CN114533949A - Magnesium alloy pipe support with bifunctional chitosan coating, preparation method and application - Google Patents
Magnesium alloy pipe support with bifunctional chitosan coating, preparation method and application Download PDFInfo
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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
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
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Abstract
The invention belongs to the technical field of magnesium alloy pipe support models, and discloses a magnesium alloy pipe support with a bifunctional chitosan coating, a preparation method and application thereof, wherein chitosan is prepared into mixed suspension according to a certain proportion; injecting the mixed suspension into a mold, then putting the degradable magnesium alloy, continuing injecting the mixed suspension to form a sandwich coating structure, and finally forming the magnesium alloy tube support material with the chitosan coating. The invention can perform plasticity according to the requirement of the defect area of the patient, has safe material performance, does not need to be taken out in a secondary operation, provides convenience for the clinical operation of a doctor and can relieve the pain of the patient. The invention can exert the performance advantages of various materials, has a double-function biological material, and has the capabilities of inhibiting the growth invasion and metastasis of tumor cells and promoting the regeneration of surrounding normal osteoblasts; the regeneration and repair functions of bone tissues are promoted together, and the materials are convenient to obtain and manufacture.
Description
Technical Field
The invention belongs to the technical field of magnesium alloy pipe support models, and particularly relates to a magnesium alloy pipe support with a bifunctional chitosan coating, a preparation method and application thereof.
Background
Currently, osteosarcoma is a well-known primary malignant bone tumor that occurs in children and adolescents, with 75% of patients ranging in age from 15 to 25 years. OS ranks eighth (about 2.4%) among the most common cancers in children, accounting for about 8.6% of cancer-related deaths in children. The prevalence of osteosarcoma in young patients rises to 600-800 ten thousand. To date, the most common clinical treatments for bone tumors include chemotherapy, extensive surgical resection and radiation therapy, surgery often resulting in bone defects of the resected tissue, while residual cancer cells may remain. 5. Osteosarcoma, however, is not sensitive to radiation therapy and is prone to develop resistance to chemotherapy, and chemotherapy and radiation therapy also have side effects including liver dysfunction, cardiotoxicity, and damage to normal tissues. The rapid proliferation and invasion of osteosarcoma cancer cells remain the main reason why the survival rate of osteosarcoma patients is not improved for decades, and innovative and effective treatment strategies are urgently needed to solve the problems existing in the treatment of bone tumors. With the development of biological nanotechnology, people design new treatment schemes for the treatment of bone tumors. The biomaterial for bone tumor treatment needs to have two functions: killing tumor cells and promoting bone regeneration. In recent years, degradable magnesium alloys are receiving more and more attention as orthopedic implants, and some researches have reported that magnesium degradation has certain cytotoxic effect on tumor cells and has potential anti-tumor activity. But the degradation rate of the magnesium metal material is too fast. To reduce the degradation rate of magnesium, alloying or coating treatments may be used. Recent studies have shown that various alloying elements can enhance the cytotoxicity of magnesium. Wu et al investigated the cytotoxic effect of the alloy Mg-Ca-Sr-Zn on an osteosarcoma cell line. The results show that Mg-1Ca-0.5Sr-xZn (x ═ 0, 2, 4, 6 mass%) alloy can inhibit proliferation, viability, cell cycle, migration and invasion of U2OS cells. This effect is mainly due to degradation products of magnesium. The degradation products of magnesium are respectively Mg2+OH-and H2. Chitosan is a biopolymer commonly used in bone and tissue engineering applications, and recently as a pro-apoptotic agent in metastatic cell lines such as breast cancerChitosan is a linear polysaccharide produced by deacetylation of chitin, the properties of which are directly dependent on the deacetylation site, making it particularly novel in terms of modification properties such as biocompatibility, antibacterial activity and biodegradability in tissue scaffolds and coatings. Chitosan also acts as a weak base, suggesting its potential as a pH regulator in osteosarcoma regulation. This is due to the non-bonded electron pair on the primary amino group of the glucosamine group of chitosan, which has the ability to accept protons. Chitosan promotes osteoblast proliferation. Proliferation in osteosarcoma would allow a targeted, local and controlled therapeutic strategy.
