CN112773945B - Method for preparing ceramic-magnetofluid composite bracket - Google Patents

Method for preparing ceramic-magnetofluid composite bracket Download PDF

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CN112773945B
CN112773945B CN202110137322.0A CN202110137322A CN112773945B CN 112773945 B CN112773945 B CN 112773945B CN 202110137322 A CN202110137322 A CN 202110137322A CN 112773945 B CN112773945 B CN 112773945B
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support
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CN112773945A (en
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邵慧萍
吴佳蕾
林涛
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University of Science and Technology Beijing USTB
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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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—Inorganic materials
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
    • 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
    • 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
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention provides a method for preparing a ceramic-magnetofluid composite bracket, belonging to the field of preparation of composite materials. The invention firstly prints out the biological ceramic bracket by adopting 3D gel, and then prepares Fe by adopting an ultrasonic emulsification composite chemical coprecipitation method3O4Magnetic nano particles are added with different amounts of deionized water and surfactant to prepare Fe with different volume fractions3O4The magnetofluid is prepared by soaking the ceramic support which is printed and sintered by 3D printing in the magnetofluid, centrifuging and drying to obtain uniform Fe with different magnetism on the surface of the support3O4And (4) coating the magnetic fluid. The method for preparing the magnetic nano coating is simple and stable to operate, can save cost and improve production efficiency.

Description

Method for preparing ceramic-magnetofluid composite bracket
Technical Field
The invention relates to a method for preparing a ceramic-magnetofluid composite bracket, belonging to the field of preparation of composite materials.
Background
The magnetic fluid consists of three parts of nano-scale solid magnetic particles, base liquid and surfactant. Magnetic nanoparticles are generally prepared by a chemical coprecipitation method, and then a surfactant is added to coat and modify the nanoparticles so that the nanoparticles are uniformly suspended in a base solution to form a stable colloid. The magnetic material is a novel functional material which has the fluidity of liquid and the magnetism of a solid magnetic material. The fluid is non-magnetic in a static state, and only shows magnetism when an external magnetic field acts. The solid magnetic particles widely used at present are Fe3O4、γ-Fe2O3、MeFe2O4(Me is divalent cation such as Co, Ni, Mg), magnetic metal Co, Fe, Ni and alloy particles thereof, iron nitride particles, wherein Fe3O4Has high coercive force, high magnetic susceptibility, larger specific surface area, unique magnetic property and excellent biocompatibility, and has wide application in the biomedical field. The base liquid is the carrier of magnetic particles, gives the magnetic fluid the flowing characteristic as a magnetic material, and mainly comprises water base, organic base and goldThe base fluid can affect the physical properties of the magnetic fluid such as density, viscosity, boiling point, electrical conductivity, thermal conductivity and the like, and the selection of the base fluid is different according to the required properties. The surface active agent plays an important role in the stability of the magnetic fluid. The magnetic nano-particles belong to inorganic solid particles, can not be dissolved and are difficult to disperse in base liquid, the surfactant belongs to a long-chain molecule with a polar functional group structure, and consists of a nonpolar hydrophobic group hydrocarbon chain and a polar hydrophilic group, the two parts are respectively arranged at two ends of the functional group, one end of the surfactant can form firm combination with the surface of the magnetic particles through the actions of hydrogen bonds, ion pairs or van der Waals force and the like, and the other end of the surfactant is suspended in the base liquid. The surface of the magnetic nano-particles is coated with a layer of surfactant, when the magnetic nano-particles are close to each other, the outer ends of the surfactant molecular groups carry the same charges and repel each other, thereby reducing the agglomeration and the uneven dispersion of the magnetic nano-particles, and separating the magnetic micro-particles from each other and suspending the magnetic micro-particles in the base liquid.
