CN113476184A - Method for preparing magnetic biological implant - Google Patents
Method for preparing magnetic biological implant Download PDFInfo
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- CN113476184A CN113476184A CN202110616450.3A CN202110616450A CN113476184A CN 113476184 A CN113476184 A CN 113476184A CN 202110616450 A CN202110616450 A CN 202110616450A CN 113476184 A CN113476184 A CN 113476184A
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- 239000007943 implant Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000007639 printing Methods 0.000 claims abstract description 72
- 239000000243 solution Substances 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
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- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 19
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 11
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
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- 239000005642 Oleic acid Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 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 3
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- 239000002131 composite material Substances 0.000 claims 1
- 210000000988 bone and bone Anatomy 0.000 abstract description 13
- 238000005119 centrifugation Methods 0.000 abstract description 6
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000000015 thermotherapy Methods 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 210000002901 mesenchymal stem cell Anatomy 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
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- 238000002560 therapeutic procedure Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/28—Bones
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2/30771—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth applied in original prostheses, e.g. holes or grooves
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2/30942—Designing or manufacturing processes for designing or making customized prostheses, e.g. using templates, CT or NMR scans, finite-element analysis or CAD-CAM techniques
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2/30771—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth applied in original prostheses, e.g. holes or grooves
- A61F2002/30772—Apertures or holes, e.g. of circular cross section
- A61F2002/30784—Plurality of holes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2002/3093—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth for promoting ingrowth of bone tissue
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/3094—Designing or manufacturing processes
- A61F2002/30985—Designing or manufacturing processes using three dimensional printing [3DP]
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2210/00—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof
- A61F2210/009—Particular material properties of prostheses classified in groups A61F2/00 - A61F2/26 or A61F2/82 or A61F9/00 or A61F11/00 or subgroups thereof magnetic
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—Metals or alloys
- A61F2310/00035—Other metals or alloys
- A61F2310/00041—Magnesium or Mg-based alloys
Landscapes
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Vascular Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Transplantation (AREA)
- Cardiology (AREA)
- Biomedical Technology (AREA)
- Heart & Thoracic Surgery (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
Abstract
The invention provides a method for preparing a magnetic biological bone tissue engineering implant, belonging to the field of preparation of magnetic materials. Firstly, a certain amount of MgCl is added2·6H2O and FeCl3·6H2Dissolving O in deionized water, and heating to about 50 deg.C in water bath. Stirring the mixed solution by an electric stirrer, dissolving the mixed solution uniformly, and adding excessive NH3·H2Slowly dripping O into the solution, and continuously stirring to obtain alkaline turbid solution. At this time, Mg (OH) is formed in the solution2And Fe (OH)3And (3) washing the prepared precursor particles with deionized water through centrifugation and inversion to obtain the precursor particles. Preparing slurry with the solid content of 40-65 vol% by using the prepared PVA solution, printing a porous implant by setting parameters such as nozzle aperture, printing layer height, printing speed and the like, and then carrying out degreasing and sintering, and decomposing and volatilizing an organic solvent to obtain MgFe2O4Magnetic implantAnd (4) inserting the parts. The method for preparing the magnetic implant has the advantages of simple operation, low cost and strong repeatability.
Description
Technical Field
The invention relates to a method for preparing MgFe2O4A method of magnetic implant belongs to the field of magnetic material manufacture.
Background
Compared with the traditional manufacturing technology, the 3D printing technology can realize the near-net-shape forming of the product and has the characteristics of direct and rapid performance, personalized design, simple and convenient operation and the like. The 3D printing is applied to the preparation of the bone tissue engineering implant, and the porous implant with proper shape, aperture and porosity can be designed and manufactured to induce bone regeneration according to different requirements of patients. The 3D gel printing is a novel 3D printing technology based on a slurry direct-writing forming technology, wherein printing ink is composed of slurry with low viscosity and high solid-phase volume fraction content, the slurry is extruded to a printing platform through a needle tube by a printer, the printing platform is rapidly solidified and formed, green body parts are formed by printing layer by layer, and then the green body parts with certain compressive strength are obtained after degreasing and sintering. The technology is suitable for various materials, the shape of the product is not limited, the equipment cost is low, and the production efficiency is high.
