is 50-200mm3The printing speed is 5-10mm/s, and when one layer of printing is finished, a layer of atomized initiator Benzoyl Peroxide (BPO) and catalyst N, N, N ', N' -tetramethyl ethylenediamine (TEMED) are sprayed on the printing surface by a spraying device to realize printing and curing;
(4) vacuum drying the blank obtained by printing at 30-50 ℃ for 8-24h, degreasing the dried blank at 400 ℃ for 5-10h in a protective atmosphere, then sintering at 520 ℃ in a protective atmosphere or vacuum at 420 ℃ for 1-2h, and cooling to 350 ℃ and 380 ℃ for 6-8h to obtain the zinc-magnesium alloy product.
Further, as described above: the granularity of the zinc powder and the magnesium powder is less than 150 mu m.
Further, as described above: the organic solvent A is one of benzene, toluene and xylene.
Further, as described above: the organic monomer is one of acrylamide, methacrylamide and hydroxyethyl methacrylate (HEMA); the organic solvent B is one of methanol, ethanol and isopropanol.
Further, as described above: the dispersant is one of oleic acid, lauric acid, ammonium citrate or DISPERBYK-110.
Furthermore, the invention also provides the zinc-magnesium alloy porous scaffold prepared by the method, wherein the porosity is 45-75%, and the compressive strength is 34-56 MPa.
The invention provides a novel zinc-magnesium alloy 3D gel printing preparation technology, which is used for solving the defects of the prior art. The method comprises the steps of preparing powder and organic components into slurry, realizing 3D forming in a mode of printing while gelling, and removing the organic components and sintering to obtain a final product. The key technology is as follows:
(1) design of zinc-magnesium alloy: magnesium is a degradable metal in vivo, but its activity is high and it degrades rapidly in vivo. Hydrogen gas is also generated during degradation, forming bubbles, causing problems with healing and inflammation. Zinc is also degradable, but at a slower rate. In the method of the present invention, first, there is providedThe zinc-magnesium alloy containing 15.5-48.5 wt.% of Mg15 is used for coordinating the degradability of zinc and magnesium, the degradation rate of the zinc-magnesium alloy in body fluid is proper, and the problems that magnesium is degraded quickly and hydrogen bubbles are generated and zinc is degraded slowly to influence bone growth are solved. After zinc powder and magnesium powder are sintered, densified and isothermally aged to form zinc-magnesium alloy, MgZn and Mg are arranged on a zinc matrix2Zn3、MgZn2And the strength of the material is improved by 22-34% compared with pure zinc. And has the characteristics of slow degradation in the early stage and fast degradation in the later stage. Therefore, the zinc-magnesium alloy stent product maintains the shape and the supporting strength in the early stage of implantation, tissues grow into the macropores of the stent, and the stent accelerates the degradation and absorption after the later-stage tissue growth is basically completed, so that the secondary operation is avoided.
(2) Coating zinc powder and magnesium powder: the zinc powder and the magnesium powder are taken as raw materials and are uniformly mixed according to the proportion, zinc naphthenate accounting for 0.5 to 2.5 wt.% of the weight of the powder is dissolved in an organic solvent A, the uniformly mixed zinc powder and the magnesium powder are added and stirred for dispersion, and the zinc-magnesium mixed powder is obtained by vacuum drying at the temperature of between 40 and 50 ℃. The granularity of the zinc powder and the magnesium powder is less than 150 mu m, and the organic solvent A is benzene, toluene or xylene. Zinc and magnesium are highly active metals, and particularly magnesium has higher activity, and the activity after being made into powder is particularly high, and the powder is more easily oxidized as the powder is finer, so that the powder is not easily too fine. And too tiny magnesium powder is too dangerous and easy to ignite spontaneously and even explode. The oxide layer covers the powder surface, so that the powder characteristics are changed, and the subsequent sintering is greatly hindered. The invention adopts zinc naphthenate to coat active zinc and magnesium powder. The zinc naphthenate is dissolved in benzene, toluene or xylene, and then a layer of zinc naphthenate is coated on the surfaces of zinc powder and magnesium powder through vacuum drying. Active zinc and magnesium powder are coated by zinc naphthenate, so that oxidation of the zinc naphthenate in slurry preparation, printing and drying processes is slowed down, and alloy can be formed in a sintering process and sintering compactness is guaranteed. After being coated, the zinc naphthenate can not be dissolved again by organic solvent methanol, ethanol or isopropanol in the subsequent slurry preparation process, and still plays a role in protection. This is advantageous over citric acid. And the slurry prepared after the zinc naphthenate is coated has high stability and high solid content, and meanwhile, the zinc-magnesium powder slurry has high viscosity at a low shear rate (static state) and low viscosity at a high shear rate (extrusion), so that the smooth 3D printing and forming process is ensured. Experiments show that after the powder is subjected to coating treatment, 3D printing and sintering, the density of the zinc-magnesium alloy is improved by more than 32% compared with that of the zinc-magnesium alloy without the coating treatment, and the compressive strength is improved by more than 41%.
