CN116983484A - Degradable copper-based shape memory alloy vascular stent and preparation method thereof - Google Patents
Degradable copper-based shape memory alloy vascular stent and preparation method thereof Download PDFInfo
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- CN116983484A CN116983484A CN202311246609.2A CN202311246609A CN116983484A CN 116983484 A CN116983484 A CN 116983484A CN 202311246609 A CN202311246609 A CN 202311246609A CN 116983484 A CN116983484 A CN 116983484A
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- 239000010949 copper Substances 0.000 title claims abstract description 94
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 230000002792 vascular Effects 0.000 title claims abstract description 48
- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 68
- 239000000956 alloy Substances 0.000 claims abstract description 60
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 58
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- 239000007943 implant Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
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- QBOMBCGAEZXOSM-UHFFFAOYSA-N [Si].[Zn].[Cu] Chemical compound [Si].[Zn].[Cu] QBOMBCGAEZXOSM-UHFFFAOYSA-N 0.000 description 14
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- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- HLXZNVUGXRDIFK-UHFFFAOYSA-N nickel titanium Chemical compound [Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ti].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni].[Ni] HLXZNVUGXRDIFK-UHFFFAOYSA-N 0.000 description 1
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- 230000008733 trauma Effects 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/148—Materials at least partially resorbable by the body
-
- 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
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/04—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire
- B21C37/047—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of bars or wire of fine wires
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- 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
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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
- 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
- A61L2300/602—Type of release, e.g. controlled, sustained, slow
- A61L2300/604—Biodegradation
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- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Mechanical Engineering (AREA)
- Epidemiology (AREA)
- Vascular Medicine (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a degradable copper-based shape memory alloy vascular stent and a preparation method thereof, and relates to the technical field of medical appliances. The copper-based shape memory alloy material comprises 15-42 wt% of Zn, 0-10 wt% of Si and the balance of Cu according to mass percent. The preparation method comprises the following steps: and (3) mixing the selected metal powder, placing the mixture into a high-purity graphite crucible, smelting in a vacuum smelting furnace, forming an alloy cast ingot, and cooling along with the furnace. And heating the cast ingot to be molten, and drawing the molten metal for multiple times to obtain the copper-based alloy implant material wire. Weaving a metal wire into a shape required by a stent, performing two-step heat treatment and electrochemical polishing to obtain a vascular stent; the copper-based alloy shape memory alloy material has the unique advantages of biodegradability, good mechanical property, excellent shape memory effect and superelasticity and the like, and can meet the basic requirements of vascular stents.
Description
Technical Field
The invention relates to the technical field of medical equipment, in particular to a degradable copper-based shape memory alloy vascular stent and a preparation method thereof.
Background
With the increasing life expectancy and aging population of humans, vascular diseases such as atherosclerosis, hemangiomas and interlayer threats will become exacerbated over time. Besides the traditional drug treatment, the intravascular stent can play roles of supporting and guiding blood flow, and is widely applied to the treatment of cardiovascular diseases, cerebrovascular diseases, vascular trauma, vascular defects and other diseases due to the good performance of the intravascular stent in the aspect of vascular reconstruction. However, conventional non-degradable metallic stents remain in the patient for the life after treatment, and users must take anticoagulants, etc. for a long period of time. These characteristics of non-degradable stents determine their limitations of use and the potential safety hazards present.
The stent effect exerted by the stent on the vessel after the first 6-12 months of arterial remodeling and healing is considered unnecessary. Bioabsorbable stents can provide mechanical support early and be gradually absorbed within 1-2 years, thereby reducing or even eliminating adverse effects such as thrombus and restenosis within the stent. Biodegradable polymers such as biodegradable metals made of iron, magnesium or zinc and polylactic acid are suitable candidates for bioabsorbable stents. Because the mechanical properties of the polymer material are limited, the defects of low radial supporting force, too thick wall thickness and the like of the polymer material cannot be overcome at present. The biodegradable metal stent has excellent mechanical properties, wherein the corrosion degradation rate of the zinc alloy stent is moderate, and the requirement of maintaining the vascular supporting effect for 4-12 months can be met. The patent application with publication number of CN106913916B discloses application of a degradable zinc-based alloy implant material in preparation of vascular stents, fe and Cu are introduced into the material, so that the mechanical properties of the implant material are improved, and the strong plasticity meets the basic requirements of vascular stent materials. However, degradable iron-, magnesium-or zinc-based metallic vascular stents have a small elastic deformation, and there is a risk that the stent deforms with the movement of muscles and joints, resulting in partial or complete occlusion of the vessel. Therefore, the existing degradable metal stents are applied to the cardiovascular intervention field and can not be applied to the fields such as peripheral vascular or nerve intervention.
