CN117085185A - Biodegradable alloy for improving biocompatibility and degradation controllability and preparation method thereof - Google Patents
Biodegradable alloy for improving biocompatibility and degradation controllability and preparation method thereof Download PDFInfo
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- CN117085185A CN117085185A CN202311073026.4A CN202311073026A CN117085185A CN 117085185 A CN117085185 A CN 117085185A CN 202311073026 A CN202311073026 A CN 202311073026A CN 117085185 A CN117085185 A CN 117085185A
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 129
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- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 8
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
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- 150000003904 phospholipids Chemical class 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 1
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 description 1
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- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
-
- 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
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/086—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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
-
- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
Abstract
The invention provides a biodegradable alloy for an intracranial vascular stent, which can improve biocompatibility and degradation controllability and a preparation method thereof. The biodegradable alloy material adopts a multi-layer composite material structure in design and comprises the following structures: cobalt-chromium alloy A layer-phosphorylcholine coating-magnesium alloy B layer surface coating. The cobalt-chromium alloy A and the magnesium alloy B have different alloy compositions, so that the differential degradation rates of the cobalt-chromium alloy A layer and the magnesium alloy B layer are realized, and the degradation rates are respectively adjusted. Through the design of differential degradation rate, different functions and supports can be provided at different stages, and the degradation controllability of the material is realized. Meanwhile, the effect of the coating also improves the biocompatibility.
Description
Technical Field
The invention relates to the field of medical materials, in particular to a biodegradable alloy for improving biocompatibility and degradation controllability and a preparation method thereof.
Background
Medical metal materials are biological materials which are developed at a high speed in recent years, and are more suitable for implantation materials of bearing parts than nonmetallic materials due to the excellent mechanical properties. Medical metal materials commonly used today include stainless steel, titanium alloys, cobalt chromium alloys, noble metals, magnesium alloys, and the like.
Magnesium alloys are widely used as medical metal materials due to their low density, high strength, and ease of machining and welding. Magnesium in a human body is chemically reacted in a solution medium to be converted into magnesium ions, and the magnesium ions regulate balance through in-vivo absorption and kidney metabolism, so that the magnesium alloy material is gradually degraded and absorbed in the human body. The magnesium alloy is the first choice of human body bracket or support and bearing material because of the advantages of good mechanical property, controllable corrosion property, minimal side effect of degradation products and the like. However, magnesium is relatively active in nature and is easily corroded in a human body, namely, the degradation rate is too high, which is a defect that magnesium alloy is applied in the human body, but unlike other metal materials, magnesium is an important element which is necessary for the human body, and the magnesium alloy can be utilized as a material for absorbing and degrading in the human body. In the prior art, many scholars and researchers have studied on magnesium alloys applied to human bodies. In recent years, the cobalt-chromium biological alloy with safe biocompatibility becomes the first choice for non-noble metal porcelain repair of European and American patients. The cobalt-chromium biological porcelain alloy has the characteristics of high hardness, good plasticity, difficult corrosion and the like. Meanwhile, polishing is convenient, and the long bridge and the buckle are not easy to deform. However, the imported cobalt-chromium biological porcelain alloy is relatively expensive and is not easy to be popularized and applied in a large quantity in China. Meanwhile, the compatibility of the degradable cobalt-chromium alloy for the intracranial stent is almost blank in China.
CN101883592a discloses medical devices such as stents coated with calcium phosphate and a process for their manufacture. The scaffold may comprise a cobalt chrome alloy treated to improve surface adhesion with calcium phosphate and/or to improve surface finish properties. The active agent may be present in a calcium phosphate coating.
CN109536782a belongs to the field of precision alloy functional materials, in particular to a medical high-toughness cobalt-chromium alloy; the alloy can be used as an orthopaedics casting alloy, including dental porcelain alloy, porcelain bracket restoring body and the like. The chemical composition comprises 24.0-29.0% of Cr, 4.0% -8.0% of Mo, 1.3-2.0% of Fe, 0.2-0.8% of Ti, 0.1-0.5% of Mn, less than or equal to 0.010% of P, less than or equal to 0.010% of S and the balance of Co by mass. The density of the cobalt-chromium alloy provided by the invention is 8.2g/cm < 3 >; the yield strength is more than or equal to 650MPa, and the highest yield strength can exceed 700MPa; the Vickers hardness is more than or equal to 390kgf/mm < 2 >; the elongation is more than or equal to 18 percent; is higher than the traditional ceramic casting alloy in China by nearly 6 times; meanwhile, the processing performance is good, and the method can be widely applied to the biomedical field.
CN103484845a discloses a preparation method of biodegradable alloy/calcium-phosphorus coating composite material, which comprises a substrate pretreatment step, a conversion liquid preparation step and a bionic calcium-phosphorus coating preparation step, and the biodegradable alloy/calcium-phosphorus coating composite material is prepared. Compared with the prior art, the ZK60 magnesium alloy/calcium-phosphorus coating composite material prepared by the invention can obviously improve the corrosion resistance of the ZK60 magnesium alloy, greatly reduce the degradation rate of the ZK60 magnesium alloy in bionic body fluid and promote the research and application of the ZK60 magnesium alloy in the medical field.