(3) Preparing printing slurry: uniformly mixing an organic monomer and an organic solvent B according to the volume ratio of 1:5-5:1 to prepare a premixed liquid with the concentration of the organic monomer of 16.6-83.3 vol.%, mixing and stirring the zinc-magnesium mixed powder obtained in the step (2) and the premixed liquid according to the volume ratio of (1-4):1, adding 0.3-4.5 wt.% of a dispersing agent, and uniformly mixing to obtain slurry with the solid content of 50-80 vol.% and the viscosity of 1200-3600 Pa.s. The organic monomer is one of acrylamide, methacrylamide and hydroxyethyl methacrylate (HEMA), and the organic solvent B is one of methanol, ethanol and isopropanol. The gel system of the invention selects organic matters, and has no oxidation and corrosion reaction on the zinc-magnesium powder. The pre-mixed liquid with different concentrations is obtained by different proportions of the organic monomer and the organic solvent, the concentration of the pre-mixed liquid influences the viscosity of the slurry, and the solid content is selected according to the porosity requirement of the final product. Therefore, the solid content is determined according to the porosity requirement of the final product, and then the concentration of the premix is determined to make the viscosity of the slurry meet the requirement of 3D printing and forming. The 3D printing with the low concentration of the premix liquid is too slow to solidify, so that the shape cannot be formed. The premixed liquid has too high concentration, too fast solidification, large viscosity, no numerical value of solid content, too loose after sintering, too low strength and no practical value. The upper and lower limits of the solid content are obtained by integrating the product requirements and optimizing the concentration of the premix. Too low a solid content will result in too poor strength of the sintered product, and too high a solid content will result in too high a viscosity of the slurry to be printed. A dispersant, preferably one of oleic acid, lauric acid, ammonium citrate, or DISPERBYK-110, is also added during the preparation of the printing slurry. The dispersing agent is also indispensable, so that the zinc powder and the magnesium powder can be kept in a dispersed state in the premixed liquid and cannot be settled in the printing process, the slurry is extruded more uniformly in the printing process, and all parts of alloy in the product are uniformly distributed and are not deformed in sintering. The oleic acid and lauric acid in the dispersants have a general effect, and ammonium citrate or DISPERBYK-110 has a better effect, especially the latter. The solid content without zinc naphthenate coating treatment is less than 55 percent, the printing state is unstable, and the yarn is broken frequently. The viscosity of 1200-3600Pa.s can make the slurry keep its shape immediately after extruding the nozzle.
(4) Printing and forming: loading the slurry into a charging barrel of a 3D gel printer, introducing the shape of the product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.1-1.0mm, the viscosity of the slurry passing through the nozzle is 14-32Pa.s, the height of a printing layer is 0.08-0.8mm, and the extrusion rate is 50-200mm3And/min, the printing speed is 5-10mm/s, and when one layer of printing is finished, the spraying device sprays a layer of atomized initiator Benzoyl Peroxide (BPO) and catalyst N, N, N ', N' -Tetramethylethylenediamine (TEMED) on the printing surface to realize printing and curing. The 3D gel printer mainly comprises a material cylinder for storing slurry, a nozzle for extruding the slurry, a conveying part for conveying the slurry, a 3D position mechanical part, a curing agent spraying device and a computer control system. And (3) introducing a product to be printed and formed into a computer control system, conveying the slurry to the nozzle from the material cylinder by the conveying part, enabling the nozzle to be arranged on the printing head, and extruding the slurry out of the nozzle under the drive of the 3D position mechanical part to finish 3D shape printing. When one layer of printing is finished, the spraying device sprays a layer of foggy initiator and catalyst on the printing surface to induce the polymerization of the organic monomer, so as to realize gelation and fix the shape. The selection of printing parameters needs to be matched according to factors such as the shape and the dimensional accuracy of the product, the solid content of slurry, the viscosity and the like. The viscosity of the slurry of the invention is 14-32Pa.s when the slurry passes through the nozzle, while the viscosity of the powder slurry without coating treatment exceeds 300Pa.s, which causes large extrusion pressure, difficult extrusion and easy filament breakage.