The shape memory alloy has super elasticity, can generate large-amplitude reversible deformation when being subjected to external force, and then returns to the original shape after the external force is removed, and cannot generate plastic deformation. The nickel-titanium shape memory alloy stent has good super elasticity at body temperature (37 ℃), and has been widely used in the fields of peripheral vascular intervention and the like. A nickel-titanium alloy stent in a human lumen is disclosed in the patent application publication No. CN114917067a, and the stent comprises an annular port, so that the stability of stent fixation is improved. However, the nickel-titanium shape memory alloy production has larger sensitivity to components and processing, so the control difficulty of smelting and processing is larger, the processing cost of the traditional process is high, and the production period is long. The patent application with publication number of CN112427654A discloses a nickel-bowl alloy bracket prepared based on a metal additive manufacturing technology and a preparation method thereof, which overcome the difficult problems that the nickel-titanium shape memory alloy prepared by the traditional technology is difficult to process and the phase transition temperature of the nickel-titanium alloy bracket prepared by the existing 3D printing technology is higher, and the phase transition temperature of the prepared nickel-bowl alloy bracket is similar to the temperature of a human body by adjusting the component proportion in the nickel-titanium alloy and the technological parameters of the metal additive manufacturing technology. However, nitinol stents have excellent corrosion resistance and still present a problem of life-long retention in the patient.
Shape memory alloys in addition to nickel titanium shape memory alloys, iron-based shape memory alloys and copper-based shape memory alloys are also contemplated. Iron-based alloys have poor shape memory effects, lower recoverable strains than conventional nickel-titanium shape memory alloys, and do not possess the same superelasticity as nickel-titanium shape memory alloys. The copper-based shape memory alloy has large maximum recoverable strain, lower cost, easier processing and wider phase transition temperature adjustable range than nickel-titanium-based shape memory alloy, and the prior work has less attention to biomedical application. Degradation product Cu of copper 2+ The antibacterial agent has a certain antibacterial effect and can prevent infection taking the instrument as a center; degradation product Cu of copper 2+ Can promote endotheliumSecretion of nitric oxide synthase to maintain vascular endothelial integrity and endothelial cell function; is beneficial to the secretion of the growth factors of the vascular endothelium and promotes the proliferation and migration of vascular endothelial cells, thereby promoting the rapid re-endothelialization of implantation sites, the recovery and maintenance of normal functions of the vascular endothelium and inducing angiogenesis. The phase transition temperature of the copper-based shape memory alloy prepared by the prior art is higher, and the self-expansion of the stent at body temperature cannot be realized. Patent application publication number US20050263222 discloses a method for reducing the phase transition temperature of a copper-zinc-aluminum shape memory alloy, but excessive aluminum exposure after long-term ingestion may have adverse effects on the nervous system, resulting in reduced cognitive function, hypomnesis, abnormal behavior, etc.
Thus, degradable metallic stents that can simultaneously avoid lifelong retention in the body, yet have superelastic and shape memory effects would be an important focus of research in the art for vascular stents.