Through the above analysis, the problems and defects of the prior art are as follows:
(1) to date, the most common clinical treatments for bone tumors include chemotherapy, extensive surgical resection and radiation therapy, surgery often resulting in bone defects of the resected tissue, while residual cancer cells may remain. 5. Osteosarcoma, however, is not sensitive to radiation therapy and is prone to develop resistance to chemotherapy, and chemotherapy and radiation therapy also have side effects including liver dysfunction, cardiotoxicity, and damage to normal tissues. Surgical resection often fails to completely remove the tumor, which is a major cause of postoperative recurrence and metastasis.
(2) And the problem of postoperative repair is still unsolved.
The difficulty in solving the above problems and defects is: develops a bone repair defect which can inhibit the invasion and the metastasis of residual tumor cells after operation, promote the proliferation of peripheral normal cells and promote the bone repair.
The significance of solving the problems and the defects is as follows: greatly reduces the side effect of the patient after the radiotherapy and chemotherapy, can solve the problem of repairing the patient after the radiotherapy and chemotherapy, and meets the daily life requirement of the patient.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a magnesium alloy pipe bracket with a bifunctional chitosan coating, a preparation method and application thereof.
The invention is realized in this way, a method for preparing the magnesium alloy tube bracket with the bifunctional chitosan coating, which prepares chitosan into mixed suspension according to a proportion; injecting the mixed suspension into a mould, and putting the degradable magnesium alloy; and continuously injecting the mixed suspension to form a sandwich coating structure, thereby forming the magnesium alloy tube support material with the chitosan coating.
Further, the preparation method of the magnesium alloy pipe bracket with the bifunctional chitosan coating comprises the following steps:
step one, preparing magnesium alloy: preparing a Mg-Ca-Sr ternary alloy by a smelting method, and using Ca and Sr elements with good biocompatibility as microalloying elements; in the preparation process, an optimized ternary alloy structure is obtained by adjusting the process parameters of the heat preservation temperature, the heat preservation time, the cooling rate and the heat treatment;
step two, preparing a magnesium alloy pipe: carrying out linear cutting and turning on the alloy cast ingot to obtain a hollow cylindrical blank, heating, carrying out solid solution, and quenching for later use; heating an extrusion die, putting the heated extrusion die into a hollow cylindrical blank, and extruding at a high temperature to obtain a seamless extruded tube; annealing the seamless extruded tube to obtain a thin-wall magnesium alloy thin tube;
thirdly, preparing a porous magnesium alloy pipe: based on the magnesium alloy thin tube, firstly carrying out finite element analysis, designing and drawing a pattern and introducing the pattern into a laser engraving machine; precisely carving under the protection of inert gas, then performing surface brightening treatment, ultrasonically oscillating and washing in a weakly acidic organic solvent, and finally putting into a cleaning agent which does not react with metal magnesium for cleaning and airing;
step four, the mechanical property of the magnesium alloy pipe is as follows: measuring the microhardness of the magnesium alloy pipe, and performing a tensile test, a compression test and a bending test to obtain the mechanical property index of the magnesium alloy pipe;
fifthly, preparing a micro-arc oxidation coating on the surface of the porous magnesium alloy pipe: polishing the surface of the porous magnesium alloy pipe, cleaning the porous magnesium alloy pipe in a cleaning tank, oxidizing and cleaning the porous magnesium alloy pipe under the voltage of 450V, and finally drying the porous magnesium alloy pipe in a drying tank;
sixthly, preparing the chitosan coating material: dissolving chitosan powder in acetic acid, adding into the above solution, stirring, diluting with deionized water, adding sodium chloride and potassium hydroxide to adjust pH value, centrifuging, placing porous magnesium-calcium-strontium alloy tube into the solution, and freeze drying.
