CN117778801A - Degradable copper-based shape memory alloy medical implant and preparation method thereof - Google Patents
Degradable copper-based shape memory alloy medical implant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a degradable copper-based shape memory alloy medical implant and a preparation method thereof, and relates to the technical field of medical instruments. The copper-based shape memory alloy material comprises, by mass, 40-50wt% of Zn, 0-10wt% of Si and the balance of Cu. The preparation method comprises the following steps: mixing selected metal particles or silicon powder, placing the mixture into a high-purity graphite crucible, smelting the mixture in a vacuum smelting furnace, forming an alloy cast ingot, performing homogenization heat treatment, and cooling along with the furnace. Preheating cast ingot, extruding to obtain bar material. And carrying out multi-pass drawing and annealing treatment to obtain copper-based shape memory alloy wires with different diameters. Woven into the desired shape of the implant and then heat treated. The copper-based shape memory alloy material has the advantages of excellent shape memory effect, superelasticity and the like, and the braided implant can provide proper supporting force at the temperature of a human body, so that the copper-based shape memory alloy material meets the basic requirements of biomedical implants.
Description
Technical Field
The invention relates to the technical field of medical instruments, in particular to a degradable copper-based shape memory alloy medical implant and a preparation method thereof.
Background
The nickel-titanium shape memory alloy stent has good superelasticity and shape memory effect at human body temperature, and is widely used in the biomedical field. The method for treating the vascular stenosis is to support the vessel from the inside by placing a stent so as to obtain sufficient blood flow. Stents may also be used to treat sites of the trachea, esophagus, large intestine, biliary tract, etc. that are narrowed due to cancer. The former is generally a nickel titanium tube, and the latter is braided from nickel titanium wire for dimensional reasons. Both the two are the same in principle, and are delivered into a blood vessel or a digestive tract through a catheter, released at an affected part, and placed inside a lumen by utilizing the self-expansion of the super-elasticity of the catheter.
However, nitinol stents are excellent in corrosion resistance and have adverse effects such as intrastent thrombosis and intrastent restenosis that remain in the patient for the whole life after treatment. The existing iron-based, magnesium-based or zinc-based degradable metal stent and degradable polymer stent are applied to the cardiovascular intervention field, and because the elastic deformation of the stent is small, the risk of lumen blockage caused by the deformation of the stent along with the movement of muscles or joints exists, and therefore the stent cannot be applied to the fields such as peripheral vascular intervention or nerve intervention. The patent application with publication number of CN116983484B discloses a degradable copper-based shape memory alloy vascular stent and a preparation method thereof, and the copper-based alloy vascular stent 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. The Cu-Zn-Si alloy disclosed in the patent comprises 15-42 wt% of Zn, 0-10 wt% of Si and the balance of Cu, wherein the content of Cu is dominant, and the content of zinc is relatively low. Zinc is one of the essential metal elements of the human body, and the metabolite exhibits a local inflammation-inhibiting effect. Thus, increasing the zinc content of copper-based alloy shape memory alloys would be expected to provide more significant advantages and benefits.
When medical implants are implanted in different parts of the human body, the selection of the correct stent wire diameter is important for the success of surgery and for the recovery after surgery. The size of the wire diameter to be specifically adopted depends on the severity of the disease condition of the patient, the size of the blood vessel and the like. Smaller wire diameters are generally suitable for smaller vessels or lighter lesions; larger wire diameters are suitable for larger vessels or where more support is required. When the shape memory alloy is used as the medical internal support of human body, A is f (austenite transition temperature) must be below body temperature to ensure complete expansion of the stent. A is that f The higher the setting, the less stress is required to transform to martensite; conversely, A f The lower the setting, the stiffer the stent, and the greater the stress required to transform to martensite. Too low A f But also cause excessive chronic outward forces of the stent. This can lead to excessive expansion of the stent and fibrous tissue proliferation of the vessel outer wall; whereas a is too high f The elastic supporting force provided by the stent is too low to be beneficial to the stent to play a therapeutic role. Therefore, different heat treatments of shape memory alloy wires of different wire diameters are required to adapt to the performance requirements of different implantation sites.
In summary, for degradable copper-based shape memory alloy medical implants, it is possible to reduce copper content, yet have superelasticity and shape memory effect, and the mechanical properties of the implant at body temperature are adapted to the implant site, which will be the focus of research in the field.