Disclosure of Invention
The invention aims at solving the problem that the existing degradable metal vascular stent has small elastic deformation and the nickel-titanium alloy vascular stent is permanently implanted in a human body, and provides application of a degradable copper-based alloy implant material in preparing the vascular stent, wherein the copper-based alloy implant material comprises 15-42 wt% of Zn, 0-10 wt% of Si and the balance of Cu according to mass percent, and the vascular stent can be applied to the fields of peripheral blood vessels, nerve intervention or coronary blood vessels and the like. The preparation method comprises the following steps:
(1) Mixing the selected metal powder according to the mass percentage, placing the mixture into a high-purity graphite crucible, and smelting in a vacuum smelting furnace; melting the selected materials and pouring the materials into a proper mold to form an alloy cast ingot, and then cooling the alloy cast ingot along with a furnace;
(2) Heating the ingot to melt, and uniformly mixing the molten metal by stirring or other methods; drawing the molten metal by a drawing machine, and obtaining the copper-based alloy implant material wire after multi-pass drawing; the drawn metal wire is rapidly cooled by a cooling device, so that the metal wire is solidified into a metal wire;
(3) Weaving the metal wire into a shape required by the bracket, and performing two-step heat treatment; and finally, carrying out electrochemical polishing, spraying a drug coating and pressing and holding to obtain the vascular stent.
To better practice the invention, wherein the Cu-Zn alloy, preferably, comprises 38wt% to 42wt% Zn and the balance Cu; the Cu-Zn-Si alloy preferably comprises 15wt% to 30wt% Zn,5wt% to 10wt% Si and the balance Cu.
In order to realize the stability of the lower austenite transformation temperature (0-35 ℃) and the shape memory characteristic of the copper-based shape memory alloy, the heat treatment temperature range of the first step is preferably 700-850 ℃, the heat treatment time is 0.2-2 h, and then the copper-based shape memory alloy is cooled along with a furnace; the second step of heat treatment is carried out at 500-600 deg.c for 20-60 min, stepped quenching at 100 deg.c for 10 min and air cooling.
Preferably, the second heat treatment method is heating at 500 ℃ for 20min for Cu-Zn alloy; for Cu-Zn-Si alloys, heating was performed at 585℃for 60min.
In order to better realize the invention, the degradable copper-based shape memory alloy vascular stent can be further prepared by a laser engraving microtube process: mixing the selected metal powder according to the mass percentage, placing the mixture into a high-purity graphite crucible, smelting the mixture in a vacuum smelting furnace to form an alloy cast ingot, extruding a pipe, drawing the pipe for multiple times to obtain a micro pipe, then carrying out laser engraving to obtain the shape of a bracket, and carrying out two-step heat treatment. And finally polishing, spraying a drug coating and pressing and holding to obtain the vascular stent.
In order to better realize the invention, further, the degradable copper-based shape memory alloy vascular stent can be prepared by an additive manufacturing process: layering and slicing the three-dimensional model of the bracket by adopting computer software; mixing the selected metal powder according to the mass percentage. Setting proper technological parameters, laying powder, and selectively scanning and melting the powder by laser/electron beam; and stacking layer by layer until the printing of the bracket is completed. Preferably, the additive manufacturing process includes a laser selective melting, an electron beam selective melting, or an adhesive spray forming process.
Compared with the prior art, the invention has the beneficial effects that: (1) According to the invention, zn is introduced as a main component of the copper-based alloy implant material, so that the mechanical property of the copper-based alloy implant material can be obviously improved, the implant material is easy to process and form, and the performances such as strength, plasticity and the like meet the basic requirements of a vascular stent; zn itself is also a necessary nutrient element in human body, participates in the reaction of constituting a plurality of proteins and 300 kinds of enzymes, plays an important role in the growth and development of human body, immune system, metabolism and nervous system, and is a degradation product of zinc (Zn 2+ ) Has no toxicity to human body. The prior researches show that the Cu-Zn alloy can obviously reduce the initial Cu compared with the pure Cu 2+ Is released by explosion. Meanwhile, si is also a nonmetallic element existing in a human body, and can strengthen the copper-based alloy.
(2) Compared with magnesium-based, iron-based and zinc-based degradable alloy vascular stents, the degradable copper-based shape memory alloy vascular stent and the preparation method thereof provided by the invention have the following advantages: a) Shape memory effect: by adopting the alloy composition, and combining the two-step heat treatment process, the phase transition temperature of the degradable copper-based shape memory alloy is reduced to 10-32 ℃, and the bracket can realize shape memory effect under the body temperature (37 ℃) and realize self-expansion; after the stent elastically expands against the vessel wall, a gentle outward force is continued. Furthermore, the radial force of the stent may be increased or decreased without changing the design or physical dimensions; b) Superelasticity: the maximum superelastic strain can reach 8%, so that the purpose of supporting the vascular lumen can be achieved, the stent has torsion resistance, and the shape of the stent is not obviously influenced along with the movement of muscles and joints, so that the vascular is partially or completely blocked; c) Shape memory characteristics are stable: after quenching from the solution temperature, the copper-based memory alloy is aged at a temperature below As to raise the As point, and the reversible variation of the parent phase is reduced so As to degrade or even completely disappear the shape memory effect. The step quench prevents maraging stabilization and allows for optimal shape memory properties.