Further, the preparation of the Mg-Ca-Sr alloy in the Mg-Ca-Sr alloy tube comprises the following steps:
1) the cast alloy raw materials comprise 99.9 wt% of high-purity magnesium, Mg-30 wt% of Ca intermediate alloy and Mg-30 wt% of Sr intermediate alloy;
2) smelting and casting in a resistance furnace filled with mixed protective gas; preparing raw materials according to component proportions; preparing a mould and smelting; removing rust on the surfaces of all tools, heating, and keeping dry; heating the crucible and introducing protective gas;
3) adding preheated pure magnesium into a crucible, setting the temperature of a resistance furnace, keeping the temperature constant after furnace materials are completely melted, adding dried Mg-30 wt% Ca alloy, heating to 720 ℃, preserving heat, adding Mg-30 wt% Sr alloy, heating to 760 ℃, and preserving heat;
4) fully stirring and standing after furnace materials are completely melted; and after the temperature is reduced to 720 ℃, the melted material is cast on a mould, and a required magnesium-calcium-strontium alloy model is formed after solidification.
Further, the preparation of the magnesium-calcium-strontium alloy pipe comprises the following steps:
1) performing linear cutting and turning on the alloy cast ingot to obtain a hollow cylindrical blank, wherein the outer diameter of the hollow cylindrical blank is 30-50 mm, and the diameter of the middle through hole is 4.5-6.5 mm;
2) putting the hollow cylindrical blank into a box-type resistance furnace, carrying out solid solution treatment at 400-500 ℃ for 6-12 hours, and quenching with warm water at 60-90 ℃;
3) smearing a lubricant on the surface of an extrusion die, then placing the extrusion die into a resistance furnace, heating to 400-480 ℃, placing a hollow cylindrical blank, preserving heat for 5min, taking out the extrusion die and the hollow cylindrical blank, well installing, extruding at the temperature of 250-450 ℃, wherein the extrusion speed is 5mm/s, and the extrusion ratio is 10-70, thus obtaining a seamless extrusion tube;
4) and (3) annealing the seamless extruded tube in a box-type resistance furnace at the annealing temperature of 200-350 ℃ for 10min to finally obtain the thin-wall magnesium alloy thin tube with the inner diameter of 3mm, the wall thickness of L and the length of 5 mm.
Further, the wall thickness L is 1.5, 2, 2.5 mm.
Further, the preparation of the porous magnesium-calcium-strontium alloy tube comprises the following steps:
1) the porous magnesium-calcium-strontium alloy pipe is based on a magnesium alloy thin pipe, and finite element analysis is carried out according to the mechanical property of the magnesium alloy to obtain corresponding mechanical parameters;
2) designing and drawing a pattern of the porous magnesium-calcium-strontium alloy tube to be prepared according to the finite element analysis, and introducing the pattern into a laser engraving machine; precisely carving the porous magnesium-calcium-strontium alloy tube by a laser carving machine under the protection of inert gas, and then calculating the porosity;
3) post-treatment, including surface brightening: and (3) placing the precisely carved and formed porous magnesium-calcium-strontium alloy pipe into a weakly acidic organic solvent for ultrasonic oscillation washing for 1-5 minutes, and placing the porous magnesium-calcium-strontium alloy pipe subjected to surface brightening treatment into a cleaning agent which does not react with metal magnesium for cleaning and airing.
Further, the organic solvent is distilled water, absolute ethyl alcohol and weak acid with pH value more than 5.5 and less than 6.5.
Further, the preparation of the porous magnesium alloy tube stent material with the chitosan coating comprises the following steps:
1) sterilizing and disinfecting the micro-arc oxidized porous magnesium alloy pipe for later use;
2) dissolving chitosan powder in acetic acid, adding the solution, stirring uniformly, diluting with deionized water, adding sodium chloride and potassium hydroxide to adjust the pH value, centrifuging the solution, placing a porous magnesium-calcium-strontium alloy tube into the solution, and performing freeze drying and molding; and (5) finishing the porous magnesium alloy tube support material with the chitosan coating.
The invention also aims to provide the magnesium alloy pipe bracket with the bifunctional chitosan coating, which is prepared by the preparation method of the magnesium alloy pipe bracket with the bifunctional chitosan coating.
The invention also aims to provide application of the bifunctional chitosan coated magnesium alloy tube stent in a biological material for treating bone tumors.