CN108581392a discloses a preparation method and application of a biomedical degradable alloy surface fine-grain composite layer, which comprises the following steps: polishing and chemically cleaning the magnesium alloy substrate; cold spraying nano hydroxyapatite powder on the surface of the magnesium alloy substrate to obtain a nano hydroxyapatite coating; and (3) carrying out friction stir processing on the surface of the magnesium alloy substrate with the nano hydroxyapatite coating to form a nano hydroxyapatite-fine crystal composite structure on the surface of the magnesium alloy. The invention successfully prepares the nano hydroxyapatite-fine crystal composite tissue layer on the surface of the magnesium alloy based on the high-efficiency and rapid cold spray coating preparation technology and the friction stir processing technology, has the advantages of reasonable process, low cost, high efficiency, environmental protection and the like, can effectively improve the corrosion resistance of the biomedical degradable alloy, has excellent cell affinity and bone function, can regulate and control the biomedical function of osteoblasts, improves the osseointegration capability, and has wide application prospect in the medical fields such as orthopedics implantation and the like.
CN111593279a discloses a method for controlling degradation rate of medical magnesium-based material composite biological coating, which prepares medical magnesium-based material composite biological coating with different degradation rates by changing 6 technological parameters affecting degradation rate, wherein the 6 technological parameters are laser energy, shot blasting temperature, laser shot blasting times, current density, processing time and electrolyte concentration, the 6 technological parameters are used as input layer, degradation rate is used as output layer, and a BP neural network optimized by genetic algorithm is used for network training, so as to obtain a BP neural network prediction model with smaller error. The invention has good intelligent characteristics, greatly simplifies the prediction and control process of degradation rate, and saves manpower, material resources and financial resources. Effectively improves the corrosion resistance and mechanical property of the medical alloy implant material and provides possibility for the wide use of the medical magnesium alloy implant material.
In the prior art, a certain study is made for improving the performance of the biological alloy, in particular important biocompatibility and degradability. However, the research on magnesium and cobalt-chromium alloy for intracranial vascular stents has the defects of good biocompatibility and degradability, and the clinical application of the current magnesium and magnesium alloy is limited. Therefore, development of a biodegradable alloy with improved biocompatibility and degradation controllability and a preparation method thereof are needed.
Disclosure of Invention
The invention provides the biodegradable alloy for intracranial vascular stents, which has good comprehensive performance, controllable degradation and high biocompatibility, and aims to solve the problems of insufficient biocompatibility and degradation controllability of the existing biodegradable alloy.
Biocompatibility and degradation controllability are two key performance characteristics of biodegradable alloys in biomedical applications, which are critical to ensure that the material functions safely and effectively in the human body. The inventors have modified the alloy for intracranial vascular stents in the present invention mainly for the two properties described above. Specifically, the inventors used the following mechanism:
the bio-alloy material is designed to be a multi-layer composite material structure, for example, at least comprises the following structures: the inventor finds that the composite material layer structure can effectively increase the comprehensive performance of the biological alloy, in particular to biocompatibility and degradation controllability.
The invention is an effective step for improving biocompatibility by coating phosphorylcholine coating on the surface of cobalt-chromium alloy A. Phosphorylcholine is one of the main components of human intracranial bone tissue and has good biological activity. By coating the phosphorylcholine coating, a bionic phosphorus base structure can be formed on the surface of the material, which is beneficial to enhancing the interaction and integration of the material with surrounding blood vessels and blood tissues. The structure is beneficial to promoting the growth of new-born intracranial blood vessels and blood bone cells and the reconstruction of intracranial bone, thereby improving the biocompatibility of the material in medical applications such as intracranial bone fixation and the like. In particular for alloy materials used for intracranial vascular stents, phosphorylcholine coatings have a critical effect on improving the biological intracranial biocompatibility of the alloy material.
Meanwhile, the introduction of a bioactive coating on the surface of the magnesium alloy B is also an important means for improving biocompatibility. Bioactive coatings, such as calcium hydrogen phosphate silicate (Si-HA), can increase the bioactivity of the material surface and promote proliferation and differentiation of intracranial vascular endothelial cells. This facilitates better integration of the material with the surrounding tissue, improving the biocompatibility of the implant material.
In the invention, cobalt-chromium alloy A and magnesium alloy B with different compositions are used, and the design of a sandwich structure is key to the realization of the degradation controllability of the magnesium alloy. The differential degradation rate of the cobalt-chromium alloy A and the magnesium alloy B is realized by respectively adjusting the degradation rate through the different alloy compositions of the cobalt-chromium alloy A and the magnesium alloy B. Magnesium alloy B is designed as a material with a slower degradation rate, providing long-term support and stability (later persistence). Cobalt chrome alloy a, however, is designed to degrade faster, providing better conditions for initial tissue healing (early suitability). Through the design of differential degradation rate, different functions and supports can be provided at different stages, and the degradation controllability of the material is realized.