(3) Compared with the nickel-titanium shape memory alloy vascular stent, the degradable copper-based shape memory alloy vascular stent provided by the invention can be absorbed by a human body, and is prevented from being remained in the body of a patient for the whole life.
Drawings
FIG. 1 is a flow chart of a process for preparing a degradable copper-based shape memory alloy vascular stent;
FIG. 2 is a schematic diagram of the shape and structure of a degradable copper-based shape memory alloy used for a vascular stent.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, which are not intended to limit the present invention in any way.
Example 1: copper-zinc alloy
The degradable copper-based alloy vascular stent material of the embodiment is copper-zinc alloy, the preparation process is shown in figure 1, and the preparation method specifically comprises the following steps:
1) According to the mass percentage, 39wt% of Zn and the balance of Cu are mixed and then placed in a high-purity graphite crucible to be smelted in a vacuum smelting furnace; melting the selected materials and pouring the materials into a proper mold to form an alloy cast ingot, and then cooling the alloy cast ingot along with a furnace;
2) Heating the ingot to melt, and uniformly mixing the molten metal by stirring or other methods; drawing the molten metal by a drawing machine, and obtaining a copper-based alloy implant material wire with the diameter of 0.1mm after multi-pass drawing; rapidly cooling by a cooling device to solidify the metal wire into a metal wire;
3) The wire is woven into the shape required for the stent (see fig. 2) and subjected to a two-step heat treatment as follows: the first step of heat treatment is to keep the temperature at 700 ℃ for 0.2h; the second step of heat treatment is to heat at 500 deg.c for 20min, stepped quenching, isothermal at 100 deg.c for 10 min and air cooling. Removing material edges and corners by an electrochemical polishing method to enable the material edges and corners to be smooth, and the material edges and corners are intended to be used for coronary vascular stents;
and (3) effect verification:
the copper-based alloy implant material prepared by the method has the yield strength of about 240MPa and the elongation rate of 17 percent, can adapt to the processing and using processes of stent lying and expanding, and is a coronary vessel stent material with ideal mechanical properties. Special for universal tensile testing machineAnd clamping the alloy wire by using a clamp, loading at a stretching speed of 2mm/min, unloading until the load is zero after the preset stretching length is reached, obtaining a superelastic recovery curve, and determining that the maximum superelastic strain is 5.2%. The simulated body fluid degradation rate is 1.4 mu m/y according to ASTM G31-2012a 'laboratory metal infiltration corrosion test procedure', and the simulated body fluid in SBF can meet the clinical requirement on material degradation. A as measured by Differential Scanning Calorimetry (DSC) f The temperature is 27 ℃ and lower than the body temperature (37 ℃), and the material can be ensured to be fully expanded when being used as a medical stent in a human body.
Example 2: the degradable copper-based alloy implant material of this example was copper-zinc alloy containing 38wt% zinc, the balance being copper, and was prepared in the same manner as in example 1.
Example 3: the degradable copper-based alloy implant material of this example was copper-zinc alloy containing 42wt% zinc, the balance being copper, and was prepared in the same manner as in example 1.
