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CN114191616A - A kind of preparation method of reinforced absorbable medical implant material - Google Patents

A kind of preparation method of reinforced absorbable medical implant material Download PDF

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Publication number
CN114191616A
CN114191616A CN202111457063.6A CN202111457063A CN114191616A CN 114191616 A CN114191616 A CN 114191616A CN 202111457063 A CN202111457063 A CN 202111457063A CN 114191616 A CN114191616 A CN 114191616A
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magnesium alloy
amorphous nano
medical implant
calcium phosphate
composite material
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Inventor
王青青
岳�文
王尉
佘丁顺
王浩东
康嘉杰
朱丽娜
孟德忠
付志强
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Zhengzhou Research Institute China University Of Geosciences Beijing
China University of Geosciences Beijing
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Zhengzhou Research Institute China University Of Geosciences Beijing
China University of Geosciences Beijing
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Priority to CN202111457063.6A priority Critical patent/CN114191616A/en
Publication of CN114191616A publication Critical patent/CN114191616A/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
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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
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—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
    • 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
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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Abstract

本申请公开了一种增强可吸收医用植入材料的制备方法，用于增强可吸收医用植入材料的强度。本申请方法包括以下步骤：对镁合金进行清洗以及干燥预处理；将经过预处理的镁合金进行破碎，并将经过破碎处理后的镁合金进行高能球磨处理，制备非晶纳米镁合金粉末；将非晶纳米镁合金粉末置于MOCVD设备的载物台上，采用化学气相沉积的方法制备磷酸钙包覆非晶纳米镁合金核壳复合材料；称取预设量的医用植入材料，向医用植入材料中加入溶剂，配置成预设比例的溶液，向溶液中加入预设量磷酸钙包覆非晶纳米镁合金核壳复合材料进行搅拌直至分散均匀，以得到分散均匀的成品反应液；将该成品反应液进行固定成型以及干燥处理，得到成品。

Figure 202111457063

The present application discloses a preparation method of an reinforced absorbable medical implant material, which is used to enhance the strength of the absorbable medical implant material. The method of the present application includes the following steps: cleaning and drying the magnesium alloy; crushing the pretreated magnesium alloy, and subjecting the crushed magnesium alloy to high-energy ball milling to prepare amorphous nano-magnesium alloy powder; The amorphous nano-magnesium alloy powder is placed on the stage of the MOCVD equipment, and the calcium phosphate-coated amorphous nano-magnesium alloy core-shell composite material is prepared by chemical vapor deposition; A solvent is added to the implant material to configure a solution with a preset ratio, and a preset amount of calcium phosphate-coated amorphous nano-magnesium alloy core-shell composite material is added to the solution and stirred until uniformly dispersed, so as to obtain a uniformly dispersed finished reaction solution; The finished product reaction solution is subjected to fixed molding and drying treatment to obtain a finished product.

Figure 202111457063

Description

Preparation method of reinforced absorbable medical implant material
Technical Field
The application relates to the field of reinforcement of absorbable medical implant materials, in particular to a preparation method of a reinforced absorbable medical implant material.
Background
The bio-absorbable material is a material which can be degraded and absorbed in the in vivo biological environment, and with the continuous and deep research on the bio-absorbable material and the cross fusion development of multiple disciplines such as materials science, biology, medicine and the like, the bio-absorbable material is widely applied to the medical field for manufacturing the human body implantable device. The bio-absorbable material mainly comprises absorbable metal materials, high polymer materials, inorganic materials and composite materials 4.
Polylactic-co-glycolic acid (PLGA), which is a copolymer of lactic acid and glycolic acid with no functional side group, is an important biomedical polymer material, has the advantages of two polyester materials, namely Polylactic acid (PLA) and Polyglycolic acid (PGA), has better biocompatibility and degradability, and is widely applied to the biomedical field, such as surgical sutures, fracture internal fixation materials, tissue repair materials and drug controlled release systems. However, PLGA, PLA, PGA, etc. have disadvantages such as poor strength and generation of acidic substances during degradation when used alone as implant materials.