The chemical components of the biological ceramics are similar to the inorganic salt components of bones, and the biological ceramics have good biocompatibility, bone conduction and bone inductivity, and the biological ceramics such as 3D printing calcium phosphate, calcium silicate, hydroxyapatite and the like are widely applied to bone tissue engineering scaffolds. To meet the requirements of bone scaffolds for multiple properties, research is currently focused on making multiphase composite bone scaffolds from two or more different materials. The magnetic nano material has the excellent characteristics of small size effect, quantum size effect, surface effect and the like, and makes great research progress in the aspects of targeted drug delivery, tumor thermotherapy, magnetic resonance imaging and the like. The magnetic characteristics are applied to the bone tissue engineering scaffold, so that the adhesion, proliferation and differentiation of cells can be effectively enhanced, new bone formation is promoted, diseases such as bone tumor and the like can be treated through drug loading and thermotherapy, a new opportunity is provided for the functional development of the tissue engineering scaffold, the method is an effective way for designing the bone scaffold with comprehensive performance, and the method is favorable for the application of the 3D printing porous scaffold in clinic.
Disclosure of Invention
The invention provides a method for preparing a ceramic-magnetofluid composite bracket, which aims to prepare a magnetic multi-hole tissue engineering bracket and solve the defect of uneven coating on the surface of a ceramic bracket in the prior coating technology.
The principle of the invention is as follows: in order to solve the problem of insufficient osteogenesis of the bone tissue engineering scaffold, Fe3O4The magnetic fluid is adhered to the surface of the stent in a magnetic fluid mode to manufacture a novel magnetic coating. Firstly, preparing Fe by an ultrasonic emulsification composite chemical coprecipitation method3O4Nano-magnetic particles, adding certain amount of FeCl3·6H2O and FeSO4·7H2Mixing the O solution, and heating to about 50 ℃ in a water bath. Carrying out ultrasonic treatment on the mixed solution for 3-5 min by using an ultrasonic material emulsifying disperser, uniformly dissolving, and adding excessive NH3·H2Slowly dripping O into the solution, generating thousands of atmospheric pressures in a small range by ultrasonic wave to generate convection at the bottom and upper part of the liquid, generating great breaking force in the liquid, fully reacting, and preventing Fe generation3O4The nano particles grow up. Obtaining Fe after ultrasonic treatment for 10-15 min3O4Turbid liquid. Adding an external magnetic field, and repeatedly using deionized water and ethanol to react with the prepared Fe3O4Washing until the upper layer liquid is neutral, then respectively adding different amounts of deionized water, heating to 60-90 ℃ in a water bath kettle, adding a proper amount of sodium oleate surfactant, and performing ultrasonic treatment again to remove Fe formed in the washing process3O4Pulverizing the aggregates while making Fe3O4The surfaces of the particles can be completely coated by the hydrolyzed oleate ions to obtain Fe with different volume fractions3O4And (4) magnetic fluid. Immersing the prepared porous ceramic bracket in the magnetic fluid due to Fe3O4The nano particles are smaller than 0.1 micron in size, the specific surface area is large, the number of atoms on the surface of the particles is relatively increased, adjacent atoms are lacked around the surface atoms, and a plurality of dangling bonds are formed, so that the surface atoms have high activity and are extremely unstable, namely, the surface atoms have large surface energy and surface binding energy and are easy to be combined with other atoms to be stabilized, and the surface atoms can be quickly attached to the surface of the ceramic scaffold to form a uniform coating with good binding force.