Example 4: copper-zinc-silicon alloy
The degradable copper-based alloy implant material of the embodiment is copper-zinc-silicon alloy, and the preparation process specifically comprises the following steps:
1) Mixing 28 weight percent of Zn,8 weight percent of Si and the balance of Cu according to the mass percent, and then placing the mixture into a high-purity graphite crucible for smelting in a vacuum smelting furnace; melting the selected materials and pouring the materials into a proper mold to form an alloy cast ingot, and then cooling the alloy cast ingot along with a furnace;
2) Heating the ingot to melt, and uniformly mixing the molten metal by stirring or other methods; drawing the molten metal by a drawing machine, and obtaining a copper-based alloy implant material wire with the diameter of 0.1mm after multi-pass drawing; rapidly cooling by a cooling device to solidify the metal wire into a metal wire;
3) Weaving the metal wire into a shape required by the bracket, and performing the following two-step heat treatment: the first step of heat treatment is to keep the temperature at 800 ℃ for 1h; the second step of heat treatment is to heat at 585 ℃ for 60min, quench in a grading way, isothermal for 10 min at 100 ℃, and then air cool. Removing material edges and corners by an electrochemical polishing method to enable the material edges and corners to be smooth, and the material edges and corners are intended to be used for coronary vascular stents;
and (3) effect verification:
the copper-based alloy implant material prepared by the method has the yield strength of about 280MPa and the elongation of 20 percent, can adapt to the processing and using processes of stent lying and expanding, and is a coronary vessel stent material with ideal mechanical properties. And (3) clamping the alloy wire on a universal tensile testing machine by using a special clamp, loading at a tensile speed of 2mm/min, unloading until the load is zero after the preset tensile length is reached, obtaining a superelastic recovery curve, and determining the maximum superelastic strain of 8%. The simulated body fluid degradation rate is 1.12 mu m/y according to ASTM G31-2012a 'laboratory metal infiltration corrosion test procedure', and the simulated body fluid in SBF can meet the clinical requirement on material degradation. A as measured by Differential Scanning Calorimetry (DSC) f The temperature is 20 ℃ and lower than the body temperature (37 ℃), and the material can be ensured to be fully expanded when being used as a medical stent in a human body.
Example 5: the degradable copper-based alloy implant material of this example was copper-zinc-silicon alloy containing 28wt% zinc, 6wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Example 6: the degradable copper-based alloy implant material of this example was copper-zinc-silicon alloy containing 28wt% zinc, 5wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Example 7: the degradable copper-based alloy implant material of this example was copper-zinc-silicon alloy containing 28wt% zinc, 10wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Example 8: the degradable copper-based alloy implant material of this example was copper-zinc-silicon alloy containing 30wt% zinc, 10wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Example 9: the degradable copper-based alloy implant material of this example was copper-zinc-silicon alloy containing 15wt% zinc, 10wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 1: the degradable copper-based alloy implant material of this comparative example was a copper-zinc alloy containing 30wt% zinc, the balance being copper, and was prepared in the same manner as in example 1.
Comparative example 2: the degradable copper-based alloy implant material of this comparative example was a copper-zinc alloy containing 50wt% zinc, the balance being copper, and was prepared in the same manner as in example 1.
Comparative example 3: the degradable copper-based alloy implant material of this comparative example was copper-zinc-silicon alloy containing 35wt% zinc, 3wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 4: the degradable copper-based alloy implant material of this comparative example was copper-zinc-silicon alloy containing 20wt% zinc, 3wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 5: the degradable copper-based alloy implant material of this comparative example was copper-zinc-silicon alloy containing 10wt% zinc, 3wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 6: the degradable copper-based alloy implant material of this comparative example was copper-zinc-silicon alloy containing 40wt% zinc, 3wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 7: the degradable copper-based alloy implant material of this comparative example was copper-zinc-silicon alloy containing 35wt% zinc, 20wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 8: the degradable copper-based alloy implant material of this comparative example was copper-zinc-silicon alloy containing 25wt% zinc, 4wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 9: the method of this comparative example differs from example 1 only in that: the cooling mode of the second heat treatment is water quenching.
Comparative example 10: the method of this comparative example differs from example 1 only in that: the cooling mode of the second heat treatment is air cooling.
Comparative example 11: the method of this comparative example differs from example 1 only in that: the second heat treatment mode is to keep the temperature at 500 ℃ for 5min.
Comparative example 12: the method of this comparative example differs from example 1 only in that: the second heat treatment mode is to keep the temperature at 400 ℃ for 20min.
Comparative example 13: the method of this comparative example differs from example 1 only in that: the second heat treatment mode is to keep the temperature at 500 ℃ for 80min.