The calcium phosphate is used as the main inorganic component of the skeleton in the vertebrate body, and has the characteristics of good biocompatibility, bioactivity, osteoinductivity, biodegradability and the like. The magnesium alloy has the characteristics of degradability, mechanical property close to that of human bones, good mechanical compatibility, excellent biological safety and the like, and is widely used for absorbable medical implant materials, but the magnesium alloy is in a human body physiological environment, has relatively high degradation rate, can generate reaction products of magnesium ions and hydrogen gas through rapid degradation, has local corrosion, leads to accumulation of magnesium ions, hydrogen gas and corrosion precipitates in a body, and causes that the mechanical integrity and the mechanical property of the magnesium alloy are also reduced or even lost, namely, when the magnesium alloy is used as the absorbable medical implant material, the strength of the absorbable medical implant material is reduced.
Disclosure of Invention
The application provides a preparation method of a reinforced absorbable medical implant material, which is used for reinforcing the strength of the absorbable medical implant material.
The application provides a preparation method of a reinforced absorbable medical implant material, which is characterized by comprising the following steps:
s1, cleaning and drying the magnesium alloy;
s2, crushing the magnesium alloy pretreated in the step S1, and performing high-energy ball milling treatment on the crushed magnesium alloy to prepare amorphous nano magnesium alloy powder;
s3, placing the amorphous nano magnesium alloy powder obtained in the step S2 on an object stage of MOCVD equipment, and preparing the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material by adopting a chemical vapor deposition method;
s4, weighing a preset amount of medical implant materials, adding a solvent into the medical implant materials to prepare a solution with a preset proportion, adding a preset amount of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material obtained through the treatment in the step S3 into the solution, and stirring until the mixture is uniformly dispersed to obtain a uniformly dispersed finished product reaction solution;
and S5, carrying out fixing molding and drying treatment on the finished product reaction liquid obtained through the step S4 to obtain a finished product.
Optionally, the magnesium alloy in step S1 is Mg-5Zn or Mg-3 Zn.
Alternatively, the conditions of the high-energy ball milling process in step S2 are: the temperature is 10-30 ℃, and the mass ratio of the ball materials is (10-120) under the argon condition: 1, the rotating speed is 100-400 r/min, and the time is 10-100 h.
Alternatively, the precursor a of the chemical vapor deposition in step S3 is a methanol solution of calcium lactate, and the precursor B is trimethyl phosphate, wherein the molar ratio of calcium in calcium lactate to phosphorus in trimethyl phosphate is 5: (3-24), the gasification temperature is 200-300 ℃.
Optionally, the process for preparing the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material in step S3 specifically comprises: and introducing oxygen plasma into a chemical vapor deposition chamber of the MOCVD equipment, wherein the deposition temperature is 500-700 ℃, and the deposition times are 10-20.
Optionally, in step S4, the implant material for chinese medicine is a mixture of one or more of PLGA, PLA, and PGA in any ratio.
Alternatively, the solvent in step S4 is dichloromethane or N, N-dimethylformamide.
Optionally, in step S4, the mass concentration of the Chinese medicinal implant material is 5% to 10%;
in the step S4, the mass concentration of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is 1-15%, wherein the mass concentration of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is determined by the mass of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material in the medical implant material.
Optionally, the fixing and forming manner in step S4 is 3D printing or injection molding.
Optionally, the drying condition in the step S5 is a vacuum drying manner, the drying temperature is 25 to 40 ℃, and the drying time is 12 to 48 hours.