Disclosure of Invention
The invention aims to provide an application of a degradable copper-based shape memory alloy implant material in the field of medical instruments, aiming at the problem that the existing degradable copper-based shape memory alloy has higher copper content and the mechanical property of an implant at the temperature of a human body can face discomfort, wherein the copper-based alloy implant material comprises, by mass, 40-50% of Zn, 0-10% of Si and the balance Cu. The preparation method comprises the following steps:
(1) Mixing selected metal particles or silicon powder according to mass percentage, placing the mixture into a high-purity graphite crucible, and smelting in a vacuum smelting furnace; pouring into a cylindrical die to form an alloy ingot, homogenizing at 800 ℃ for 2 hours, and cooling with a furnace;
(2) Preheating cast ingots and extruding to obtain bars;
(3) Carrying out multi-pass drawing and annealing treatment to obtain copper-based alloy implanted material wires with the diameters of 0.05-0.2 mm;
(4) Weaving the alloy wires into the shape required by the implant, and then performing heat treatment;
(5) And finally, carrying out electrochemical polishing to obtain the medical implant.
To better practice the invention, wherein the Cu-Zn alloy, preferably, has a composition of 43wt% to 50wt% Zn and the balance Cu; the Cu-Zn-Si alloy preferably has a composition of 40wt% to 50wt% Zn,2wt% to 10wt% Si and the balance Cu.
In order to realize the shape memory effect and super elasticity of the copper-based shape memory alloy at the temperature of a human body, preferably, the heat treatment temperature is 300-500 ℃, the heat treatment time is 3-15 min, and ice water quenching is adopted.
The degradable copper-based shape memory alloy medical implant can be applied to the fields of coronary vessels, peripheral vessels, cerebral vascular stents, neurovascular stents, atrial/ventricular septal defect occluders, patent foramen ovale occluders, patent arterial catheter occluders, bronchi, esophagus, colon, biliary duct stents, urethral stents and the like.
In order to meet the requirements of the implant supporting force for adapting to different implantation positions, preferably, the heat treatment temperature is 400-500 ℃ for copper-based shape memory alloy wires with the diameter of 0.1-0.2 mm; for the copper-based shape memory alloy wire with the diameter of 0.07-0.17 mm, the heat treatment temperature is 350-450 ℃; for the copper-based shape memory alloy wire with the diameter of 0.05 mm-0.07 mm, the heat treatment temperature is 300-400 ℃.
In order to better realize the invention, when the degradable copper-based shape memory alloy is applied to coronary vessels, the degradable copper-based shape memory alloy can be prepared by a laser engraving microtube process: mixing selected metal particles or silicon powder according to 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 alloy cast ingot for multiple times to obtain a microtube, then carrying out laser engraving to obtain the shape of a bracket, and carrying out heat treatment. And finally polishing and spraying a drug coating to obtain the vascular stent.
Compared with the prior art, the invention has the following beneficial effects: (1) copper content decreases and zinc content increases: zinc has good biocompatibility and high toxicity threshold. Zinc is a necessary trace element for human body, and is widely distributed in cells, tissues and body fluid of human body, so that the immunity of the human body can be improved. Zinc is also a cofactor of more than 300 enzymes of a human body, plays an extremely important role in regulating the normal growth and development of the body, nucleic acid synthesis, protein metabolism, cell membrane stability and the like in terms of the structural composition and catalytic activity of the enzymes. In addition, the degradation rate of zinc is proper, and the metabolite is harmless to human body and shows the effect of local inflammation inhibition. Zinc also has antibacterial and tissue repair effects. Zinc is an essential substance for wound healing and plays an important role in the repair of damaged tissues.
(2) The supporting force of the medical implant is adapted to the corresponding implantation site of the human body: the diameter of the neurovascular stent is preferably 0.05 mm-0.07 mm; the diameter of the atrial/ventricular septal defect occluder, the patent foramen ovale occluder and the patent arterial catheter occluder is preferably 0.07-0.17 mm; the diameter of the alloy wire of the support of bronchus, esophagus, colon and bile duct is preferably 0.1 mm-0.2 mm. According to different implantation positions in a human body, different heat treatments are carried out on the shape memory alloy implants with different wire diameters, so that the shape memory alloy implants have different supporting forces to meet the requirements of different implantation positions. Such as implants woven from larger diameter (e.g., 0.2 mm) wire, preferably at higher heat treatment temperatures to reduce their holding power. Thus, the implant does not over-expand nor support the lumen too low to perform a therapeutic function.
(3) The degradation rate of the medical implant is proper, and the mechanical support requirement within one year is met: the smaller the diameter of the copper-based shape memory alloy wire, the smaller the grain size and the faster the degradation rate. For implants woven from smaller diameter (e.g., 0.05 mm) wire, it is preferable that the lower heat treatment temperature increases its support to compensate for the strength loss due to the too fast degradation rate. Therefore, by adopting different heat treatment processes for the implant woven by the wires with different wire diameters, the balance between the mechanical support requirement and the ideal degradation rate is realized.