Based on the principle, the inventionThe method comprises the following steps: preparation of porous biological ceramic scaffold and Fe3O4Preparation of nanoparticles, Fe3O4Preparation of magnetic fluid and coating of surface of ceramic support with Fe3O4And (4) magnetic fluid. The invention provides a method for preparing a ceramic-magnetofluid composite bracket with different magnetisms, which comprises the following steps:
(1) preparing a ceramic bracket: mixing ceramic powder and 4-8 wt% of PVA solution in a mass ratio (0.8-2): 1, continuously adding oleic acid in an amount which is 5-10 wt% of the mass of the ceramic powder, uniformly stirring to obtain ceramic slurry, printing a porous ceramic support through 3D gel, and then drying, degreasing and sintering the printed support to obtain a ceramic support matrix;
(2)Fe3O4preparing nano magnetic particles: preparation of Fe by ultrasonic emulsification composite chemical coprecipitation method3O4Nano-magnetic particles having the reaction equation:
FeSO4+2FeCl3+8NH4OH→Fe3O4+6NH4Cl+(NH4)2SO4+4H2O
weighing a certain amount of FeCl3·6H2O and FeSO4·7H2Respectively preparing O into 0.3mol/L solution, mixing the two solutions according to a certain mass ratio, and heating to 45-55 ℃ in a water bath kettle; carrying out ultrasonic treatment on the mixed solution for 3-5 min by using an ultrasonic emulsification disperser, uniformly dissolving, and adding excessive NH3·H2Slowly dripping O into the solution, and reacting for 10-15 min to obtain alkaline Fe3O4Turbid liquid; fe prepared by repeating pairs of external magnetic fields3O4Washing until the upper layer solution is neutral, and pouring off the liquid part to leave the generated Fe3O4Nano-magnetic particles;
(3)Fe3O4preparing nano magnetic fluid: for Fe generated in step (2)3O4Adding different amounts of deionized water into the nano magnetic particles to prepare Fe3O4The magnetic fluid with the concentration of 0.5-2 vol% is heated to 60-90 ℃ in the water bath again, and oleic acid is addedSodium, and carrying out ultrasonic treatment for 6-10 min by using an ultrasonic material emulsifying disperser to ensure Fe3O4The surfaces of the particles can be completely coated by the hydrolyzed oleate ions, and Fe with different volume fractions can be obtained3O4A magnetic fluid;
(4) preparing a ceramic-magnetic fluid composite bracket: respectively soaking the ceramic supports prepared in the step (1) in the Fe with different concentrations prepared in the step (3)3O4And (3) removing redundant fluid on the surface of the support and in pores after 4-6 minutes in the magnetic fluid to obtain a uniform surface coating, and then placing the uniform surface coating in air for drying to obtain the ceramic-magnetic fluid composite support with different magnetism.
Further, the 3D gel in the step (1) is printed to form a ceramic scaffold, which comprises hydroxyapatite, calcium phosphate, calcium silicate, magnesium phosphate, zirconium oxide and the like.
Further, the 3D gel printed porous ceramic scaffold in the step (1) has certain porosity and compressive strength. The porosity of the bracket is 52-70%, the compressive strength is 1.5-25 MPa, and the magnetic saturation strength is 60-70 emu/g.
Further, FeCl in the step (2)3·6H2O and FeSO4·7H2O solution with the mass ratio of n (Fe)3 +):n(Fe2+) 3: 2; fe with different grain diameters can be prepared by changing the heating temperature of the water bath and the ultrasonic time3O4Nano-magnetic particles.
Further, the adding amount of the sodium oleate in the step (3) is FeCl3·6H2O and FeSO4·7H2The total mass of O is 3-12 wt%; fe with different volume fractions can be prepared by changing the concentration of the magnetic fluid3O4And (4) magnetic fluid.
Further, the method for removing the excess fluid on the surface and in the pores of the scaffold in the step (4) is to remove the excess fluid by a centrifugal method, so that the magnetic fluid is uniformly attached to the surface of the scaffold.
Compared with the prior art, the method of the invention has the advantages that: the method for preparing the magnetic nano coating at present mainly uses glueThe polymer matrix such as the body and the chitosan fixes the magnetic nano particles on the surface of the bracket by the modes such as electrophoretic deposition and the like, the operation is complex, and the uniform coating is difficult to prepare. Soaking the ceramic support in the magnetic fluid by using the surface effect and capillary action of the nano magnetic fluid, and Fe3O4Can be quickly attached to the surface and in the pores of the scaffold, and can obtain bone tissue engineering scaffolds with different magnetism by preparing magnetic fluids with different volume fractions. The method has the advantages of stable process, high production efficiency and short production period, and the obtained ceramic-magnetic fluid composite bracket has controllable magnetism, uniform surface coating and good binding force between the coating and the substrate, thereby obviously reducing the cost for preparing the magnetic coating on the surface of the ceramic bracket and having good prospect in the aspects of medical and other industrial applications and the like.