According to the technical scheme, the method has the following beneficial effects:
in the invention, the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material prepared by adopting a chemical vapor deposition method has simple, efficient and easy operation, alkaline substances generated by degradation of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material and acidic substances generated by degradation of a medical high polymer material are subjected to acid-base neutralization, so that the generation of human tissue inflammation is reduced, meanwhile, elements such as magnesium, calcium, zinc, phosphorus and the like generated in the degradation process are favorable for promoting the healing and growth of bones, in addition, the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is introduced into an absorbable medical implant material, the amorphous nano magnesium alloy is taken as a core, calcium phosphate is taken as a shell, the surface of the amorphous nano magnesium alloy is coated by the calcium phosphate to form a core-shell structure, the degradation rate of the magnesium alloy is reduced, and the accumulation of magnesium ions, hydrogen and corrosive precipitates in vivo is reduced, thereby enhancing the strength of the absorbable medical implant material.
Drawings
FIG. 1 is a schematic illustration of a method of making a reinforced absorbable medical implant material of the present application.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of the present invention.
In order to solve the above technical problems, the present application provides a method for preparing a reinforced absorbable medical implant material, which can enhance the strength of the absorbable medical implant material, and specifically refers to the following examples.
Referring to fig. 1, the present application provides a method for preparing a reinforced absorbable medical implant material, comprising the following steps:
s1, cleaning and drying the magnesium alloy;
s2, crushing the magnesium alloy pretreated in the step S1, and performing high-energy ball milling treatment on the crushed magnesium alloy to prepare amorphous nano magnesium alloy powder;
s3, placing the amorphous nano magnesium alloy powder obtained in the step S2 on an object stage of MOCVD equipment, and preparing the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material by adopting a chemical vapor deposition method;
s4, weighing a preset amount of medical implant materials, adding a solvent into the medical implant materials to prepare a solution in a preset proportion, adding a preset amount of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material obtained through the treatment in the step S3 into the solution, and stirring until the mixture is uniformly dispersed to obtain a uniformly dispersed finished product reaction solution;
and S5, carrying out fixing molding and drying treatment on the finished product reaction liquid obtained through the step S4 to obtain a finished product.
According to the method, the magnesium alloy is pretreated by mainly ultrasonically cleaning the magnesium alloy by using deionized water and absolute ethyl alcohol, and then drying the magnesium alloy after ultrasonic cleaning to obtain the clean and dry magnesium alloy, so that the condition that impurities and/or moisture exist on the surface of the magnesium alloy to influence subsequent reaction is reduced.
The MOCVD equipment is Metal-organic Chemical Vapor Deposition (Metal-organic Chemical Vapor Deposition) equipment, and the working principle of the MOCVD equipment is that after Metal organic matters are gasified, carrier gas is introduced into a reaction chamber, Chemical reaction is carried out in the reaction chamber to obtain a product, and the product is deposited on a substrate to form a film. In the invention, the amorphous nano magnesium alloy powder obtained in the step S2 is placed on a conveying type objective table of a continuous vibration type MOCVD device, and the amorphous nano magnesium alloy powder and calcium phosphate are subjected to chemical reaction in a reaction chamber by adopting a chemical vapor deposition method under the condition that a carrier gas is argon, so that the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is prepared.
In the invention, amorphous nano magnesium alloy powder prepared from magnesium alloy reacts with calcium phosphate to obtain a calcium phosphate coated amorphous nano magnesium alloy core-shell composite material, the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is introduced into the absorbable medical implant material to prepare the absorbable implant medical material added with the nano core-shell composite material, the magnesium alloy added with the nano core-shell composite material can be absorbed and implanted into the medical material and is not directly in the physiological environment of the human body any more, but uses amorphous nano magnesium alloy as core and calcium phosphate as shell, and uses calcium phosphate to coat the surface of amorphous nano magnesium alloy to form core-shell structure, the degradation process is gradual, and the degradation rate of the magnesium alloy is slowed down, so that the accumulation of magnesium ions, hydrogen and corrosion precipitates in a body is reduced, and the strength of the absorbable medical implant material is enhanced. The calcium phosphate coated amorphous nano magnesium alloy core-shell composite material generates alkaline substances in the degradation process, and the absorbable medical implant material generates acidic substances in the degradation process, the acidic substances are easy to induce inflammation of human tissues, the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is introduced into the absorbable medical implant material, and the acidic substances and the alkaline substances are subjected to acid-base neutralization, so that a human body is in a weakly alkaline environment, and the probability of inflammation of the human tissues is reduced. Magnesium, calcium, zinc, phosphorus and other elements generated in the degradation process of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material are beneficial to promoting the healing and growth of bones.