Meanwhile, compared with the prior art, the multi-layer composite structure provided by the invention also has the following advantages: the phosphorylcholine coating and the surface coating improve the biocompatibility and influence the degradation controllability of the alloy. The phosphorylcholine coating forms a stable bionic alkaline phosphorus structure on the surface of the material, and the structure can slow down the degradation rate of the material. The presence of a surface coating, such as a calcium hydrogen silicate, helps to promote initial degradation of the surface of the material and increases the relative degradation rate of the material at an initial stage. Through the design, the degradation rate of the material can be adjusted, and the controllability of the degradation process is realized.
Advantages of the present invention include, but are not limited to, synergy between the multiple layers of composite material. For example, phosphorylcholine coating and cobalt chromium alloy a: the synergistic effect between the phosphorylcholine coating and the cobalt-chromium alloy A enables the surface of the material to form a bionic alkaline-phosphorus structure, which is beneficial to enhancing the interaction with intracranial peripheral blood vessels and blood tissues. Such a structure provides good support and guidance for the growth and vascular remodeling of new intracranial vascular endothelial cells. Meanwhile, the cobalt-chromium alloy A has excellent mechanical properties, so that stable support can be provided for intracranial blood vessels and blood tissues. The synergistic effect helps to achieve long-term stability and good therapeutic effect of the degradable alloy in medical applications such as aneurysm treatment. Simultaneous synergy also includes, but is not limited to, a surface coating with magnesium alloy B: the interaction between the surface coating and the magnesium alloy B ensures that the surface of the material has better biological activity and promotes proliferation and differentiation of intracranial vascular endothelial cells. This aids in enhancing the interaction and integration of the material with the surrounding tissue. Meanwhile, the cobalt-chromium alloy A is used as a material with a relatively rapid degradation rate, so that better conditions can be provided for tissue healing in the early stage, and the formation of a new tissue is promoted. The synergistic effect of the magnesium alloy B ensures that the material has better biocompatibility in the initial stage, ensures the controllable degradation of the material and avoids the material failure caused by the excessively rapid degradation.
The synergistic effect of degradation controllability includes phosphorylcholine coating and cobalt chromium alloy a: the phosphorylcholine coating forms a stable bionic alkaline phosphorus structure on the surface of the cobalt-chromium alloy A, which is helpful for slowing down the degradation rate of the material. Meanwhile, the cobalt-chromium alloy A is a material with a slower degradation rate, and long-term stability and support are provided. The synergistic effect enables the material to continuously and stably provide mechanical support in vivo, and meanwhile, the degradation rate is moderate, and failure caused by excessively rapid degradation is avoided. Synergism also includes surface coating with magnesium alloy B: the presence of the surface coating helps to accelerate the degradation of the surface of the material, increasing the degradation rate of the material. Meanwhile, the magnesium alloy B is used as a material with a rapid degradation rate, and provides better tissue healing conditions in the early stage. The synergistic effect ensures that the material is rapidly degraded in the early stage, is beneficial to the healing and reconstruction of tissues, can be gradually degraded in the later stage, and avoids instability and adverse reaction caused by excessively rapid degradation.
In summary, the synergy and interaction between the multi-layer composite structures has a positive impact on the biocompatibility and degradation controllability of the degradable alloy. Through careful design and optimization of the multi-layer composite structure, different functions and supports of the material can be provided at different stages, the excellent performance of the material is exerted to the greatest extent, and better performance and effect are brought to the degradable alloy in medical application.
Specifically, a first aspect of the present invention provides a biodegradable alloy with improved biocompatibility and degradation controllability, characterized in that: the biodegradable alloy comprises the following structures from bottom to top:
the cobalt-chromium alloy A layer comprises the following components: 60-70% Co-20-25% Cr-the balance Mo;
a phosphorylcholine coating layer coated on the surface of the cobalt-chromium alloy a layer;
the magnesium alloy B layer comprises the following components: the balance of Mg-2.0-5.0% Ca-0.1-1.0% Sr-0.1-1.0% Si, and the magnesium alloy B layer is coated on the surface of the phosphorylcholine coating; and
and a surface coating layer coated on the surface of the magnesium alloy B layer.
In some embodiments, the biodegradable alloy comprises a cobalt-chromium alloy layer a: phosphorylcholine coating: magnesium alloy layer B: surface coating = 40-49%:10-20%:30-39%:1-10%.
In some embodiments, the composition of the surface coating comprises calcium hydrogen phosphate silicate (Si-HA).
A second aspect of the present invention provides a biodegradable alloy having improved biocompatibility and degradation controllability, characterized in that: the biodegradable alloy comprises the following structures from bottom to top:
the cobalt-chromium alloy A layer comprises the following components: 60-70% Co-20-25% Cr-the balance Mo;
a phosphorylcholine coating layer coated on the surface of the cobalt-chromium alloy a layer;
the magnesium alloy B layer comprises the following components: the balance of Mg-2.0-5.0% Ca-0.1-1.0% Sr-0.1-1.0% Si, and the magnesium alloy B layer is coated on the surface of the phosphorylcholine coating; and
and a surface coating layer coated on the surface of the magnesium alloy B layer.