Detailed Description
Bioceramic materials, such as calcium silicate salts, calcium phosphate salts, etc., have good biocompatibility, biodegradability and bioactivity, and have been playing an important role in the field of scaffolds for bone tissue engineering in recent years. However, single-phase ceramic scaffolds have a weak effect on bone ingrowth, and it is still difficult to reconstruct large bone defects due to trauma, tumors or infections, etc., and the interface plays a crucial role in achieving bone ingrowth. Fe3O4Has good magnetism and biocompatibility, and Fe is prepared on the surface of the bracket3O4The coating can obtain a functional scaffold with magnetocaloric ability and bone formation activity, and the research on the ceramic-magnetic composite scaffold is necessary to improve the application of the bone tissue engineering scaffold.
The invention provides a method for preparing a ceramic-magnetofluid composite bracket, which is used for solving the problems of complex technology and non-uniform coating of the existing magnetic coating preparation technology. The principle of the invention is that Fe is attached to a ceramic bracket based on the surface effect of the nano magnetofluid3O4And the magnetofluid is centrifuged and dried to obtain the ceramic bracket with certain magnetism. The key step of the invention is to coat the surfactant on all Fe3O4The surface of the magnetic nano-particles is uniformly dispersed in deionized water to form stable magnetismA fluid. And then the composite stent with good magnetism and uniform surface coating is obtained by dipping and centrifuging.
Based on the above principle, the process of the present invention includes: preparation of porous biological ceramic scaffold and Fe3O4Preparation of nanoparticles, Fe3O4Preparation of magnetic fluid and coating of surface of ceramic support with Fe3O4And (4) magnetic fluid. The invention provides a method for preparing a ceramic-magnetofluid composite bracket with different magnetisms, which comprises the following steps:
(1) preparing a ceramic bracket: mixing ceramic powder and 4-8 wt% of PVA solution according to a mass ratio (0.8-2) to 1, continuously adding oleic acid with the mass being 5-10 wt% of that of the ceramic powder, uniformly stirring to obtain ceramic slurry, printing a porous ceramic support through 3D gel, and then drying, degreasing and sintering the printed support to obtain the ceramic matrix.
(2)Fe3O4Preparing nano magnetic particles: preparation of Fe by ultrasonic emulsification composite chemical coprecipitation method3O4Nano-magnetic particles having the reaction equation:
FeSO4+2FeCl3+8NH4OH→Fe3O4+6NH4Cl+(NH4)2SO4+4H2O
weighing a certain amount of FeCl3·6H2O and FeSO4·7H2O is respectively prepared into 0.3mol/L solution according to the mass proportion n (Fe)3+):n(Fe2+) The two solutions were mixed 3:2 and heated to about 50 ℃ in a water bath. Carrying out ultrasonic treatment on the mixed solution for 3-5 min by using an ultrasonic emulsification disperser, uniformly dissolving, and adding excessive NH3·H2Slowly dripping O into the solution, and reacting for 10-15 min to obtain alkaline Fe3O4Turbid liquid. Fe prepared by repeating pairs of external magnetic fields3O4Washing until the upper layer solution is neutral, and pouring off the liquid part to leave the generated Fe3O4Nano-magnetic particles.
(3)Fe3O4Preparing nano magnetic fluid: for the product generated in step (2)Fe3O4Adding different amounts of deionized water into the nano magnetic particles to prepare Fe3O4The magnetic fluid with the concentration of 0.5-2 vol% is heated to 60-90 ℃ in the water bath again, and FeCl is added3·6H2O and FeSO4·7H2Sodium oleate with the total weight of 3-12 wt% of O, and ultrasonically treating for 6-10 min by using an ultrasonic material emulsifying disperser to ensure Fe3O4The surfaces of the particles can be completely coated by the hydrolyzed oleate ions, and Fe with different volume fractions can be obtained3O4And (4) magnetic fluid.
(4) Preparing a ceramic-magnetic fluid composite bracket: respectively soaking the ceramic supports prepared in the step (1) in the Fe with different concentrations prepared in the step (3)3O4And (3) removing redundant fluid on the surface of the support and in pores by centrifugation after 5 minutes in the magnetic fluid, obtaining a uniform surface coating, and then drying in air to obtain the ceramic-magnetic fluid composite support with different magnetism.