Conventional tissue engineering implants, once implanted, cannot be reloaded with biological agents necessary to promote and induce tissue regeneration, and studies have shown that the synergistic effects of an applied magnetic field and a superparamagnetic responsive implant can promote bone repair and regeneration. The superparamagnetic nano-particle can carry biological agents such as growth factors, hormones and the like, and can generate mechanical stimulation on cells on the surface of the bone implant under the action of an external static magnetic field, so that the osteogenic differentiation of the cells is enhanced, and the formation of new bone tissues is promoted; can also be used for treating bone tumor by drug loading and thermotherapy. General formula XFe2O4The nano spinel ferrite (X is divalent metal cation of Mg, Mn, Fe, Co, Ni, etc.) is an important magnetic metal oxide containing trivalent (Fe)3+) And divalent (i.e. Mg)2+，Mn2+，Fe2+，Co2 +，Ni2+) The metal ions are respectively coordinated in the crystal structure and occupy tetrahedral and octahedral cation positions, and have wide application in the fields of adsorption, communication, electronic devices, biomedicine and the like. Mg (magnesium)2+Is the main cation in human body, has the content next to calcium, sodium and potassium elements in human body, can activate various enzymes, participate in a series of metabolism in the human body, can promote the deposition of calcium, and has the capabilities of enhancing the activity of osteoblast and promoting the healing of bones. MgFe2O4With lighter metallic Mg2+Substituted Fe3O4Fe in (1)2+More defect active sites can be generated on the surface, the heating response is high, and the coating has excellent chemical stability, superparamagnetism, electromagnetic wave absorption performance and biocompatibility, andbecause of its high resistivity, it will not cause harm to human body under high frequency, it is the ideal choice of magnetic thermal therapy, targeted medicine carrying. Preparation of MgFe2O4The methods of (3) include coprecipitation, sol-gel, mechanochemical, hydrothermal synthesis and the like. Wherein, the chemical coprecipitation method has simple operation and low production cost.
MgFe prepared by using 3D gel printing technology2O4The magnetic implant has the advantages of simple forming process, high repeatability and cost saving.
Disclosure of Invention
The invention provides a method for preparing MgFe for preparing magnetic multi-hole tissue engineering implant, which solves the problems of insufficient functionality and magnetic material preparation process of the existing implant2O4A method of magnetic implant.
The principle of the invention is as follows: firstly, MgFe is prepared by a chemical coprecipitation method2O4Precursor nanoparticles, adding a certain amount of MgCl2·6H2O and FeCl3·6H2Dissolving O in 200-500 ml of deionized water, and heating to about 50 ℃ in a water bath kettle. Stirring the mixed solution for 5-20 min by using an electric stirrer, uniformly dissolving, and adding excessive NH3·H2And slowly dripping O into the solution, and continuously stirring for 20-60 min to obtain alkaline turbid solution. At this time, Mg (OH) is formed in the solution2And Fe (OH)3And (3) washing the prepared precursor particles with deionized water through centrifugation and inversion to obtain the precursor particles. Preparing slurry with the solid content of 40-65 vol% by using the prepared PVA solution, printing a porous implant by setting parameters such as nozzle aperture, printing layer height, printing speed and the like, degreasing and sintering, decomposing and volatilizing an organic solvent, and synthesizing magnetic MgFe from precursor particles2O4Obtaining MgFe2O4A magnetic implant.
