CN111761066B - A method for preparing zinc-magnesium alloy products by 3D gel printing - Google Patents
A method for preparing zinc-magnesium alloy products by 3D gel printing Download PDFInfo
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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
- magnesium
- powder
- magnesium alloy
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- 238000007639 printing Methods 0.000 title claims abstract description 91
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 51
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 47
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000011777 magnesium Substances 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 14
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 14
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 14
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- 239000002270 dispersing agent Substances 0.000 claims description 13
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- 238000001125 extrusion Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
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- 239000003054 catalyst Substances 0.000 claims description 8
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005639 Lauric acid Substances 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 239000007790 solid phase Substances 0.000 claims description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims 1
- 230000008676 import Effects 0.000 claims 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 abstract description 18
- 238000010146 3D printing Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 13
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- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 238000001035 drying Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
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- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 5
- 210000001124 body fluid Anatomy 0.000 abstract description 4
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- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 27
- 238000002156 mixing Methods 0.000 description 21
- 238000005516 engineering process Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910001297 Zn alloy Inorganic materials 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008468 bone growth Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000019522 cellular metabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004512 die casting Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000008467 tissue growth Effects 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910017706 MgZn Inorganic materials 0.000 description 1
- 229910017708 MgZn2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000035876 healing Effects 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 210000001519 tissue Anatomy 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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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
- B22F3/227—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 by organic binder assisted extrusion
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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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
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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
- A61L31/148—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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with 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
- 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
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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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
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
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- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
-
- 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
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
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- Health & Medical Sciences (AREA)
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- Vascular Medicine (AREA)
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- Structural Engineering (AREA)
- Ceramic Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
本发明提供一种3D凝胶打印制备锌镁合金制品的方法。先将锌镁合金粉末预处理，再与有机预混液混合，制备出稳定、不易沉降、不易团聚、固相含量高、具有剪切变稀特点的料浆，采用3D凝胶打印机进行打印，将打印坯体经过干燥和烧结获得锌镁合金制品。本发明料浆制备采用环烷酸锌对活泼的锌和镁粉末包覆，减缓其在料浆制备、打印过程、干燥过程中的氧化，保证烧结过程能够形成合金并且烧结致密。本发明的方法能够便捷地解决常用金属3D打印方法难以制备的活泼金属锌镁合金的增材制造，从而容易地用3D打印制备锌镁合金制品；制得的锌镁合金在体液中的降解速率适宜，多孔支架在较高孔隙率下具有较高强度和良好医用前景。The invention provides a method for preparing zinc-magnesium alloy products by 3D gel printing. The zinc-magnesium alloy powder is pretreated first, and then mixed with the organic premix to prepare a slurry that is stable, not easy to settle, not easy to agglomerate, has a high solid content, and has the characteristics of shear thinning. The 3D gel printer is used for printing. The printed body is dried and sintered to obtain a zinc-magnesium alloy product. The preparation of the slurry of the present invention adopts zinc naphthenate to coat the active zinc and magnesium powders, so as to slow down the oxidation during the preparation of the slurry, the printing process and the drying process, and ensure that the sintering process can form an alloy and the sintering is dense. The method of the invention can conveniently solve the additive manufacturing of active metal zinc-magnesium alloys that are difficult to prepare by common metal 3D printing methods, so that zinc-magnesium alloy products can be easily prepared by 3D printing; the degradation rate of the prepared zinc-magnesium alloys in body fluids Suitably, porous scaffolds have higher strength and good medical prospects at higher porosity.
Description
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.
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