In some embodiments, the biodegradable alloy comprises a cobalt-chromium alloy layer a: phosphorylcholine coating: magnesium alloy layer B: surface coating = 40-49%:10-20%:30-39%:1-10%.
In some embodiments, the composition of the surface coating comprises calcium hydrogen phosphate silicate (Si-HA).
The second aspect of the present invention provides a method for preparing a biodegradable alloy having improved biocompatibility and degradation controllability, comprising the steps of:
1) Preparing a cobalt-chromium alloy A layer;
2) The phosphorylcholine coating is coated on the surface of the cobalt-chromium alloy A layer;
3) The magnesium alloy B layer is coated on the surface of the phosphorylcholine coating;
4) The surface coating is coated on the surface of the magnesium alloy B layer.
In some embodiments, the step of applying the phosphorylcholine coating to the surface of the cobalt-chromium alloy a layer comprises:
step 1: surface treatment of a substrate of the cobalt-chromium alloy A layer: removing oxides and impurities on the surface, and cleaning;
step 2: coating a phosphorylcholine coating: hydroxylating the alloy, namely treating the obtained alloy by using a sodium hydroxide alkaline solution, wherein the concentration range of the sodium hydroxide is 5% -50%, the treatment time is 30 min-5 h, and the treatment temperature is 30-80 ℃;
step 3: silanization: the gamma-aminopropyl triethoxy silane is used for treating the alloy, and the solvent of the silane consists of water, absolute ethyl alcohol and glacial acetic acid according to the following proportion: 1-10% of silane, 5-50% of absolute ethyl alcohol, 20-80% of water and 0-5% of glacial acetic acid, and hydrolyzing after the silane solution is prepared, wherein the hydrolysis time is 1-6 h, the hydrolysis temperature is 25-50 ℃, and the silane solution is dried in a drying oven after the hydrolysis is finished, wherein the drying temperature is 50-120 ℃ and the drying time is 30 min-2 h;
step 4: post-treatment: after coating, carrying out post-treatment on the alloy;
in some embodiments, the post-processing includes: sintering or heat treatment at 500-1000 deg.c for 1-5 hr.
In some embodiments, the step of coating the magnesium alloy B layer on the surface of the phosphorylcholine coating comprises melting the prepared magnesium alloy and coating the magnesium alloy B layer on the surface of the phosphorylcholine coating by thermal spraying.
In some embodiments, the thermal spray rate is 10-40g/s.
In some embodiments, the step of applying a surface coating to the surface of the magnesium alloy B layer comprises:
pretreatment of a magnesium alloy B layer: comprises surface impurity removal and polishing.
Preparing a coating solution: mixing proper amount of silicic acid and calcium hydrophosphate in deionized water, and stirring and mixing under proper conditions to form a coating solution containing Si-HA;
the coating process comprises the following steps: immersing the biodegradable alloy substrate subjected to surface treatment in a Si-HA coating solution to fully impregnate the biodegradable alloy substrate, taking out the impregnated alloy, and depositing Si-HA compounds in the solution on the surface of the alloy to form a coating by drying or heat treatment;
sintering or heat treatment: after coating, sintering or heat treating the alloy;
surface treatment: after coating the Si-HA, the coating is subjected to further surface treatments including sanding and polishing to improve the smoothness and overall quality of the coating.
In some embodiments, the sintering or heat treatment is at a temperature in the range of 500-1000 ℃ for a time in the range of 1-5 hours.
In some embodiments, the method of preparing the magnesium alloy B layer includes:
1) And (3) melt casting: fully adding each metal powder into a melting bag according to the required proportion in a closed container, controlling the temperature to be 700-800 ℃ for melting, blowing argon for stirring, casting and cooling;
2) And (3) heat treatment: heating the alloy obtained by casting, controlling the temperature to be 200-250 ℃, annealing for 1-5min, and cooling;
3) Hot extrusion: placing the alloy after heat treatment into a hot extrusion die, controlling the temperature to be 250-300 ℃, controlling the extrusion rate to be 2-5mm/s, and setting the extrusion ratio to be 10-15:1;
4) And (3) rolling and forming: rolling at 320-350 deg.c at speed of 20-30m/min and pressing amount of 50-80% to obtain the magnesium alloy matrix.
In some embodiments, the rolling is complete, and a heat treatment process can be further performed as needed.
In some embodiments, the preheating is performed prior to rolling for no more than 10 minutes.
In some embodiments, the rolling pass is no more than 10 times.
In some embodiments, the argon stirring is by blowing argon from a gas port in the bottom of the ladle during the melt casting.
In some embodiments, the cobalt-chromium alloy a layer is prepared using a melt casting process.