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.
A preparation method of a degradable copper-based shape memory alloy medical implant comprises the following specific steps:
example 1: the degradable copper-based shape memory alloy implant material of the embodiment is a copper-zinc alloy, and specifically comprises the following steps:
1) Mixing 43wt% of Zn and the balance of Cu according to the mass percentage, placing the mixture into a high-purity graphite crucible, smelting the mixture in a vacuum smelting furnace, pouring the mixture into a cylindrical mold to form an alloy cast ingot, carrying out homogenization heat treatment at 800 ℃ for 2 hours, and cooling the alloy cast ingot along with the furnace;
2) Preheating cast ingots and extruding to obtain bars; carrying out multi-pass drawing and annealing treatment to obtain a copper-based alloy implant material wire with the diameter of 0.15mm;
3) Alloy wires were woven into a mesh stent having a diameter of 10mm, and subjected to the following heat treatment: heating at 425 ℃ for 10min, and quenching by ice water.
And (3) effect verification: the copper-based alloy implant material prepared by the method is A measured by Differential Scanning Calorimetry (DSC) f The temperature is 24 ℃ and lower than the body temperature (37 ℃), and the material can be ensured to be fully expanded when being used for medical stents in human bodies. The mesh stent was compressed to 5mm (50% strain) to give a radial support force of 2.3N. The nickel-titanium stent is used as a contrast, and the radial supporting force of the nickel-titanium stent is 1.2-2.9N.
Example 2: the degradable copper-based alloy implant material of this example was copper-zinc alloy containing 45wt% zinc, the balance being copper, and the preparation process was the same as that of example 1.
Example 3: the degradable copper-based alloy implant material of this example was copper-zinc alloy containing 50wt% zinc, the balance being copper, and was prepared in the same manner as in example 1.
Example 4: 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 40wt% of Zn,2wt% of Si and the balance of Cu according to the mass percentage, placing the mixture into a high-purity graphite crucible, smelting the mixture in a vacuum smelting furnace, pouring the mixture into a cylindrical mold to form an alloy cast ingot, carrying out homogenization heat treatment at 800 ℃ for 2 hours, and cooling the alloy cast ingot along with the furnace;
2) Preheating cast ingots and extruding to obtain bars; carrying out multi-pass drawing and annealing treatment to obtain a copper-based alloy implant material wire with the diameter of 0.15mm;
3) Alloy wires were woven into a mesh stent having a diameter of 10mm, and subjected to the following heat treatment: heating at 375 deg.c for 10min, and quenching with ice water.
And (3) effect verification: the copper-based alloy implant material prepared by the method is A measured by DSC f The temperature is 15 ℃ and lower than the body temperature, and the material can be ensured to be fully expanded when being used as a medical stent in a human body. The mesh stent was compressed to 5mm (50% strain) and the resulting radial support force was 1.6N.
Example 5: the degradable copper-based alloy implant material of this example was copper-zinc-silicon alloy containing 45wt% 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 50wt% zinc, 10wt% 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 the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.05mm; the woven mesh stent is subjected to the following heat treatment: heating at 375 deg.C for 10min, quenching with ice water, and the rest preparation process is the same as in example 1.
Example 8: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.2mm; the woven mesh stent is subjected to the following heat treatment: heating at 475 deg.C for 10min, quenching with ice water, and the rest preparation process is the same as in example 1.
Example 9: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.15mm; the woven mesh stent is subjected to the following heat treatment: heating at 350deg.C for 10min, quenching with ice water, and the rest preparation process is the same as in example 1.
Example 10: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.15mm; the woven mesh stent is subjected to the following heat treatment: heating at 450 ℃ for 10min, quenching by ice water, and the rest preparation process is the same as that of the example 1.
Example 11: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.05mm; the woven mesh stent is subjected to the following heat treatment: heating at 300 ℃ for 10min, quenching by ice water, and the rest preparation process is the same as that of the example 1.
Example 12: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.05mm; the woven mesh stent is subjected to the following heat treatment: heating at 400 ℃ for 10min, quenching by ice water, and the rest preparation process is the same as that of the example 1.
Example 13: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.2mm; the woven mesh stent is subjected to the following heat treatment: heating at 400 ℃ for 10min, quenching by ice water, and the rest preparation process is the same as that of the example 1.
Example 14: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.2mm; the woven mesh stent is subjected to the following heat treatment: heating at 500 deg.C for 10min, quenching with ice water, and the rest preparation process is the same as in example 1.