By combining all the technical schemes, the invention has the advantages and positive effects that: the bone regeneration device has the advantages of good bone formation effect, simple structure, reliable performance and convenient use, and the mechanical strength of the bone regeneration device can not only maintain the contour and the shape of bone regeneration, provide enough space for newly-grown bone to maintain, but also inhibit the growth invasion and proliferation of tumor cells. The magnesium alloy and the chitosan material are not required to be taken out in a secondary operation, the pain of a patient is relieved, the operation times and cost are reduced, finally the material is gradually degraded, the growth of residual tumor cells around is inhibited, the growth of normal osteoblasts around is promoted to achieve the purpose of repairing a defect area, and the magnesium alloy and the chitosan material can be used for repairing the bone defect after the osteosarcoma operation is removed to meet the daily life needs of the patient after the operation.
The invention can perform plasticity according to the requirement of the defect area of the patient, has safe material performance, does not need to be taken out in a secondary operation, provides convenience for the clinical operation of a doctor and can relieve the pain of the patient.
The invention can exert the performance advantages of various materials, has a biological material with double functions, not only inhibits the growth invasion and metastasis of tumor cells, but also has the capability of promoting the regeneration of surrounding normal osteoblasts, and jointly promotes the regeneration and repair functions of bone tissues, and the material is convenient to obtain and manufacture. Degradable magnesium alloys have received increasing attention as orthopedic implants and some studies have reported potential anti-tumor activity. Magnesium-based alloys can actively interfere with the growth of tumor cells, such as osteosarcoma, breast cancer and oral epidermoid carcinoma. Chitosan is a natural high molecular polymer with viscosity, good biocompatibility, biodegradability, film-forming property and drug-carrying property, and is often used as a growth factor carrier and a scaffold material to be applied to bone tissue engineering.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained from the drawings without creative efforts.
FIG. 1 is a flow chart of a preparation method of a bifunctional chitosan coated magnesium alloy tube stent provided by an embodiment of the present invention.
Fig. 2 and fig. 3 are flowcharts of experimental operations provided by the embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides a magnesium alloy pipe bracket with a bifunctional chitosan coating, a preparation method and application thereof, and the invention is described in detail with reference to the attached drawings.
As shown in fig. 1, the preparation method of the bifunctional chitosan coated magnesium alloy tube stent provided by the embodiment of the present invention includes the following steps:
s101: preparing a magnesium alloy: the Mg-Ca-Sr ternary alloy is prepared by a smelting method, and Ca and Sr elements with good biocompatibility are used as microalloying elements. In the preparation process, the optimized ternary alloy structure is obtained by adjusting the process parameters such as heat preservation temperature, heat preservation time, cooling rate and the like and heat treatment.
S102: preparing a magnesium alloy pipe: carrying out linear cutting and turning on the alloy cast ingot to obtain a hollow cylindrical blank, heating, carrying out solid solution, and quenching for later use; heating an extrusion die, putting the heated extrusion die into a hollow cylindrical blank, and extruding at a high temperature to obtain a seamless extruded tube; and annealing the seamless extruded tube to obtain the thin-wall magnesium alloy thin tube.
S103: preparing a porous magnesium alloy pipe: based on a magnesium alloy thin tube, carrying out finite element analysis, designing and drawing a pattern and introducing the pattern into a laser engraving machine; precisely carving under the protection of inert gas, then performing surface brightening treatment, ultrasonically shaking and washing in a weakly acidic organic solvent, and finally putting into a cleaning agent which does not react with the metal magnesium for cleaning and airing.
S104: mechanical property research of the magnesium alloy pipe: the mechanical property index of the magnesium alloy pipe is obtained by measuring the microhardness of the magnesium alloy pipe and performing a tensile test, a compression test and a bending test on the magnesium alloy pipe.
S105: preparing a micro-arc oxidation coating on the surface of the porous magnesium alloy pipe: and (3) polishing the surface of the porous magnesium alloy pipe, then placing the porous magnesium alloy pipe in a cleaning tank for cleaning, oxidizing and cleaning the porous magnesium alloy pipe under the voltage of 450V, and finally drying the porous magnesium alloy pipe in a drying tank.
S106: preparing a chitosan coating material: dissolving chitosan powder in acetic acid, adding into the above solution, stirring, diluting with deionized water, adding sodium chloride and potassium hydroxide to adjust pH value, centrifuging the solution, placing porous magnesium-calcium-strontium alloy tube into the solution, and freeze drying.