The technical effects obtained by the invention include the following:
in the multi-layer composite biodegradable alloy for the intracranial vascular stent, the cobalt-chromium alloy A is obtained by optimizing the composition proportion and the structure of alloy elements, has slower degradation rate, and has better mechanical property and biocompatibility. This layer provides long-term support and stability. The surface of cobalt-chromium alloy A is coated with phosphorylcholine coating to enhance the integration with intracranial peripheral blood vessels and blood tissues. The phosphorylcholine coating has good biological activity and biocompatibility. The magnesium alloy B is Mg-Ca-Sr-Si, and the degradation rate of the alloy B is high by adding Sr and Si elements, so that the healing and reconstruction of surrounding tissues are promoted; and the bionic structure can improve the proliferation of the neointima of the blood vessel, reduce the thrombosis and accelerate the repair and reconstruction of the lesion blood vessel. This layer provides support and directs the healing process at the beginning of the biomaterial. A bioactive coating, such as calcium hydrogen phosphate silicate (Si-HA), is introduced on the surface of magnesium alloy B to further promote the healing process. The composition of the calcium hydrophosphate coating is Si-HA, which is helpful for proliferation and differentiation of intracranial vascular endothelial cells.
The design of the multi-layer composite material of the invention enables the degradable alloy biological material to provide different functions and supports at different stages. The various coatings play different roles and the synergistic effect between the layers has a positive effect on the overall properties of the biodegradable alloy.
Drawings
FIG. 1 is a schematic structural view of a multi-layered composite biodegradable alloy material according to the present invention.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar modules or modules having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the description of the present specification, reference to the term "one embodiment," "another embodiment," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
[ biocompatibility ]
Biocompatibility means that the biological material, when contacted with an organism, does not cause significant toxicity, irritation or immune response, but is well compatible and synergistic with surrounding tissues. The excellent biocompatibility of the biodegradable alloy means that it can well interact with surrounding biological tissues while being implanted in the body, minimizing foreign body reactions and immune rejection.
In medical applications such as nerve and cardiovascular stents, particularly in intracranial vascular stents, the biodegradable alloy is in direct contact with blood and vascular wall biological tissues, which may lead to adverse consequences such as inflammatory reactions, tissue necrosis or thrombosis if the material does not have good biocompatibility. The material with excellent biocompatibility can effectively promote the formation and healing of new tissues, and is beneficial to realizing the seamless connection of the material and the tissues, thereby improving the treatment effect and the rehabilitation speed of patients.
[ degradation controllability ]
Degradation controllability means that the biodegradable alloy can be gradually degraded in a human body at a certain rate, and simultaneously release beneficial ions or compounds, and finally be metabolized and discharged out of the body. This property is particularly important for biodegradable alloys, as it ensures the controllability and stability of the material during implantation in vivo.
If the degradation rate of the biodegradable alloy is too high, the material may lose necessary mechanical support at critical time, and the rehabilitation of the patient may be affected. Conversely, if the degradation rate is too slow, the material may be implanted in the body for too long, increasing the risk and cost of secondary surgery. Thus, ensuring a controllable degradation rate of the biodegradable alloy is critical for successful application of the material in medical applications.
Degradation controllability also helps to ensure the safety of the material degradation products. When the biodegradable alloy is gradually degraded, magnesium, calcium and other ions are released, and the ions have positive effects on the physiological functions of human bodies and the growth of blood vessels and blood tissues for intracranial vascular stents. However, excessive release of these ions may also cause adverse reactions. Therefore, by controlling the degradation rate of the material, a proper amount of ion release can be ensured, and excessive adverse reaction is avoided.
In summary, biocompatibility and degradation controllability are important factors for the performance of biodegradable alloys, which determine the safety, effectiveness and stability of the materials in medical applications. By ensuring that the material has good biocompatibility and controllable degradability, the biodegradable alloy can become an ideal medical material, and provides better treatment effect and health benefit for patients.
[ phosphorylcholine coating ]
Phosphorylcholine coating (phosphotidyline) is a phospholipid, which is one of the most common phospholipid molecules. It is a molecule consisting of glycerol, phosphoric acid, choline and two fatty acid residues. Phosphorylcholine, which is widely present in organisms, particularly in cell membranes, is one of the major components of the phospholipid bilayer of cell membranes.
Phosphorylcholine plays a variety of important biological functions in organisms. One of the important functions is as one of the major structural components of the cell membrane, which helps to maintain the stability and integrity of the cell membrane. In addition, phosphorylcholine plays an important role in bile, contributing to metabolism and transport of cholesterol. It is also considered to be a precursor substance for the synthesis of the neurotransmitter acetylcholine, which is critical for the neurotransmission process. In summary, phosphorylcholine has a number of important biological functions in organisms, involving cell membrane structures, metabolic processes, neurotransmitter synthesis, and the like.
A phosphorylcholine coating is a coating on the surface of the biodegradable alloy of the present invention, wherein phosphorylcholine molecules are used as one of the main components. Such coatings are commonly used to improve the surface properties and performance of materials, and have a variety of applications, particularly in biomedical, drug delivery, material science, and the like.
Description figure 1 is a schematic diagram of a multi-layer composite structure of a biodegradable alloy of the present invention with enhanced biocompatibility and degradation controllability. The surface coating is sequentially formed by a cobalt-chromium alloy A layer, a phosphorylcholine coating, a magnesium alloy B layer and a surface coating from bottom to top, namely from the near end to the far end of a tissue organ of a receptor.
Embodiments of the present invention are as follows.