Optionally, the magnesium alloy in step S1 is Mg-5Zn or Mg-3 Zn.
The figure in front of Zn in the Mg-Zn (magnesium-zinc) alloy in the invention is the mass fraction of Zn in the alloy, such as: the mass fraction of Zn in Mg-5Zn was 5%, which indicates that the content of Zn in the alloy was 5%. The higher the Zn content in the Mg-Zn alloy is, the better, and when the Zn mass fraction is less than 6%, the strength of the Mg-Zn alloy increases with the increase of the Zn content; when the mass fraction of Zn is more than 6%, the strength and plasticity of the Mg-Zn alloy are remarkably reduced along with the increase of the content of Zn, so that Mg-5Zn and Mg-3Zn with the mass fraction of Zn less than 6% in the Mg-Zn alloy are used for preparation in the scheme, and the prepared finished products have no obvious difference because the content difference of Zn in Mg-5Zn and Mg-3Zn is small.
It is understood that the magnesium alloy used in the present scheme may be Mg-5Zn, Mg-3Zn, or other Mg-Zn alloys with a Zn mass fraction of less than 6%, such as: mg-4Zn, and the specific definition is not limited herein.
Alternatively, the conditions of the high-energy ball milling process in step S2 are: the temperature is 10-30 ℃, and the mass ratio of the ball materials is (10-120) under the argon condition: 1, the rotating speed is 100-400 r/min, and the time is 10-100 h.
During ball milling, the metal powder particles and the grinding balls undergo severe collisions, and the particles are repeatedly crushed, fractured, welded, and re-crushed. Under the action of each impact load, the powder particles generate new surfaces, the surfaces of the new surfaces are high and easy to be oxidized and recombined, so the ball milling treatment is generally carried out under the protection of vacuum or inert gas, the rest of the inert gas except argon has little content in the atmosphere, the price of argon in the inert gas is relatively lower, and the argon in the inert gas is generally adopted as protective gas to react in practical application so as to reduce the recombination of the oxidized metal powder particles.
Alternatively, the precursor a of the chemical vapor deposition in step S3 is a methanol solution of calcium lactate, and the precursor B is trimethyl phosphate, wherein the molar ratio of calcium in calcium lactate to phosphorus in trimethyl phosphate is 5: (3-24), the gasification temperature is 200-300 ℃.
The precursor A is the methanol solution of calcium lactate, which is obtained by placing the calcium lactate in the methanol solution, sealing and stirring until the calcium lactate is uniformly dispersed, and transferring the uniformly dispersed methanol solution of the calcium lactate to a raw material bottle. Adopt sealed mode to stir and reduce on the one hand and spill the condition that causes the waste outside the material in the stirring process, on the other hand reduces to stir under sealed condition and can reduce the impurity of introducing in the environment.
Optionally, the process for preparing the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material in step S3 specifically comprises: and introducing oxygen plasma into a chemical vapor deposition chamber of the MOCVD equipment, wherein the deposition temperature is 500-700 ℃, and the deposition times are 10-20.
Optionally, in step S4, the implant material for chinese medicine is a mixture of one or more of poly (lactic-co-glycolic acid), poly (lactic acid), and poly (glycolic acid) in any proportion.
Alternatively, the solvent in step S4 is dichloromethane or N, N-dimethylformamide.
The solvent used in the invention should be completely volatilized in the finished product theoretically, in order to save the time required for completely volatilizing the solvent in the drying treatment, the selected solvent is volatile and has small influence on human bodies in toxicological research, and the solvent in the invention can be dichloromethane or N, N-dimethylformamide.
Optionally, in step S4, the mass concentration of the Chinese medicinal implant material is 5% to 10%; in the step S4, the mass concentration of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is 1-15%, wherein the mass concentration of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is determined by the mass of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material in the medical implant material.