The preparation method of the magnesium alloy pipe bracket with the bifunctional chitosan coating provided by the embodiment of the invention specifically comprises the following steps:
1) preparing the magnesium-calcium-strontium alloy:
a. the raw materials of the as-cast alloy used in the experiment comprise high-purity magnesium (99.9 wt%), Mg-30 wt% Ca intermediate alloy and Mg-30 wt% Sr intermediate alloy.
b. Smelting and casting in a resistance furnace filled with mixed protective gas; preparing raw materials according to the proportion of experimental design components; preparing a mould and preparing for smelting. Removing rust on the surfaces of all tools, heating, and keeping dry; heating the crucible and introducing protective gas.
c. Adding preheated pure magnesium into a crucible, setting the temperature of a resistance furnace, keeping the temperature constant after furnace materials are completely melted, adding dried Mg-30 wt% Ca alloy, heating to 720 ℃, preserving heat, adding Mg-30 wt% Sr alloy, heating to 760 ℃, and preserving heat.
d. And fully stirring and standing after the furnace burden is completely melted. After the temperature is reduced to 720 ℃, the melted material is cast on a mould (the process needs to be communicated with protective gas), and a required magnesium-calcium-strontium alloy model is formed after solidification.
2) Preparing a magnesium-calcium-strontium alloy pipe:
the thin-wall magnesium alloy thin pipe has the specification of 3mm of inner diameter, different pipe wall thicknesses L (1.5, 2 and 2.5mm) and 5mm of length. The mechanical property parameter range is as follows: the tensile strength is more than or equal to 210MPa, the yield strength is more than or equal to 100MPa, the flattening strength is more than or equal to 600MPa, and the elongation is more than or equal to 10%. The method comprises the following steps of preparing the thin-wall magnesium alloy thin tube with excellent comprehensive mechanical properties:
a. performing linear cutting and turning on the alloy cast ingot to obtain a hollow cylindrical blank, wherein the outer diameter of the hollow cylindrical blank is 30-50 mm, and the diameter of the middle through hole is 4.5-6.5 mm;
b. putting the hollow cylindrical blank into a box-type resistance furnace, carrying out solid solution treatment at 400-500 ℃ for 6-12 hours, and quenching by adopting warm water (60-90 ℃);
c. smearing a lubricant on the surface of an extrusion die, then placing the extrusion die into a resistance furnace, heating to 400-480 ℃, then placing a hollow cylindrical blank, preserving heat for 5min, taking out the extrusion die and the hollow cylindrical blank, well installing, extruding at the temperature of 250-450 ℃, wherein the extrusion speed is 5mm/s, and the extrusion ratio is 10-70, thus obtaining a seamless extruded tube;
d. and (3) annealing the seamless extruded tube in a box-type resistance furnace at the annealing temperature of 200-350 ℃ for 10min to finally obtain the thin-wall magnesium alloy thin tube with the inner diameter of 3mm, the wall thickness L (1.5, 2, 2.5mm) and the length of 5 mm.
3) Preparing a porous magnesium-calcium-strontium alloy tube:
a. the porous magnesium-calcium-strontium alloy pipe is based on a magnesium alloy thin pipe, and finite element analysis is firstly carried out according to the mechanical property of the magnesium alloy to obtain corresponding mechanical parameters, so that the porous magnesium-calcium-strontium alloy pipe is suitable for the mechanical requirements of a model with the inner diameter of 3mm, the wall thickness L (1.5 mm, 2 mm and 2.5mm), the length of 5mm and the aperture of 1mm in the experiment.
b. Designing and drawing a pattern of the porous magnesium-calcium-strontium alloy tube to be prepared according to the finite element analysis, and introducing the pattern into a laser engraving machine; under the protection of inert gas, the porous magnesium-calcium-strontium alloy tube is precisely carved by a laser carving machine, and then the porosity is calculated.
c. Post-treatment, including surface brightening: placing the porous magnesium calcium strontium alloy pipe formed by precise carving into a weakly acidic organic solvent (distilled water, absolute ethyl alcohol and weak acid with the pH value of 5.5 being more than 5.5 and less than 6.5) to perform ultrasonic oscillation washing for 1-5 minutes, placing the porous magnesium calcium strontium alloy pipe subjected to surface brightening treatment into a cleaning agent which does not react with metal magnesium to clean and dry.