Example 1:
a biodegradable alloy for improving biocompatibility and degradation controllability and a preparation method thereof are as follows:
melting and casting to obtain a cobalt-chromium alloy layer A matrix, carrying out surface treatment, removing oxides and impurities on the surface, and cleaning; treating the alloy obtained by using a sodium hydroxide alkaline solution, wherein the concentration range of the sodium hydroxide is 10%, the treatment time is 1h, and the treatment temperature is 30 ℃; treating the alloy with gamma-aminopropyl triethoxy silane, wherein the solvent of the silane consists of water, absolute ethyl alcohol and glacial acetic acid according to the following proportion: 10% of silane, 10% of absolute ethyl alcohol, 1% of glacial acetic acid and the balance of water, wherein the silane solution is hydrolyzed after being prepared, the hydrolysis time is 1h, the hydrolysis temperature is 25 ℃, and the silane solution is dried in a drying oven after being hydrolyzed, the drying temperature is 120 ℃ and the drying time is 2h; then, taking out the impregnated cobalt-chromium alloy A layer substrate, and depositing a phosphorylcholine compound in the solution on the surface of the substrate to form a coating through heat treatment at 650 ℃; melting the magnesium alloy B layer matrix obtained by casting, connecting the molten magnesium alloy B layer matrix into a high-temperature metal liquid pump, controlling the spraying rate to be 30g/s, and coating the magnesium alloy B layer on the surface of the phosphorylcholine coating; cleaning and polishing the surface of the magnesium alloy B layer again, mixing a proper amount of silicic acid and calcium hydrophosphate in deionized water, and stirring and mixing under proper conditions to form a coating solution; immersing the surface-treated alloy into a Si-HA coating solution to fully impregnate the alloy, then taking out the impregnated alloy, depositing Si-HA compound in the solution on the surface of a substrate to form a surface coating by drying, and sintering the obtained alloy structure at 800 ℃ after coating. Through the steps, the biodegradable alloy with improved biocompatibility and degradation controllability is obtained, and the composition of the biodegradable alloy is 45% cobalt-chromium alloy A (70% Co-25% Cr-5% Mo) -15% phosphorylcholine coating-35% magnesium alloy B (balance Mg-2.0% Ca-1.0% Sr-1.0% Si) -5% calcium silicon hydrogen phosphate surface coating.
Example 2:
a biodegradable alloy for improving biocompatibility and degradation controllability and a preparation method thereof are as follows:
melting and casting to obtain a cobalt-chromium alloy layer A matrix, carrying out surface treatment, removing oxides and impurities on the surface, and cleaning; treating the alloy obtained by using a sodium hydroxide alkaline solution, wherein the concentration range of the sodium hydroxide is 10%, the treatment time is 1h, and the treatment temperature is 30 ℃; treating the alloy with gamma-aminopropyl triethoxy silane, wherein the solvent of the silane consists of water, absolute ethyl alcohol and glacial acetic acid according to the following proportion: 10% of silane, 10% of absolute ethyl alcohol, 1% of glacial acetic acid and the balance of water, wherein the silane solution is hydrolyzed after being prepared, the hydrolysis time is 1h, the hydrolysis temperature is 25 ℃, and the silane solution is dried in a drying oven after being hydrolyzed, the drying temperature is 120 ℃ and the drying time is 2h; then, taking out the impregnated cobalt-chromium alloy A layer substrate, and depositing a phosphorylcholine compound in the solution on the surface of the substrate to form a coating through heat treatment at 650 ℃; melting the magnesium alloy B layer matrix obtained by casting, connecting the molten magnesium alloy B layer matrix into a high-temperature metal liquid pump, controlling the spraying rate to be 35g/s, and coating the magnesium alloy B layer on the surface of the phosphorylcholine coating; cleaning and polishing the surface of the magnesium alloy B layer again, mixing a proper amount of silicic acid and calcium hydrophosphate in deionized water, and stirring and mixing under proper conditions to form a coating solution; immersing the alloy substrate subjected to surface treatment into a Si-HA coating solution to fully impregnate the alloy substrate, then taking out the impregnated alloy, depositing Si-HA compound in the solution on the surface of the substrate by drying to form a surface coating, and sintering the obtained alloy structure at 830 ℃ after coating is finished. Through the steps, the biodegradable alloy with improved biocompatibility and degradation controllability is obtained, and the composition of the biodegradable alloy is 45% cobalt-chromium alloy A (70% Co-25% Cr-5% Mo) -17% phosphorylcholine coating-30% magnesium alloy B (balance Mg-2.0-5.0% Ca-0.1-1.0% Sr-0.1-1.0% Si) -8% calcium hydrogen phosphate surface coating.