Based on the above principle, the process of the present invention includes: MgFe2O4Preparing a magnetic nanoparticle precursor, preparing printing slurry, printing 3D gel, degreasing and sintering. The invention provides a magnetic biological implant prepared by 3D gel printingThe method of the piece comprises the following steps:
(1)MgFe2O4preparing a magnetic nanoparticle precursor: preparing a precursor by a chemical coprecipitation method, and respectively weighing 20-60 g of MgCl2·6H2O and 40-120 gFeCl3·6H2Mixing and dissolving O in 200-500 ml of deionized water, and heating to 45-80 ℃ in a water bath kettle; stirring the mixed solution for 5-20 min by using an electric stirrer, uniformly dissolving, and adding 25-28% excessive NH3·H2Slowly dripping O into the solution, and continuously stirring for 20-60 min to obtain alkaline turbid solution; washing the prepared precursor nano-particles by using a centrifugal process repeatedly until the solution is neutral, and pouring off the liquid part to leave the generated precursor nano-particles;
(2) preparing printing slurry: mixing PVA solid particles and deionized water according to a mass ratio of 1 (9-24), heating to 60-95 ℃, stirring for 1-3 h to obtain a powder cross-linking solution, mixing the precursor powder obtained in the step (1) and the PVA solution according to a mass ratio of (0.5-3.5) to 1, continuously adding a dispersing agent accounting for 0.5-2 wt% of the total weight of the powder, and uniformly stirring to obtain printing slurry;
(3) filling the printing slurry obtained in the step (2) into a charging barrel of a 3D gel printer, setting the aperture of a printing nozzle to be 0.4-0.8 mm, the height of a printing layer to be 0.3-0.7 mm, and setting the printing speed to be 6-15 mm/s; guiding the slice code of the three-dimensional implant into a printer, extruding slurry out of a needle tube under the action of air pressure, and printing the porous implant;
(4) drying the printed implant blank in air for 24-48 h, then carrying out heat preservation at 600-800 ℃ for 1-2 h for degreasing, sintering at 1200-1400 ℃ for 1-3 h, and obtaining the magnetic implant after sintering.
Further, MgCl described in step (1)2·6H2O and FeCl3·6H2O solution with the mass ratio of n (Mg)2 +):n(Fe3+) 2: 3; precursor nano-particles with different particle sizes can be prepared by changing the water bath heating temperature and the stirring time.
Further, the dispersant in the step (2) is one or a combination of oleic acid, ammonium citrate, polyethylene glycol, sodium hexametaphosphate and polyvinylpyrrolidone.
Further, the setting of the printing in the step (3) is that the aperture of the nozzle is smaller than the size of the needle head, the printing layer height is smaller than the aperture of the nozzle, two adjacent printing wires are partially overlapped, and the air pressure setting is matched with the printing speed during printing.
Further, the prepared magnetic bioimplant in the step (4) has certain porosity, compressive strength and magnetism. The porosity of the implant is 45-65%, the compressive strength is 1.5-15 MPa, and the magnetic saturation strength is 2-25 emu/g.
Compared with the prior art, the method of the invention has the advantages that: MgFe2O4The magnetic implant can generate mechanical stimulation to bone cells under the action of an external static magnetic field to promote bone regeneration, and different magnetism can be obtained by changing the calcination temperature. Firstly, printing and molding precursor powder by a 3D gel printing technology, and then synthesizing MgFe in the sintering process2O4The magnetic implant is obtained, the operation is simple, the cost is low, the near-net forming of the workpiece with the complex shape can be realized, and the magnetic implant has good application prospect in the aspects of biomedicine and other industries.
Detailed Description
Research shows that the magnetic characteristics are applied to the bone tissue engineering implant, a signal path can be activated by applying an external static magnetic field, and the expression of osteogenic genes is triggered, so that the adhesion, proliferation and osteogenic differentiation of human mesenchymal stem cells are enhanced, the formation of new bones is promoted, diseases such as bone tumors and the like can be treated by drug loading and thermotherapy, and the method is an effective way for designing the bone implant with good comprehensive performance and complex shape. At present, the magnetic implant is mainly prepared by doping magnetic nano particles, and the magnetism obtained by the method is small and the magnetic characteristic is not obvious. MgFe2O4Has good biocompatibility and magnetism, good magnetic heating capacity and bone formation activity, and MgFe for improving the clinical application of the bone tissue engineering implant2O4The incorporation of magnetic implants is necessary.