4) The porous magnesium alloy pipe bracket material of the chitosan coating comprises the following components:
a. and (4) disinfecting and sterilizing the micro-arc oxidized porous magnesium alloy pipe according to the experimental size requirement for use.
b. Dissolving chitosan powder in acetic acid, adding the solution into the acetic acid, stirring uniformly, diluting with deionized water, adding sodium chloride and potassium hydroxide to adjust the pH value, centrifuging the solution, placing the porous magnesium-calcium-strontium alloy tube into the solution, and freeze-drying and forming. And (5) finishing the porous magnesium alloy tube support material with the chitosan coating.
The technical effects of the present invention will be described in detail with reference to experimental operations.
The specific operation flow of the experiment is shown in fig. 2 and 3.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a difunctional chitosan coated magnesium alloy tube bracket is characterized in that chitosan is prepared into mixed suspension according to a proportion; injecting the mixed suspension into a mould, and putting the degradable magnesium alloy; and continuously injecting the mixed suspension to form a sandwich coating structure, thereby forming the magnesium alloy tube support material with the chitosan coating.
2. The method for preparing a bifunctional chitosan-coated magnesium alloy tube scaffold according to claim 1, wherein the method for preparing a bifunctional chitosan-coated magnesium alloy tube scaffold comprises the steps of:
step one, preparing magnesium alloy: preparing a Mg-Ca-Sr ternary alloy by a smelting method, and using Ca and Sr elements with good biocompatibility as microalloying elements; in the preparation process, an optimized ternary alloy structure is obtained by adjusting the process parameters of the heat preservation temperature, the heat preservation time, the cooling rate and the heat treatment;
step two, preparing a magnesium alloy pipe: carrying out linear cutting and turning on the alloy cast ingot to obtain a hollow cylindrical blank, heating, carrying out solid solution, and quenching for later use; heating an extrusion die, putting the heated extrusion die into a hollow cylindrical blank, and extruding at a high temperature to obtain a seamless extruded tube; annealing the seamless extruded tube to obtain a thin-wall magnesium alloy thin tube;
step three, preparing a porous magnesium alloy pipe: based on a magnesium alloy thin tube, carrying out finite element analysis, designing and drawing a pattern and introducing the pattern into a laser engraving machine; precisely carving under the protection of inert gas, then performing surface brightening treatment, ultrasonically oscillating and washing in a weakly acidic organic solvent, and finally putting into a cleaning agent which does not react with metal magnesium for cleaning and airing;
fourthly, the mechanical property of the magnesium alloy pipe is as follows: measuring the microhardness of the magnesium alloy pipe, and performing a tensile test, a compression test and a bending test to obtain the mechanical property index of the magnesium alloy pipe;
fifthly, preparing a micro-arc oxidation coating on the surface of the porous magnesium alloy pipe: polishing the surface of the porous magnesium alloy pipe, cleaning the porous magnesium alloy pipe in a cleaning tank, oxidizing and cleaning the porous magnesium alloy pipe under the voltage of 450V, and finally drying the porous magnesium alloy pipe in a drying tank;
sixthly, preparing the chitosan coating material: dissolving chitosan powder in acetic acid, adding into the above solution, stirring, diluting with deionized water, adding sodium chloride and potassium hydroxide to adjust pH value, centrifuging, placing porous magnesium-calcium-strontium alloy tube into the solution, and freeze drying.
3. The method for preparing the bifunctional chitosan coated magnesium alloy tube stent as recited in claim 2, wherein the preparation of the magnesium-calcium-strontium alloy in the magnesium-calcium-strontium alloy tube comprises:
1) the cast alloy raw materials comprise 99.9 wt% of high-purity magnesium, Mg-30 wt% of Ca intermediate alloy and Mg-30 wt% of Sr intermediate alloy;
2) smelting and casting in a resistance furnace filled with mixed protective gas; preparing raw materials according to component proportions; preparing a mould and smelting; removing rust on the surfaces of all tools, heating, and keeping dry; heating the crucible and introducing protective gas;
3) adding preheated pure magnesium into a crucible, setting the temperature of a resistance furnace, keeping the temperature constant after furnace materials are completely melted, adding dried Mg-30 wt% Ca alloy, heating to 720 ℃, preserving heat, adding Mg-30 wt% Sr alloy, heating to 760 ℃, and preserving heat;
4) fully stirring and standing after the furnace burden is completely melted; and after the temperature is reduced to 720 ℃, the melted material is cast on a mould, and a required magnesium-calcium-strontium alloy model is formed after solidification.