Example 3:
a biodegradable alloy for improving biocompatibility and degradation controllability and a preparation method thereof are as follows:
melting and casting to obtain a cobalt-chromium alloy layer A matrix, carrying out surface treatment, removing oxides and impurities on the surface, and cleaning; treating the alloy obtained by using a sodium hydroxide alkaline solution, wherein the concentration range of the sodium hydroxide is 10%, the treatment time is 1h, and the treatment temperature is 30 ℃; treating the alloy with gamma-aminopropyl triethoxy silane, wherein the solvent of the silane consists of water, absolute ethyl alcohol and glacial acetic acid according to the following proportion: 10% of silane, 10% of absolute ethyl alcohol, 1% of glacial acetic acid and the balance of water, wherein the silane solution is hydrolyzed after being prepared, the hydrolysis time is 1h, the hydrolysis temperature is 25 ℃, and the silane solution is dried in a drying oven after being hydrolyzed, the drying temperature is 120 ℃ and the drying time is 2h; then, taking out the impregnated cobalt-chromium alloy A layer substrate, and depositing a phosphorylcholine compound in the solution on the surface of the substrate to form a coating through heat treatment at 650 ℃; melting the magnesium alloy B layer matrix obtained by casting, connecting the molten magnesium alloy B layer matrix into a high-temperature metal liquid pump, controlling the spraying rate to be 30g/s, and coating the magnesium alloy B layer on the surface of the phosphorylcholine coating; cleaning and polishing the surface of the magnesium alloy B layer again, mixing a proper amount of silicic acid and calcium hydrophosphate in deionized water, and stirring and mixing under proper conditions to form a coating solution; immersing the magnesium alloy substrate subjected to surface treatment into a Si-HA coating solution to fully impregnate the magnesium alloy substrate, then taking out the impregnated magnesium alloy, depositing Si-HA compound in the solution on the surface of the substrate by drying to form a surface coating, and sintering the obtained magnesium alloy structure at 800 ℃ after coating is completed. The biodegradable alloy with improved biocompatibility and degradation controllability is obtained through the steps, and the composition of the biodegradable alloy is 43% cobalt-chromium alloy A (63% Co-20% Cr-17% Mo) -16% phosphorylcholine coating-35% magnesium alloy B (balance Mg-2.0-5.0% Ca-0.1-1.0% Sr-0.1-1.0% Si) -6% calcium hydrogen phosphate surface coating.
Example 4:
a biodegradable alloy for improving biocompatibility and degradation controllability and a preparation method thereof are as follows:
melting and casting to obtain a cobalt-chromium alloy layer A matrix, carrying out surface treatment, removing oxides and impurities on the surface, and cleaning; treating the alloy obtained by using a sodium hydroxide alkaline solution, wherein the concentration range of the sodium hydroxide is 10%, the treatment time is 1h, and the treatment temperature is 30 ℃; treating the alloy with gamma-aminopropyl triethoxy silane, wherein the solvent of the silane consists of water, absolute ethyl alcohol and glacial acetic acid according to the following proportion: 10% of silane, 10% of absolute ethyl alcohol, 1% of glacial acetic acid and the balance of water, wherein the silane solution is hydrolyzed after being prepared, the hydrolysis time is 1h, the hydrolysis temperature is 25 ℃, and the silane solution is dried in a drying oven after being hydrolyzed, the drying temperature is 120 ℃ and the drying time is 2h; then, taking out the impregnated cobalt-chromium alloy A layer substrate, and depositing a phosphorylcholine compound in the solution on the surface of the substrate to form a coating through heat treatment at 650 ℃; melting the magnesium alloy B layer matrix obtained by casting, connecting the molten magnesium alloy B layer matrix into a high-temperature metal liquid pump, controlling the spraying rate to be 30g/s, and coating the magnesium alloy B layer on the surface of the phosphorylcholine coating; cleaning and polishing the surface of the magnesium alloy B layer again, mixing a proper amount of silicic acid and calcium hydrophosphate in deionized water, and stirring and mixing under proper conditions to form a coating solution; immersing the alloy substrate subjected to surface treatment into a Si-HA coating solution to fully impregnate the alloy substrate, then taking out the impregnated alloy, depositing Si-HA compound in the solution on the surface of the substrate by drying to form a surface coating, and sintering the obtained magnesium alloy structure at 780 ℃ after coating is finished. Through the steps, the biodegradable alloy with improved biocompatibility and degradation controllability is obtained, and the composition of the biodegradable alloy is 41% cobalt-chromium alloy A (70% Co-25% Cr-5% Mo) -17% phosphorylcholine coating-33% magnesium alloy B (balance Mg-4.0% Ca-1.0% Sr-1.0% Si) -9% calcium silicon hydrogen phosphate surface coating.
Comparative example 1: comparative example 1 was obtained from example 1 of prior art CN114561579 a.
Comparative example 2: comparative example 2 was obtained with the sample of example 1 of the prior art CN114990370 a.
The above examples and comparative examples were evaluated for biocompatibility using a cell count kit according to the ISO10993-5 standard.
The degradation rate was evaluated according to the soak test (alloy samples were soaked in simulated body fluids (Simulated Body Fluid, SBF), samples were taken periodically, and mass changes and surface morphology changes were measured.
The test structures of all examples and comparative examples are shown in the following table.