The invention provides a method for producingA method for preparing a magnetic biological implant is used for solving the problems that the traditional tissue engineering implant is insufficient in repairing bone tumor and large bone defect and the existing magnetic implant is complex to prepare and insufficient in magnetism. MgFe prepared by chemical coprecipitation method2O4The precursor particles are nano particles, and the prepared slurry has high solid phase content and good fluidity. The key steps of the invention are that the implant is printed by using the precursor powder, then solid phase synthesis is carried out in the sintering process, the problem of repeated sintering is avoided, the porous implant which meets the compressive strength and porosity required by the bone tissue engineering implant can be obtained, and the magnetic implant materials with different magnetic properties are obtained along with the difference of sintering temperature and sintering time.
Based on the above principle, the preparation process of the invention comprises the following steps: MgFe2O4Preparing a magnetic nanoparticle precursor, preparing printing slurry, printing 3D gel, degreasing and sintering. The invention provides a method for preparing magnetic biological implants with different magnetism, which comprises the following steps:
(1)MgFe2O4preparing a magnetic nanoparticle precursor: preparing a precursor by a chemical coprecipitation method, and respectively weighing 20-60 g of MgCl2·6H2O and 40-120 gFeCl3·6H2O, mixing and dissolving the materials in 200-500 ml of deionized water, and heating the materials to 45-80 ℃ in a water bath kettle; stirring the mixed solution for 5-20 min by using an electric stirrer, uniformly dissolving, and adding 25-28% excessive NH3·H2Slowly dripping O into the solution, and continuously stirring for 20-60 min to obtain alkaline turbid solution; washing the prepared precursor nano-particles by using a centrifugal process repeatedly until the solution is neutral, and pouring off the liquid part to leave the generated precursor nano-particles;
(2) preparing printing slurry: mixing PVA solid particles and deionized water according to a mass ratio of 1 (9-24), heating to 60-95 ℃, stirring for 1-3 h to obtain a powder cross-linking solution, mixing the precursor powder obtained in the step (1) and the PVA solution according to a mass ratio of (0.5-3.5) to 1, continuously adding a dispersing agent accounting for 0.5-2 wt% of the total weight of the powder, and uniformly stirring to obtain printing slurry;
(3) filling the printing slurry obtained in the step (2) into a charging barrel of a 3D gel printer, setting the aperture of a printing nozzle to be 0.4-0.8 mm, the height of a printing layer to be 0.3-0.7 mm, and setting the printing speed to be 6-15 mm/s; guiding the slice code of the three-dimensional implant into a printer, extruding slurry out of a needle tube under the action of air pressure, and printing the porous implant;
(4) drying the printed implant blank in air for 24-48 h, then carrying out heat preservation at 600-800 ℃ for 1-2 h for degreasing, sintering at 1200-1400 ℃ for 1-3 h, and obtaining the magnetic implant after sintering.
The method can obtain MgFe with crystal grains of different sizes by changing the sintering temperature and the sintering time of the implant2O4So as to obtain the implant with different magnetic properties, but the sintering temperature can not be too low or too high, the temperature is not too low to obtain the required crystal phase, and the structure is loose; too high a temperature increases oxygen defects to degrade the magnetic properties of the product.
The porous bone implant with good biocompatibility and certain magnetic property is prepared by a chemical coprecipitation method and a 3D gel printing technology.
Specific example 1:
(1) 20.3g of MgCl were added separately2·6H2O and 40.5g FeCl3·6H2Adding O into 200ml deionized water, heating to 50 deg.C in water bath, stirring with electric stirrer, stirring, and adding dropwise NH3·H2Until the solution is alkaline, fully reacting after 20min, and washing the generated MgFe by using deionized water repeatedly by utilizing centrifugation2O4Precursor particles, to an upper layer liquid pH of 7.
(2) Adding 4g of PVA solid particles into 96g of deionized water, heating to 80 ℃, stirring for 2h to obtain a powder cross-linking solution, adding 18g of precursor powder into 8g of PVA solution, continuously adding 0.2g of oleic acid, and uniformly stirring to obtain printing slurry.
(3) Filling the printing slurry obtained in the step (2) into a charging barrel of a 3D gel printer, selecting a 0.5-degree needle head, setting the aperture of a printing nozzle to be 0.4mm, the height of a printing layer to be 0.38mm, and setting the printing speed to be 6 mm/s; and (3) introducing the slice code of the three-dimensional implant into a printer, extruding the slurry out of the needle tube through the action of air pressure, and printing the porous implant.