(5) Drying and sintering a printing blank body: vacuum drying the blank obtained by printing at 30-50 ℃ for 8-24h, degreasing the dried blank at 400 ℃ for 5-10h in a protective atmosphere, then sintering at 520 ℃ in a protective atmosphere or vacuum at 420 ℃ for 1-2h, and cooling to 350 ℃ and 380 ℃ for 6-8h to obtain the zinc-magnesium alloy product. Vacuum drying is to further solidify the printing blank and to evaporate part of the organic solvent. Degreasing is to decompose and remove organic components in the printing blank body and only leave the original zinc-magnesium powder. Sintering is carried out under the protection of nitrogen or argon or under vacuum to prevent the zinc-magnesium powder from being oxidized. The zinc naphthenate is firstly converted into zinc oxide in the process for protection, and then is volatilized so as to avoid the obstruction to sintering. The sintering temperature will depend on the alloy composition and may also vary depending on the article properties. The heat preservation at the temperature of 350-380 ℃ for 6-8h after sintering is an aging process, and the aim is to separate out the magnesium-zinc compound to play a role in strengthening and regulating the degradation rate. The zinc-magnesium alloy product is obtained after sintering, the porosity of the product can be adjusted according to different application requirements, the porosity can be 45-75%, and the compressive strength is 34-56 MPa. According to the shape requirement of the product, the zinc-magnesium alloy product prepared by the method comprises implants such as cartilage scaffolds, blood vessel scaffolds and the like, and the structure of the product is latticed, so that a plurality of spaces are left for tissue growth.
Compared with the prior art, the method has the advantages that: the zinc-magnesium alloy containing 15.5-48.5 wt.% of Mg15 is suitable in degradation rate in body fluid, so that the problems of rapid magnesium degradation and generation of hydrogen bubbles and slow zinc degradation and influence on bone growth are solved. Meanwhile, the porous scaffold has higher strength at higher porosity. In the slurry preparation process, zinc naphthenate is adopted to coat active zinc and magnesium powder, so that the oxidation of the active zinc and magnesium powder in the slurry preparation, printing and drying processes is slowed down, and the alloy can be formed in the sintering process and the sintering is compact. By coating the zinc naphthenate, the prepared slurry has high stability and high solid content, and meanwhile, the zinc-magnesium powder slurry has high viscosity at a low shear rate (static state) and low viscosity at a high shear rate (extrusion), so that the smooth 3D printing and forming process is ensured. Therefore, the method can conveniently solve the problem of additive manufacturing of the active metal zinc-magnesium alloy which is difficult to prepare by a common metal 3D printing method such as SLM (spatial light modulation) and the like, so that the zinc-magnesium alloy product can be easily prepared by 3D printing. In addition, the zinc-magnesium alloy porous support product prepared by the method has high porosity, flexible porosity adjustment and high strength, and has good medical prospect.
Detailed Description
Example 1:
(1) the zinc-magnesium alloy comprises the following components: mg15.5 wt.% and Zn in balance, zinc powder and magnesium powder are used as raw materials and are uniformly mixed according to a proportion, the particle size of the zinc powder and the particle size of the magnesium powder are less than 150 mu m, zinc naphthenate accounting for 0.5 wt.% of the mass of the powder is dissolved in organic solvent benzene, the uniformly mixed zinc powder and magnesium powder are added and stirred for dispersion, and the zinc-magnesium mixed powder is obtained after vacuum drying at 40 ℃;
(2) uniformly mixing an organic monomer acrylamide and an organic solvent methanol according to the volume ratio of 1:5 to prepare a premixed liquid with the concentration of the organic monomer of 16.6 vol.%, mixing and stirring zinc-magnesium mixed powder and the premixed liquid according to the volume ratio of 1:1, adding 0.3 wt.% of dispersant DISPERBYK-110, and uniformly mixing to obtain slurry with the solid phase content of 50 vol.% and the viscosity of 1200 Pa.s;
(3) loading the slurry into a charging barrel of a 3D gel printer, introducing the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.1mm, the viscosity of the slurry passing through the nozzle is 14Pa.s, the printing layer height is 0.08mm, and the extrusion rate is 50mm3The printing speed is 5mm/s, and when one layer of printing is finished, a layer of foggy initiator Benzoyl Peroxide (BPO) and catalyst N, N, N ', N' -tetramethyl ethylenediamine (TEMED) are sprayed on the printing surface by a spraying device to realize printing and curing;
(4) and (2) drying the blank obtained by printing at 30 ℃ in vacuum for 24h, degreasing the dried blank at 400 ℃ for 10h in a protective atmosphere, then sintering at 520 ℃ in the protective atmosphere or in vacuum for 1h, cooling to 350 ℃, and preserving heat for 8h to obtain the zinc-magnesium alloy porous support, wherein the porosity is 45% and the compressive strength is 34 MPa.