The method of the invention can be used for generating Fe3O4Adding different amounts of deionized water into the magnetic particles, and then adding sodium oleate surfactant for ultrasonic treatment to obtain Fe with different volume fractions3O4The magnetic fluid, but the volume fraction can not be too large, the coating on the surface of the bracket is too thick due to too large volume fraction, the bonding force of the outer layer is not strong and is easy to peel off, and the coating is not good due to too small volume fraction and the magnetism is not strong.
The method of the invention is carried out by mixing Fe3O4The magnetic nano particles are prepared into magnetic fluid, the magnetic fluid is coated on the surface of the ceramic bracket, and finally the ceramic-magnetic composite bracket with uniform surface coating, certain magnetism and good biocompatibility can be prepared by centrifugation and drying.
Example 1: preparation of 2% volume fraction Fe on calcium phosphate scaffolds3O4Magnetic fluid
(1) Taking 10g of 6 wt% PVA solution, adding 16g of calcium phosphate powder, continuously adding 0.7ml of oleic acid, uniformly stirring to obtain calcium phosphate slurry, printing a porous calcium phosphate ceramic support by 3D gel, and then drying, degreasing and sintering the printed support to obtain the ceramic support substrate.
(2) Respectively adding 8.34g of FeSO4·7H2O and 8.1gFeCl3·6H2Adding O into 100ml deionized water, taking Fe2+40ml of solution and Fe3+Mixing 60ml of solution, heating to 50 ℃ in water bath, carrying out ultrasonic treatment on the mixed solution by using an ultrasonic material emulsifying disperser until the mixed solution is uniformly mixed, measuring 10ml of NH3·H2O, in the ultrasonic process, slowly dripping into the solution by using a rubber head dropper, fully reacting after 7min, and repeatedly washing the generated Fe by using deionized water and alcohol by using the attraction of a magnet3O4Magnetic particles, the upper layer liquid pH is 7.
(3) Pouring off all the liquid and adding deionized water to Fe3O4The total volume of the magnetic particles and the deionized water is 20ml, the mixture is heated to 60 ℃ in water bath again, 0.3g of sodium oleate powder is added, the mixture is put into an ultrasonic material emulsifying disperser for ultrasonic treatment for 6min, and then Fe with the volume fraction of 2 percent is prepared3O4And (4) magnetic fluid.
(4) And (3) immersing the 3D printed porous calcium phosphate scaffold into the magnetic fluid, taking out after a few minutes, putting into a centrifuge tube, setting the rotating speed of the centrifuge to be 400r/min, taking out the scaffold after centrifuging for 3 minutes, and drying in the air for 1 day to obtain the composite scaffold. The porosity of the stent is 62.1 percent, the compressive strength is 22.6MPa, and the magnetic saturation strength is 63.2 emu/g.
Example 2: preparation of 1% volume fraction Fe on calcium silicate scaffolds3O4Magnetic fluid
(1) And adding 24g of calcium silicate powder into 12g of PVA (polyvinyl alcohol) with the weight percent of 8%, continuously adding 1ml of oleic acid, uniformly stirring to obtain calcium silicate slurry, printing a porous calcium silicate ceramic bracket by using 3D gel, and drying, degreasing and sintering the printed bracket to obtain the ceramic bracket substrate.
(2) Respectively adding 8.34g of FeSO4·7H2O and 8.1gFeCl3·6H2Adding O into 100ml deionized water, taking Fe2+40ml of solution and Fe3+Mixing 60ml of solution, heating to 50 ℃ in water bath, carrying out ultrasonic treatment on the mixed solution by using an ultrasonic material emulsifying disperser until the mixed solution is uniformly mixed, measuring 15ml of NH3·H2O in an ultrasonic processSlowly dripping into solution with rubber dropper, reacting for 10min, attracting with magnet, and repeatedly washing the generated Fe with deionized water and alcohol3O4Magnetic particles, the upper layer liquid pH is 7.
(3) Pouring off all the liquid and adding deionized water to Fe3O4The total volume of the magnetic particles and the deionized water is 40ml, the mixture is heated to 70 ℃ again in water bath, 0.5g of sodium oleate powder is added, the mixture is put into an ultrasonic material emulsifying disperser and is subjected to ultrasound for 7.5min, and then Fe with the volume fraction of 1 percent is prepared3O4And (4) magnetic fluid.