(4) Drying the printed implant blank in the air for 24h, then carrying out heat preservation at 600 ℃ for 2h for degreasing, sintering at 1200 ℃ for 2h, and obtaining the magnetic implant after sintering. The porosity of the implant was 48%, the compressive strength was 2.6MPa, and the magnetic saturation strength was 13.2 emu/g.
Specific example 2:
(1) respectively adding 30g of MgCl2·6H2O and 59.8gFeCl3·6H2Adding O into 300ml deionized water, heating to 60 ℃ in water bath, stirring the mixed solution evenly by an electric stirrer, continuing stirring and dropwise adding NH3·H2Until the solution is alkaline, fully reacting after 30min, and washing the generated MgFe by using deionized water repeatedly by utilizing centrifugation2O4Precursor particles, to an upper layer liquid pH of 7.
(2) Adding 6g of PVA solid particles into 94g of deionized water, heating to 90 ℃, stirring for 2h to obtain a powder cross-linking solution, adding 20g of precursor powder into 8g of PVA solution, continuously adding 0.2g of ammonium citrate, and uniformly stirring to obtain printing slurry.
(3) Filling the printing slurry obtained in the step (2) into a charging barrel of a 3D gel printer, selecting a 0.6 needle head, setting the aperture of a printing nozzle to be 0.5mm, the height of a printing layer to be 0.48mm, and setting the printing speed to be 8 mm/s; and (3) introducing the slice code of the three-dimensional implant into a printer, extruding the slurry out of the needle tube through the action of air pressure, and printing the porous implant.
(4) Drying the printed implant blank in the air for 32h, then carrying out heat preservation at 700 ℃ for 2h for degreasing, sintering at 1300 ℃ for 2h, and obtaining the magnetic implant after sintering. The porosity of the implant was 54.2%, the compressive strength was 7.25MPa, and the magnetic saturation strength was 22.4 emu/g.
Specific example 3:
(1) respectively mixing 38g of MgCl2·6H2O and 75.8gFeCl3·6H2Adding O into 400ml deionized water, heating to 70 ℃ in water bath, uniformly stirring the mixed solution by using an electric stirrer, continuously stirring and dropwise adding NH3·H2Until the solution is alkaline, fully reacting after 40min, and washing the generated MgFe by using deionized water repeatedly by utilizing centrifugation2O4Precursor particles, to an upper layer liquid pH of 7.
(2) Adding 8g of PVA solid particles into 92g of deionized water, heating to 95 ℃, stirring for 2h to obtain a powder cross-linking solution, adding 16g of precursor powder into 8g of PVA solution, continuously adding 0.15g of polyethylene glycol, and uniformly stirring to obtain printing slurry.
(3) Filling the printing slurry obtained in the step (2) into a charging barrel of a 3D gel printer, selecting a 0.7 needle head, setting the aperture of a printing nozzle to be 0.6mm, the height of a printing layer to be 0.58mm, and setting the printing speed to be 10 mm/s; and (3) introducing the slice code of the three-dimensional implant into a printer, extruding the slurry out of the needle tube through the action of air pressure, and printing the porous implant.
(4) Drying the printed implant blank in the air for 48h, then preserving the heat at 800 ℃ for 2h for degreasing, sintering at 1350 ℃ for 2h, and obtaining the magnetic implant after sintering. The porosity of the implant is 50.2%, the compressive strength is 8.5MPa, and the magnetic saturation strength is 10.6 emu/g.
Specific example 4:
(1) separately adding 40g of MgCl2·6H2O and 79.8gFeCl3·6H2Adding O into 500ml deionized water, heating to 60 deg.C in water bath, stirring with electric stirrer, stirring, and adding dropwise NH3·H2Until the solution is alkaline, fully reacting after 40min, and washing the generated MgFe by using deionized water repeatedly by utilizing centrifugation2O4Precursor particles, to an upper layer liquid pH of 7.