Example 2:
(1) the zinc-magnesium alloy comprises the following components: mg48.5 wt.% and Zn in balance, zinc powder and magnesium powder are used as raw materials and are uniformly mixed according to a proportion, the particle size of the zinc powder and the particle size of the magnesium powder are less than 150 mu m, zinc naphthenate accounting for 2.5 wt.% of the mass of the powder is dissolved in organic solvent toluene, the uniformly mixed zinc powder and magnesium powder are added and stirred for dispersion, and the zinc-magnesium mixed powder is obtained after vacuum drying at 50 ℃;
(2) uniformly mixing organic monomer hydroxyethyl methacrylate (HEMA) and organic solvent isopropanol according to the volume ratio of 5:1 to prepare premixed liquid with the organic monomer concentration of 83.3 vol.%, mixing zinc-magnesium mixed powder and the premixed liquid according to the volume ratio of 4:1, stirring, adding 4.5 wt.% dispersant oleic acid, and uniformly mixing to obtain slurry with the solid phase content of 80 vol.% and the viscosity of 3600 Pa.s;
(3) loading the slurry into a charging barrel of a 3D gel printer, introducing the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 1.0mm, the viscosity of the slurry passing through the nozzle is 32Pa.s, the height of a printing layer is 0.8mm, and the extrusion rate is 200mm3The printing speed is 10mm/s, and when one layer of printing is finished, a layer of foggy initiator Benzoyl Peroxide (BPO) and catalyst N, N, N ', N' -tetramethyl ethylenediamine (TEMED) are sprayed on the printing surface by a spraying device to realize printing and curing;
(4) and (2) drying the printed blank in vacuum at 50 ℃ for 8h, degreasing the dried blank in a protective atmosphere at 100-400 ℃ for 5h, sintering at 420 ℃ in a protective atmosphere or vacuum for 2h, cooling to 380 ℃, and preserving heat for 6h to obtain the zinc-magnesium alloy porous support, wherein the porosity is 75% and the compressive strength is 56 MPa.
Example 3:
(1) the zinc-magnesium alloy comprises the following components: mg25 wt%, and Zn in balance, taking zinc powder and magnesium powder as raw materials, uniformly mixing the raw materials according to a proportion, wherein the particle size of the zinc powder and the magnesium powder is less than 150 mu m, dissolving zinc naphthenate accounting for 1.2 wt% of the powder mass in organic solvent xylene, adding the uniformly mixed zinc powder and magnesium powder, stirring and dispersing, and performing vacuum drying at 45 ℃ to obtain zinc-magnesium mixed powder;
(2) uniformly mixing an organic monomer methacrylamide and an organic solvent ethanol according to a volume ratio of 1:1 to prepare a premixed liquid with an organic monomer concentration of 50 vol.%, mixing and stirring zinc-magnesium mixed powder and the premixed liquid according to a volume ratio of 2:1, adding 3.0 wt.% of dispersant lauric acid, and uniformly mixing to obtain slurry with a solid phase content of 66.7 vol.% and a viscosity of 2400 Pa.s;
(3) loading the slurry into a charging barrel of a 3D gel printer, introducing the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.5mm, the viscosity of the slurry passing through the nozzle is 25Pa.s, the height of a printing layer is 0.48mm, and the extrusion rate is 100mm3The printing speed is 7mm/s, and when one layer of printing is finished, a layer of foggy initiator Benzoyl Peroxide (BPO) and catalyst N, N, N ', N' -tetramethyl ethylenediamine (TEMED) are sprayed on the printing surface by a spraying device to realize printing and curing;
(4) and (3) drying the blank obtained by printing at 40 ℃ in vacuum for 16h, degreasing the dried blank at 400 ℃ in a protective atmosphere for 7h, then sintering at 490 ℃ in the protective atmosphere or in vacuum for 1.5h, cooling to 360 ℃, and preserving the heat for 7h to obtain the zinc-magnesium alloy porous support, wherein the porosity is 55%, and the compressive strength is 41 MPa.