Comparative example 14: the method of this comparative example differs from example 1 only in that: the second heat treatment mode is to keep the temperature at 800 ℃ for 20min.
Comparative example 15: the method of this comparative example differs from example 4 only in that: the cooling mode of the second heat treatment is water quenching.
Comparative example 16: the method of this comparative example differs from example 4 only in that: the cooling mode of the second heat treatment is air cooling.
Comparative example 17: the method of this comparative example differs from example 4 only in that: the second heat treatment mode is that the temperature is kept at 585 ℃ for 35min.
Comparative example 18: the method of this comparative example differs from example 4 only in that: the second heat treatment mode is heat preservation for 60min at 400 ℃.
Comparative example 19: the method of this comparative example differs from example 4 only in that: the second heat treatment mode is that the temperature is kept at 585 ℃ for 80min.
Comparative example 20: the method of this comparative example differs from example 4 only in that: the second heat treatment mode is heat preservation for 60min at 800 ℃.
The copper-based alloy implant materials of examples 1-9 were intended for the preparation of vascular stents, and were mechanical properties, A f And corrosion performance (SBF simulated body fluid, 37 ℃) are shown in Table 1. The mechanical properties, phase transition temperatures and corrosion properties of comparative examples 1 to 8 are also shown in Table 1.
TABLE 1 mechanical Properties, phase transition temperatures and Corrosion Properties of examples 1-9 and comparative examples 1-8
For the material used for the vascular stent, the yield strength reaches more than 200Mpa, and the breaking elongation reaches 15% -18% so as to meet the requirement. Room temperature tensile Properties according to GB/T228.1-2021 section 1 of Metal Material tensile experiment: room temperature test method. The results in Table 1 show that the degradable zinc-based alloy implant material of the present invention satisfies the requirements of strength and plasticity as a support and workability in the implant body of a vascular stent.
For copper-zinc alloys, the mechanical properties of the materials of comparative examples 1 and 2 are low and the maximum superelastic strain is low, which cannot meet the requirements for support and workability, as compared with the copper-based alloy implant materials of examples 1 to 3 in the present invention.
For copper-zinc-silicon alloys, compared with the copper-base alloy implant materials of examples 4-9 of the present invention, the materials of comparative examples 3-8 either have too low mechanical strength to provide the desired supporting effect (as in comparative example 5), or have too low elongation to accommodate deformation during instrument processing and use (as in comparative examples 3-7), or A f The shape memory effect can not be realized at the temperature higher than the body temperature (such as comparative examples 3-6), or the degradation speed is too slow to meet the clinical requirements on the material degradation (such as comparative example 4, comparative example 5 and comparative example 8).
The corrosion rate of the material is suitable for being used as a degradable in-vivo implantation material, and meets the requirement of the degradation rate of the degradable vascular stent material (< 0.02 mm/y). The weight of a common standard type coronary stent made of copper as a matrix material is about 25mg. Although excessive Cu 2+ And Zn 2+ The composition has certain toxic and side effects on human bodies, but the release rate of the composition and the corrosion rate is smaller than that of an adult, namely, the copper daily average intake is 1.3 mg/d, the zinc daily average intake is 15 mg/d, and the influence on the human bodies can be ignored.
The mechanical properties of the copper-based shape memory alloy are also greatly affected by different heat treatment processes. The results in tables 2 and 3 show that the adoption of the cooling mode of the step quenching can improve the plasticity of the material, so that the copper-based alloy implant material has good cold workability.
TABLE 2 mechanical Properties of Cu-39Zn under different heat treatment Process in example 1 and comparative examples 9-14
As is clear from the comparison of the data of example 1 and comparative example 9 in Table 2, the cooling method was water quenching, and the cold workability was close to that of the sample obtained by the classification quenching, but the classification quenching could prevent the maraging stabilization and obtain the best shape memory property.
As is clear from the comparison of the data of example 1 and comparative example 10 in Table 2, the cooling system by air cooling deteriorates the cold workability of the samples.
From the comparison of the data of example 1 and comparative example 11 in Table 2, comparative example 12 shows that a shorter holding time or a lower heating temperature results in deterioration of cold workability of the material.