Optionally, the fixing and forming manner in step S4 is 3D printing or injection molding.
Optionally, the drying condition in the step S5 is a vacuum drying manner, the drying temperature is 25 to 40 ℃, and the drying time is 12 to 48 hours.
The following embodiments will be described in further detail with reference to the following examples, which are implemented on the premise of the technology of the present invention, and the detailed embodiments and the specific operation procedures are given to illustrate the inventive concept of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1:
(1) pretreating the magnesium alloy: sequentially using deionized water and absolute ethyl alcohol to ultrasonically clean Mg-5Zn alloy for 10min, and drying for 8h under the vacuum condition at the temperature of 60 ℃;
(2) crushing the Mg-5Zn alloy pretreated in the step (1), and carrying out high-energy ball milling treatment on the crushed magnesium alloy at normal temperature under the argon condition, wherein the mass ratio of ball materials is 10: 1, preparing amorphous nano magnesium alloy powder at the rotating speed of 100r/min for 10 hours;
(3) weighing 1g of amorphous nano magnesium alloy powder in the step (2), and placing the amorphous nano magnesium alloy powder on a transmission type objective table of a continuous vibration type MOCVD device;
(4) weighing 2.18g of calcium lactate, placing the calcium lactate in 100mL of methanol, sealing and stirring, transferring the calcium lactate into a raw material bottle (precursor A) after uniform dispersion, and introducing argon for 30 min; measuring 55.3mL trimethyl phosphate, placing the trimethyl phosphate in a raw material bottle (precursor B), and introducing argon for 30 min;
(5) respectively sending the precursor A and the precursor B in the raw material bottle to a vaporization chamber by using a precision pump, vaporizing the precursor A and the precursor B into steam at the vaporization temperature of 250 ℃, directionally transmitting the steam of the metal organic precursor to a heated object stage at the heating temperature of 600 ℃, introducing oxygen plasma to react with the precursor, and generating calcium phosphate on the surface of the amorphous nano magnesium alloy to obtain the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material;
(6) dissolving 5g of polylactic acid-glycolic acid copolymer in 95g of dichloromethane to prepare 5% polylactic acid-glycolic acid copolymer solution, adding 0.5g of calcium phosphate coated amorphous nano magnesium alloy core-shell composite material, stirring vigorously for 5h to obtain a uniformly dispersed finished reaction solution, solidifying and forming the finished reaction solution to obtain a semi-finished product, and drying the semi-finished product under the vacuum condition, wherein the drying temperature is 35 ℃ and the drying time is 12h to obtain the finished product.
Example 2:
(1) pretreating the magnesium alloy: ultrasonically cleaning Mg-3Zn alloy with deionized water and absolute ethyl alcohol for 20min in sequence, and drying for 12h under the vacuum condition at the temperature of 50 ℃;
(2) crushing the Mg-3Zn alloy pretreated in the step (1), and carrying out high-energy ball milling treatment on the crushed magnesium alloy at normal temperature under the argon condition, wherein the mass ratio of ball materials is 20: 1, preparing amorphous nano magnesium alloy powder at the rotating speed of 200r/min for 10 hours;
(3) weighing 0.8g of amorphous nano magnesium alloy powder in the step (2), and placing the amorphous nano magnesium alloy powder on a transmission type objective table of continuous vibration type MOCVD equipment;
(4) weighing 2.18g of calcium lactate, placing the calcium lactate in 100mL of methanol, sealing and stirring, transferring the calcium lactate into a raw material bottle (precursor A) after uniform dispersion, and introducing argon for 30 min; measuring 46.3mL trimethyl phosphate, placing the trimethyl phosphate in a raw material bottle (precursor B), and introducing argon for 30 min;
(5) respectively sending the precursor A and the precursor B in the raw material bottle to a vaporization chamber by using a precision pump, vaporizing the precursor A and the precursor B into steam at the vaporization temperature of 230 ℃, directionally transmitting the steam of the metal organic precursor to a heated object stage at the heating temperature of 550 ℃, introducing oxygen plasma to react with the precursor, and generating calcium phosphate on the surface of the amorphous nano magnesium alloy to obtain the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material;
(6) dissolving 7g of polylactic acid-glycolic acid copolymer in 93g of dichloromethane to prepare 7% polylactic acid-glycolic acid copolymer solution, adding 0.7g of calcium phosphate coated amorphous nano magnesium alloy core-shell composite material, stirring vigorously for 7h to obtain a uniformly dispersed finished reaction solution, carrying out solid forming on the finished reaction solution to obtain a semi-finished product, and drying the semi-finished product under the vacuum condition, wherein the drying temperature is 25 ℃ and the drying time is 48h to obtain the finished product.