Example 4:
(1) the zinc-magnesium alloy comprises the following components: mg35 wt%, and the balance Zn, zinc powder and magnesium powder are taken as raw materials and uniformly mixed according to the proportion, the particle size of the zinc powder and the magnesium powder is less than 150 mu m, zinc naphthenate accounting for 1.8 wt% of the powder mass is dissolved in organic solvent xylene, the uniformly mixed zinc powder and magnesium powder are added and stirred for dispersion, and the zinc-magnesium mixed powder is obtained after vacuum drying at the temperature of 45 ℃;
(2) uniformly mixing an organic monomer acrylamide and an organic solvent ethanol according to a volume ratio of 3:1 to prepare a premixed liquid with an organic monomer concentration of 75 vol.%, mixing and stirring zinc-magnesium mixed powder and the premixed liquid according to a volume ratio of 1.5:1, adding 2.5 wt.% of dispersant ammonium citrate, and uniformly mixing to obtain slurry with a solid phase content of 60 vol.% and a viscosity of 2100 Pa.s;
(3) filling the slurry obtained in the step (3) into a charging barrel of a 3D gel printer, introducing the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.8mm, the viscosity of the slurry passing through the nozzle is 21Pa.s, the height of a printing layer is 0.75mm, and the extrusion rate is 150mm3Min, printing speed 8mm/s, perCompleting one layer of printing, wherein a spraying device sprays a layer of foggy initiator Benzoyl Peroxide (BPO) and catalyst N, N, N ', N' -Tetramethylethylenediamine (TEMED) on the printing surface to realize printing and curing;
(4) and (3) drying the blank obtained by printing at 40 ℃ in vacuum for 20h, degreasing the dried blank at 400 ℃ for 8h in a protective atmosphere, then sintering at 460 ℃ in the protective atmosphere or vacuum for 2h, cooling to 360 ℃, and preserving heat for 7h to obtain the zinc-magnesium alloy porous support, wherein the porosity is 65%, and the compressive strength is 38 MPa.

Claims (6)

1. A method for preparing a zinc-magnesium alloy product by 3D gel printing is characterized by comprising the following preparation steps:
(1) the zinc-magnesium alloy comprises the following components: mg15.5-48.5 wt.%, and Zn in balance, uniformly mixing zinc powder and magnesium powder in proportion, dissolving zinc naphthenate accounting for 0.5-2.5 wt.% of the powder mass in an organic solvent A, adding the uniformly mixed zinc powder and magnesium powder, stirring and dispersing, and performing vacuum drying at 40-50 ℃ to obtain zinc-magnesium mixed powder;
(2) uniformly mixing an organic monomer and an organic solvent B according to the volume ratio of 1:5-5:1 to prepare a premixed liquid with the concentration of the organic monomer of 16.6-83.3 vol.%, mixing and stirring the zinc-magnesium mixed powder obtained in the step (1) and the premixed liquid according to the volume ratio of (1-4):1, adding 0.3-4.5 wt.% of a dispersing agent, and uniformly mixing to obtain slurry with the solid content of 50-80 vol.% and the viscosity of 1200-3600 Pa.s;
(3) filling the slurry obtained in the step (2) into a charging barrel of a 3D gel printer, introducing the shape of a product to be printed into a computer control system for printing, wherein the diameter of a nozzle selected for printing is 0.1-1.0mm, the viscosity of the slurry passing through the nozzle is 14-32Pa.s, the height of a printing layer is 0.08-0.8mm, and the extrusion rate is 50-200mm3The printing speed is 5-10mm/s, and when one layer of printing is finished, a layer of atomized initiator Benzoyl Peroxide (BPO) and catalyst N, N, N ', N' -tetramethyl ethylenediamine (TEMED) are sprayed on the printing surface by a spraying device to realize printing and curing;
(4) vacuum drying the blank obtained by printing at 30-50 ℃ for 8-24h, degreasing the dried blank at 400 ℃ for 5-10h in a protective atmosphere, then sintering at 520 ℃ in a protective atmosphere or vacuum at 420 ℃ for 1-2h, and cooling to 350 ℃ and 380 ℃ for 6-8h to obtain the zinc-magnesium alloy product.
2. The method of 3D gel printing to produce a zinc-magnesium alloy article according to claim 1, wherein: the granularity of the zinc powder and the magnesium powder is less than 150 mu m.
3. The method of 3D gel printing to produce a zinc-magnesium alloy article according to claim 1, wherein: the organic solvent A is one of benzene, toluene and xylene.
4. The method of 3D gel printing to produce a zinc-magnesium alloy article according to claim 1, wherein: the organic monomer is one of acrylamide, methacrylamide and hydroxyethyl methacrylate (HEMA); the organic solvent B is one of methanol, ethanol and isopropanol.
5. The method of 3D gel printing to produce a zinc-magnesium alloy article according to claim 1, wherein: the dispersant is one of oleic acid, lauric acid, ammonium citrate or DISPERBYK-110.
6. A zinc-magnesium alloy porous scaffold prepared by the method of claim 1, having a porosity of 45-75% and a compressive strength of 34-56 MPa.
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