4. The method for preparing the bifunctional chitosan coated magnesium alloy tube stent as recited in claim 2, wherein the preparation of the magnesium-calcium-strontium alloy tube comprises:
1) performing linear cutting and turning on the alloy cast ingot to obtain a hollow cylindrical blank, wherein the outer diameter of the hollow cylindrical blank is 30-50 mm, and the diameter of the middle through hole is 4.5-6.5 mm;
2) putting the hollow cylindrical blank into a box-type resistance furnace, carrying out solid solution treatment at 400-500 ℃ for 6-12 hours, and quenching with warm water at 60-90 ℃;
3) smearing a lubricant on the surface of an extrusion die, then placing the extrusion die into a resistance furnace, heating to 400-480 ℃, placing a hollow cylindrical blank, preserving heat for 5min, taking out the extrusion die and the hollow cylindrical blank, well installing, extruding at the temperature of 250-450 ℃, wherein the extrusion speed is 5mm/s, and the extrusion ratio is 10-70, thus obtaining a seamless extrusion tube;
4) and (3) annealing the seamless extruded tube in a box-type resistance furnace at the annealing temperature of 200-350 ℃ for 10min to finally obtain the thin-wall magnesium alloy thin tube with the inner diameter of 3mm, the wall thickness of L and the length of 5 mm.
5. The method for preparing the bifunctional chitosan coated magnesium alloy tube scaffold of claim 4, wherein the wall thickness L is 1.5, 2, 2.5 mm.
6. The preparation method of the bifunctional chitosan coated magnesium alloy tube scaffold as recited in claim 2, wherein the preparation of the porous magnesium calcium strontium alloy tube comprises:
1) the porous magnesium-calcium-strontium alloy pipe is based on a magnesium alloy thin pipe, and finite element analysis is carried out according to the mechanical property of the magnesium alloy to obtain corresponding mechanical parameters;
2) designing and drawing a pattern of the porous magnesium-calcium-strontium alloy tube to be prepared according to the finite element analysis, and introducing the pattern into a laser engraving machine; precisely carving the porous magnesium-calcium-strontium alloy tube by a laser carving machine under the protection of inert gas, and then calculating the porosity;
3) post-treatment, including surface brightening: and (3) placing the precisely carved and formed porous magnesium-calcium-strontium alloy pipe into a weakly acidic organic solvent for ultrasonic oscillation washing for 1-5 minutes, and placing the porous magnesium-calcium-strontium alloy pipe subjected to surface brightening treatment into a cleaning agent which does not react with metal magnesium for cleaning and airing.
7. The method for preparing a bifunctional chitosan coated magnesium alloy tube scaffold of claim 6, wherein the organic solvent is distilled water, absolute ethanol and weak acid with pH value of 5.5 < pH < 6.5.
8. The method for preparing the bifunctional chitosan-coated magnesium alloy tube scaffold as recited in claim 2, wherein the preparing of the chitosan-coated porous magnesium alloy tube scaffold material comprises:
1) sterilizing and disinfecting the micro-arc oxidized porous magnesium alloy pipe for later use;
2) dissolving chitosan powder in acetic acid, adding the solution, stirring uniformly, diluting with deionized water, adding sodium chloride and potassium hydroxide to adjust the pH value, centrifuging the solution, putting a porous magnesium-calcium-strontium alloy tube into the solution, and freeze-drying and forming; and (5) finishing the porous magnesium alloy tube support material with the chitosan coating.
9. The bifunctional chitosan coated magnesium alloy tube stent prepared by the preparation method of the bifunctional chitosan coated magnesium alloy tube stent as claimed in any one of claims 1 to 8.
10. Use of the bifunctional chitosan-coated magnesium alloy tube scaffold of claim 9 in a biomaterial for bone tumor treatment.
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