(2) Adding 10g of PVA solid particles into 90g of deionized water, heating to 95 ℃, stirring for 3h to obtain a powder cross-linked solution, adding 15g of precursor powder into 8g of PVA solution, continuously adding 0.1g of sodium hexametaphosphate, and uniformly stirring to obtain printing slurry.
(3) Filling the printing slurry obtained in the step (2) into a charging barrel of a 3D gel printer, selecting a 0.84 needle head, setting the aperture of a printing nozzle to be 0.75mm, the height of a printing layer to be 0.68mm, and setting the printing speed to be 12 mm/s; the slice code of the three-dimensional implant is led into a printer, slurry is extruded from a needle tube under the action of air pressure, and the porous implant is printed
(4) Drying the printed implant blank in the air for 36h, then carrying out heat preservation at 800 ℃ for 2h for degreasing, sintering at 1400 ℃ for 2h, and obtaining the magnetic implant after sintering. The porosity of the implant was 52%, the compressive strength was 12.3MPa, and the magnetic saturation strength was 7.8 emu/g.
Claims (5)
1. Preparation of MgFe2O4A method of magnetic implant characterized by the steps of:
(1)MgFe2O4preparing a magnetic nanoparticle precursor: preparing a precursor by a chemical coprecipitation method, and respectively weighing 20-60 g of MgCl2·6H2O and 40-120 gFeCl3·6H2Mixing and dissolving O in 200-500 ml of deionized water, and heating to 45-80 ℃ in a water bath kettle; stirring the mixed solution for 5-20 min by using an electric stirrer, uniformly dissolving, and adding 25-28% excessive NH3·H2Slowly dripping O into the solution, and continuously stirring for 20-60 min to obtain alkaline turbid solution; washing the prepared precursor nano-particles by using a centrifugal process repeatedly until the solution is neutral, and pouring off the liquid part to leave the generated precursor nano-particles;
(2) preparing printing slurry: mixing PVA solid particles and deionized water according to a mass ratio of 1 (9-24), heating to 60-95 ℃, stirring for 1-3 h to obtain a powder cross-linking solution, mixing the precursor powder obtained in the step (1) and the PVA solution according to a mass ratio of (0.5-3.5) to 1, continuously adding a dispersing agent accounting for 0.5-2 wt% of the total weight of the powder, and uniformly stirring to obtain printing slurry;
(3) filling the printing slurry obtained in the step (2) into a charging barrel of a 3D gel printer, setting the aperture of a printing nozzle to be 0.4-0.8 mm, the height of a printing layer to be 0.3-0.7 mm, and setting the printing speed to be 6-15 mm/s; guiding the slice code of the three-dimensional implant into a printer, extruding slurry out of a needle tube under the action of air pressure, and printing the porous implant;
(4) drying the printed implant blank in air for 24-48 h, then carrying out heat preservation at 600-800 ℃ for 1-2 h for degreasing, sintering at 1200-1400 ℃ for 1-3 h, and obtaining the magnetic implant after sintering.
2. Preparation of MgFe according to claim 12O4A method of magnetic implant, characterized by: MgCl described in step (1)2·6H2O and FeCl3·6H2O solution of Mg2+With Fe3+Is 2: and 3, precursor nano-particles with different particle sizes can be prepared by changing the heating temperature of the water bath and the stirring time.
3. Preparation of MgFe according to claim 12O4A method of magnetic implant, characterized by: the dispersant in the step (2) is one or a plurality of composite materials of oleic acid, ammonium citrate, polyethylene glycol, sodium hexametaphosphate and polyvinylpyrrolidone.
4. Preparation of MgFe according to claim 12O4A method of magnetic implant, characterized by: and (3) the aperture of the printed nozzle is smaller than the size of the needle head, the height of the printing layer is smaller than the aperture of the nozzle, two adjacent printing wires are partially overlapped, and meanwhile, the printing air pressure is matched with the printing speed.
5. Preparation of MgFe according to claim 12O4A method of magnetic implant, characterized by: according to the magnetic biological implant prepared in the step (4), the porosity of the implant ranges from 45% to 65%, the compressive strength ranges from 1.5 MPa to 15MPa, and the magnetic saturation strength ranges from 2emu/g to 25 emu/g.
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