(4) Immersing the 3D printed porous calcium silicate scaffold into the magnetic fluid, taking out after a few minutes, putting into a centrifuge tube, setting the rotation speed of a centrifuge to be 400r/min, taking out the scaffold after centrifuging for 3 minutes, and drying in the air for 1 day to obtain the composite scaffold. The porosity of the stent is 62%, the compressive strength is 16.52MPa, and the magnetic saturation strength is 69.6 emu/g.
Example 3: preparation of 0.7% volume fraction Fe on hydroxyapatite scaffolds3O4Magnetic fluid
(1) Taking 10g of 4 wt% PVA, adding 16g of hydroxyapatite powder, continuously adding 0.5ml of oleic acid, uniformly stirring to obtain hydroxyapatite slurry, printing a porous hydroxyapatite ceramic support by using 3D gel, and then drying, degreasing and sintering the printed support to obtain the ceramic support substrate.
(2) Respectively adding 8.34g of FeSO4·7H2O and 8.1gFeCl3·6H2Adding O into 100ml deionized water, taking Fe2+40ml of solution and Fe3+Mixing 60ml of solution, heating to 50 ℃ in water bath, carrying out ultrasonic treatment on the mixed solution by using an ultrasonic material emulsifying disperser until the mixed solution is uniformly mixed, and measuring 18ml of NH3·H2O, in the ultrasonic process, slowly dripping into the solution by using a rubber head dropper, reacting fully after 12min, then utilizing a magnet to attract, and repeatedly washing the generated Fe by using deionized water and alcohol3O4Magnetic particles, the upper layer liquid pH is 7.
(3) Pouring off all the liquid and adding deionized water to Fe3O4The total volume of the magnetic particles and the deionized water is 60mlHeating in water bath to 75 deg.C again, adding 0.7g sodium oleate powder, and ultrasonic treating in ultrasonic material emulsifying disperser for 8min to obtain Fe with volume fraction of 0.7%3O4And (4) magnetic fluid.
(4) And (3) immersing the 3D printed porous calcium phosphate scaffold into the magnetic fluid, taking out after a few minutes, putting into a centrifuge tube, setting the rotating speed of the centrifuge to be 400r/min, taking out the scaffold after centrifuging for 3 minutes, and drying in the air for 1 day to obtain the composite scaffold. The porosity of the stent is 52.26%, the compressive strength is 16.77MPa, and the magnetic saturation strength is 63.1 emu/g.
Example 4: preparation of 0.5% volume fraction Fe on magnesium phosphate scaffolds3O4Magnetic fluid
(1) And (2) adding 8g of magnesium phosphate powder into 10g of 4 wt% PVA, continuously adding 1ml of oleic acid, uniformly stirring to obtain magnesium phosphate slurry, printing a porous magnesium phosphate ceramic support by using 3D gel, and drying, degreasing and sintering the printed support to obtain the ceramic support substrate.
(2) Respectively adding 8.34g of FeSO4·7H2O and 8.1gFeCl3·6H2Adding O into 100ml deionized water, taking Fe2+40ml of solution and Fe3+Mixing 60ml of solution, heating to 50 ℃ in water bath, carrying out ultrasonic treatment on the mixed solution by using an ultrasonic material emulsifying disperser until the mixed solution is uniformly mixed, and measuring 20ml of NH3·H2O, in the ultrasonic process, slowly dripping into the solution by using a rubber head dropper, reacting fully after 15min, then utilizing a magnet to attract, and repeatedly washing the generated Fe by using deionized water and alcohol3O4Magnetic particles, the upper layer liquid pH is 7.
(3) Pouring off all the liquid and adding deionized water to Fe3O4The total volume of the magnetic particles and the deionized water is 80ml, the mixture is heated to 80 ℃ in water bath again, 1g of sodium oleate powder is added, the mixture is put into an ultrasonic material emulsifying disperser for ultrasonic treatment for 10min, and then Fe with the volume fraction of 0.5 percent is prepared3O4And (4) magnetic fluid.