Although the invention has been illustrated and described with respect to specific embodiments, it should be appreciated that many other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (10)

1. A preparation method of a reinforced absorbable medical implant material is characterized by comprising the following steps:
s1, cleaning and drying the magnesium alloy;
s2, crushing the magnesium alloy pretreated in the step S1, and performing high-energy ball milling treatment on the crushed magnesium alloy to prepare amorphous nano magnesium alloy powder;
s3, placing the amorphous nano magnesium alloy powder obtained in the step S2 on an object stage of MOCVD equipment, and preparing the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material by adopting a chemical vapor deposition method;
s4, weighing a preset amount of medical implant materials, adding a solvent into the medical implant materials to prepare a solution with a preset proportion, adding a preset amount of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material obtained through the treatment in the step S3 into the solution, and stirring until the mixture is uniformly dispersed to obtain a uniformly dispersed finished product reaction solution;
and S5, carrying out fixing molding and drying treatment on the finished product reaction liquid obtained through the step S4 to obtain a finished product.
2. The method according to claim 1, wherein the magnesium alloy in the step S1 is Mg-5Zn or Mg-3 Zn.
3. The preparation method according to claim 1, wherein the conditions of the high-energy ball milling treatment in step S2 are as follows: under the condition of argon, the temperature is 10-30 ℃, and the mass ratio of the ball materials is (10-120): 1, the rotating speed is 100-400 r/min, and the time is 10-100 h.
4. The method according to claim 1, wherein the precursor A obtained in step S3 by chemical vapor deposition is a methanol solution of calcium lactate, and the precursor B is trimethyl phosphate, wherein the molar ratio of calcium in calcium lactate to phosphorus in trimethyl phosphate is 5: (3-24), the gasification temperature is 200-300 ℃.
5. The preparation method according to claim 1, wherein the process for preparing the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material in step S3 specifically comprises: and introducing oxygen plasma into a chemical vapor deposition chamber of the MOCVD equipment, wherein the deposition temperature is 500-700 ℃, and the deposition times are 10-20.
6. The method for preparing the reinforced absorbable medical implant material of claim 1, wherein the step S4 is performed by mixing one or more of poly (lactic-co-glycolic acid), and poly (glycolic acid) at any ratio.
7. The method for preparing a reinforced absorbable medical implant material as claimed in claim 1, wherein the solvent in step S4 is dichloromethane or N, N-dimethylformamide.
8. The method according to any one of claims 1 to 7, wherein the mass concentration of the implant material for chinese medical science in step S4 is 5% to 10%; in the step S4, the mass concentration of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is 1-15%, wherein the mass concentration of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material is determined by the mass of the calcium phosphate coated amorphous nano magnesium alloy core-shell composite material in the medical implant material.
9. The production method according to any one of claims 1 to 7, wherein the fixing molding manner in step S4 is 3D printing or injection molding.
10. The method according to any one of claims 1 to 7, wherein the drying in step S5 is performed in a vacuum manner at a temperature of 25 to 40 ℃ for 12 to 48 hours.
CN202111457063.6A 2021-12-01 2021-12-01 A kind of preparation method of reinforced absorbable medical implant material Pending CN114191616A (en)

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