As is clear from the comparison of the data of example 1 and comparative example 13 in Table 2, the cold workability of the materials is also deteriorated due to an excessively long holding time or an excessively high heating temperature.
TABLE 3 mechanical Properties of Cu-28Zn-8Si under different heat treatment Processes in example 4 and comparative examples 15-20
As is clear from the comparison of the data of example 4 and comparative example 15 in Table 3, the cooling method was water quenching, and the cold workability was close to that of the sample obtained by the classification quenching, but the classification quenching could prevent the maraging stabilization and obtain the best shape memory property.
As is clear from the comparison of the data of example 4 and comparative example 16 in Table 3, the cooling system by air cooling deteriorates the cold workability of the samples.
From the comparison of the data of example 4 and comparative example 17 in Table 3, comparative example 18 shows that a shorter holding time or a lower heating temperature results in deterioration of cold workability of the material.
From the comparison of the data of example 4 and comparative example 19 in Table 3, comparative example 20 shows that too long a holding time or too high a heating temperature also results in deterioration of cold workability of the materials.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The degradable copper-based shape memory alloy vascular stent is characterized in that the copper-based shape memory alloy implant material consists of 15-42 wt% of Zn, 0-10 wt% of Si and the balance of Cu according to mass percent.
2. The degradable copper-based shape memory alloy vascular stent of claim 1, wherein the copper-based shape memory alloy is a Cu-Zn alloy, a Cu-Zn-Si alloy; wherein the Cu-Zn alloy comprises 38wt% to 42wt% Zn and the balance Cu; the Cu-Zn-Si alloy comprises 15wt% to 30wt% of Zn,5wt% to 10wt% of Si and the balance of Cu.
3. A method of preparing a degradable copper-based shape memory alloy vascular stent as defined in claim 1, comprising the steps of:
(1) Mixing the selected metal powder according to the mass percentage, placing the mixture into a high-purity graphite crucible, and smelting in a vacuum smelting furnace; melting the selected materials and pouring the materials into a proper mold to form an alloy cast ingot, and then cooling the alloy cast ingot along with a furnace;
(2) Heating the ingot to melt, and uniformly mixing the molten metal by stirring or other methods;
(3) Drawing the molten metal by a drawing machine, and obtaining the copper-based shape memory alloy implantation material wire after multi-pass drawing;
(4) The drawn metal wire is rapidly cooled by a cooling device, so that the metal wire is solidified into a metal wire;
(5) Weaving the metal wire into a shape required by the bracket, and performing two-step heat treatment;
(6) And finally, carrying out electrochemical polishing, spraying a drug coating and pressing and holding to obtain the vascular stent.
4. The method for preparing a degradable copper-based shape memory alloy vascular stent according to claim 3, wherein the first heat treatment temperature range in the two heat treatments in the step (5) is 700-850 ℃, the heat treatment time is 0.2-2 h, and then the vascular stent is cooled along with a furnace; the second step of heat treatment is carried out at 500-600 deg.c for 20-60 min, stepped quenching at 100 deg.c for 10 min and air cooling.
5. The method for preparing a degradable copper-based shape memory alloy vascular stent according to claim 3, wherein the two-step heat treatment in the step (5) is performed for a Cu-Zn alloy, and the second step heat treatment is performed for a further 20 minutes at 500 ℃.
6. The method for preparing a degradable copper-based shape memory alloy vascular stent according to claim 3, wherein the two-step heat treatment in the step (5) is performed for a Cu-Zn-Si alloy, and the second step heat treatment is performed for a further 60 minutes at 585 ℃.
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| CN106702212A (en) * | 2015-11-16 | 2017-05-24 | 上海交通大学 | Medical degradable Zn-Cu-X alloy material and preparation method thereof |
| CN111154992A (en) * | 2019-07-02 | 2020-05-15 | 山东瑞安泰医疗技术有限公司 | Preparation method and application of zinc-copper supersaturated solid solution intravascular stent material |
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| CN111154992A (en) * | 2019-07-02 | 2020-05-15 | 山东瑞安泰医疗技术有限公司 | Preparation method and application of zinc-copper supersaturated solid solution intravascular stent material |
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