(4) Immersing the 3D printed porous calcium silicate scaffold into the magnetic fluid, taking out after a few minutes, putting into a centrifuge tube, setting the rotation speed of a centrifuge to be 400r/min, taking out the scaffold after centrifuging for 3 minutes, and drying in the air for 1 day to obtain the composite scaffold. The porosity of the stent is 60%, the compressive strength is 1.5MPa, and the magnetic saturation strength is 62.4 emu/g.

Claims (4)

1. A method for preparing a ceramic-magnetofluid composite scaffold is characterized by comprising the following steps of:
(1) preparing a ceramic bracket: mixing ceramic powder and 4-8 wt% of PVA solution in a mass ratio (0.8-2): 1, continuously adding oleic acid in an amount which is 5-10 wt% of the mass of the ceramic powder, uniformly stirring to obtain ceramic slurry, printing a porous ceramic support through 3D gel, and then drying, degreasing and sintering the printed support to obtain a ceramic support matrix;
(2)Fe3O4preparing nano magnetic particles: preparation of Fe by ultrasonic emulsification composite chemical coprecipitation method3O4Nano-magnetic particles having the reaction equation:
FeSO4+2FeCl3+8NH4OH→Fe3O4+6NH4Cl+(NH4)2SO4+4H2O
weighing a certain amount of FeCl3·6H2O and FeSO4·7H2Respectively preparing O into 0.3mol/L solution, mixing the two solutions according to a certain mass ratio, and heating to 45-55 ℃ in a water bath kettle; carrying out ultrasonic treatment on the mixed solution for 3-5 min by using an ultrasonic emulsification disperser, uniformly dissolving, and adding excessive NH3·H2Slowly dripping O into the solution, and reacting for 10-15 min to obtain alkaline Fe3O4Turbid liquid; fe prepared by repeating pairs of external magnetic fields3O4Washing until the upper layer solution is neutral, and pouring off the liquid part to leave the generated Fe3O4Nano-magnetic particles;
(3)Fe3O4preparing nano magnetic fluid: for Fe generated in step (2)3O4Adding different amounts of deionized water into the nano magnetic particles to prepare Fe3O4The magnetic fluid with the concentration of 0.5-2 vol% is heated to 60-90 ℃ in the water bath again, and sodium oleate is added for useThe ultrasonic material emulsifying disperser performs ultrasonic treatment for 6-10 min to ensure Fe3O4The surfaces of the particles can be completely coated by the hydrolyzed oleate ions, and Fe with different volume fractions can be obtained3O4A magnetic fluid;
(4) preparing a ceramic-magnetic fluid composite bracket: respectively soaking the ceramic supports prepared in the step (1) in the Fe with different concentrations prepared in the step (3)3O4Removing redundant fluid on the surface of the support and in pores after 4-6 minutes in the magnetic fluid to obtain a uniform surface coating, and then placing the uniform surface coating in air for drying to obtain the ceramic-magnetic fluid composite support with different magnetism;
printing a ceramic support comprising hydroxyapatite, calcium phosphate, calcium silicate, magnesium phosphate and zirconium oxide by using the 3D gel in the step (1);
and (4) removing the redundant fluid on the surface and in the pores of the stent by a centrifugal method to ensure that the magnetic fluid is uniformly attached to the surface of the stent.
2. The method of preparing a ceramic-magnetic fluid composite scaffold according to claim 1, wherein: the porous ceramic support printed by the 3D gel in the step (1) has certain porosity and compressive strength, the porosity range of the support is 52-70%, the compressive strength range is 1.5-25 MPa, and the magnetic saturation strength range is 60-70 emu/g.
3. The method of preparing a ceramic-magnetic fluid composite scaffold according to claim 1, wherein: FeCl described in step (2)3·6H2O and FeSO4·7H2O solution with the mass ratio of n (Fe)3+):n(Fe2+) 3: 2; fe with different grain diameters can be prepared by changing the heating temperature of the water bath and the ultrasonic time3O4Nano-magnetic particles.
4. The method of preparing a ceramic-magnetic fluid composite scaffold according to claim 1, wherein: the addition amount of the sodium oleate in the step (3) is FeCl3·6H2O and FeSO4·7H2The total mass of O is 3-12 wt%; fe with different volume fractions can be prepared by changing the concentration of the magnetic fluid3O4And (4) magnetic fluid.
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