TABLE 1 biocompatibility test results
The biodegradable alloys obtained in examples 1 to 4 and comparative examples 1 and 2 were prepared into bars, each bar was prepared by immersing a material having a thickness of 1mm and a diameter of 10mm in 37% physiological saline to simulate degradation of body fluid in a human body, and the simulation test results (variation in diameter reduction of samples) are shown in the following table:
TABLE 2 degradation rate
TABLE 3 mechanical Properties
| Sample of | Tensile strength MPa | Yield strength MPa | Elongation percentage |
| Example 1 | 361 | 332 | 21 |
| Example 2 | 359 | 294 | 22 |
| Example 3 | 344 | 265 | 21 |
| Example 4 | 353 | 299 | 21 |
The mechanical property test results of the samples of the embodiments 1-4 of the invention are shown in Table 3, and also show that the mechanical properties of the biodegradable alloy of the invention can meet the mechanical property requirements of the biological implant while improving the biocompatibility and degradation controllability.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A biodegradable alloy for improving biocompatibility and degradation controllability, characterized in that: the biodegradable alloy comprises the following structures from bottom to top:
the cobalt-chromium alloy A layer comprises the following components: 60-70% Co-20-25% Cr-the balance Mo;
a phosphorylcholine coating layer coated on the surface of the cobalt-chromium alloy a layer;
the magnesium alloy B layer comprises the following components: the balance of Mg-2.0-5.0% Ca-0.1-1.0% Sr-0.1-1.0% Si; and
and a surface coating layer coated on the surface of the magnesium alloy B layer.
2. The biodegradable alloy according to claim 1, wherein the mass ratio between layers is cobalt-chromium alloy a layer: phosphorylcholine coating: magnesium alloy layer B: surface coating = 40-49%:10-20%:30-39%:1-10%.
3. The biodegradable alloy of claim 1, the composition of the surface coating comprising calcium hydrogen phosphate silicate (Si-HA).
4. A method of preparing a biodegradable alloy of any one of claims 1-5 having improved biocompatibility and degradation controllability, comprising the steps of:
1) Preparing a cobalt-chromium alloy A layer;
2) The phosphorylcholine coating is coated on the surface of the cobalt-chromium alloy A layer;
3) The magnesium alloy B layer is coated on the surface of the phosphorylcholine coating;
4) The surface coating is coated on the surface of the magnesium alloy B layer.
5. The biodegradable alloy of claim 1, the step of applying the phosphorylcholine coating to a surface of a cobalt-chromium alloy a layer comprising:
step 1: surface treatment of a substrate of the cobalt-chromium alloy A layer: removing oxides and impurities on the surface, and cleaning;
step 2: coating a phosphorylcholine coating: hydroxylating the alloy, namely treating the obtained alloy by using a sodium hydroxide alkaline solution, wherein the concentration range of the sodium hydroxide is 5% -50%, the treatment time is 30 min-5 h, and the treatment temperature is 30-80 ℃;
step 3: silanization: the gamma-aminopropyl triethoxy silane is used for treating the alloy, and the solvent of the silane consists of water, absolute ethyl alcohol and glacial acetic acid according to the following proportion: 1-10% of silane, 5-50% of absolute ethyl alcohol, 20-80% of water and 0-5% of glacial acetic acid, and hydrolyzing after the silane solution is prepared, wherein the hydrolysis time is 1-6 h, the hydrolysis temperature is 25-50 ℃, and the silane solution is dried in a drying oven after the hydrolysis is finished, wherein the drying temperature is 50-120 ℃ and the drying time is 30 min-2 h;
step 4: post-treatment: after the coating is completed, the alloy is subjected to post-treatment.
6. The method for preparing biodegradable alloy according to claim 6, wherein the step of coating the magnesium alloy B layer on the surface of the phosphorylcholine coating comprises melting the prepared magnesium alloy B layer, and coating the melted magnesium alloy B layer on the surface of the phosphorylcholine coating by thermal spraying.
7. The method for producing a biodegradable alloy according to claim 7, wherein the thermal spraying rate is 10-40g/s.
8. The biodegradable alloy according to claim 6, wherein the step of applying a surface coating on the surface of the magnesium alloy B layer comprises:
1) Pretreatment of a magnesium alloy B layer: comprises surface impurity removal and polishing.
2) Preparing a coating solution: a coating solution containing Si-HA was prepared. Typically, a suitable amount of silicic acid and dibasic calcium phosphate are mixed in deionized water and stirred and mixed under suitable conditions to form a coating solution;
3) The coating process comprises the following steps: immersing the surface-treated biodegradable alloy in a Si-HA coating solution to fully impregnate the biodegradable alloy, then taking out the impregnated alloy, and depositing Si-HA compounds in the solution on the surface of the alloy to form a coating by drying or heat treatment;
4) Sintering or heat treatment: after coating, sintering or heat treating the alloy;
5) Surface treatment: after coating the Si-HA, the coating is subjected to further surface treatment including grinding and polishing to improve the smoothness and overall quality of the coating.
9. The method for producing a biodegradable alloy according to claim 9, wherein the temperature range of sintering or heat treatment is 500-1000 ℃ and the time range is 1-5 hours.
10. A biodegradable alloy according to any one of claims 1-3 for use in intracranial vascular stents, having improved biocompatibility and degradability controllability.
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