Example 15: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.2mm; the woven mesh stent is subjected to the following heat treatment: heating at 475 deg.C for 3min, quenching with ice water, and the rest preparation process is the same as in example 1.
Example 16: the degradable copper-based alloy implant material of the embodiment is copper-zinc alloy, the alloy composition is the same as that of the embodiment 1, and the diameter of the wire obtained after multi-pass drawing is 0.2mm; the woven mesh stent is subjected to the following heat treatment: heating at 475 deg.C for 15min, quenching with ice water, and the rest preparation process is the same as in example 1.
Comparative example 1: the degradable copper-based alloy implant material of this comparative example was a copper-zinc alloy containing 52wt% 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 copper-zinc-silicon alloy containing 35wt% zinc, 2wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 3: the degradable copper-based alloy implant material of this comparative example was a copper-zinc alloy containing 55wt% zinc, 2wt% 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 a copper-zinc alloy containing 45wt% zinc, 1wt% 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 a copper-zinc alloy containing 45wt% zinc, 15wt% silicon, and the balance copper, and was prepared in the same manner as in example 4.
Comparative example 6: the method of this comparative example differs from example 1 only in that: the heat treatment temperature was 200 ℃.
Comparative example 7: the method of this comparative example differs from example 1 only in that: the heat treatment temperature was 600 ℃.
Comparative example 8: the method of this comparative example differs from example 1 only in that: the diameter of the wire obtained after drawing was 0.05mm, and the heat treatment temperature was 200 ℃.
Comparative example 9: the method of this comparative example differs from example 1 only in that: the diameter of the wire rod obtained after drawing is 0.05mm, and the heat treatment temperature is 600 ℃.
Comparative example 10: the method of this comparative example differs from example 1 only in that: the diameter of the wire obtained after drawing was 0.2mm, and the heat treatment temperature was 200 ℃.
Comparative example 11: the method of this comparative example differs from example 1 only in that: the diameter of the wire obtained after drawing was 0.2mm, and the heat treatment temperature was 600 ℃.
Comparative example 12: the method of this comparative example differs from example 8 only in that: the heat treatment time was 60min.
Comparative example 13: the method of this comparative example differs from example 8 only in that: the heat treatment time was 1min.
For medical implants made of shape memory alloys, the implants need to have superelasticity and shape memory effects at body temperature, and mechanical properties are also adapted to the implant site. A is that f Must be below body temperature to ensure complete expansion of the stent. A is that f The higher the setting, the lower the elastic supporting force the bracket can provide; conversely, A f The lower the setting, the higher the chronic outward force of the stent. A of copper-based shape memory alloys of examples 1 to 6 and comparative examples 1 to 5 f And radial supporting force after the bracket is woven is shown in table 1. The results in Table 1 show that A of the degradable copper-based alloy implant material of the present invention f And the radial supporting force of the bracket meet the requirement of the material as a medical implant.
Compared with the copper-base alloy implant materials of examples 1-3 in the invention, the copper-base alloy of comparative example 1 has no shape memory effect, and the radial supporting force is too small to meet the requirements.
For copper-zinc-silicon alloys, comparative examples 2 to 5 are compared with the copper-based alloy implant materials of examples 4 to 6 in the present inventionMaterial either A f High and low radial support force, and cannot achieve the proper support effect at body temperature (e.g., comparative examples 2, 4) or have no shape memory effect (e.g., comparative examples 3, 5).
TABLE 1 phase transition temperatures and stent radial support forces for examples 1-6 and comparative examples 1-5
The diameter of the alloy wire of the atrial/ventricular septal defect occluder, the patent foramen ovale occluder, and the patent ductus arteriosus occluder is preferably 0.07mm to 0.17mm, as in example 1. The diameter of the alloy wire is preferably 0.1mm to 0.2mm for bronchi, esophagus, colon, bile duct stents, as in example 8. The nerve vessel diameter is generally 2mm to 6mm, and the preferred alloy wire diameter for the stent used is 0.05mm to 0.07mm, as in example 7. If the wire diameter is too large, the risk of lumen blockage exists, and the corresponding excessive supporting force can cause damage to the implantation site; if the wire diameter is too small, the implant support force is insufficient.
Different heat treatment processes have great influence on the mechanical properties of copper-based shape memory alloys with different diameters. The results in table 2 show that the material can have a suitable phase transition temperature and radial support force using the heat treatment process of the present invention.
As is clear from the comparison of the data of examples 1, 7-14 and comparative examples 6-11 in Table 2, when the heat treatment temperature is too low (comparative examples 6, 8, 10), there is no shape memory effect, and the supporting force is too great, which results in excessive expansion of the stent and fibrous tissue proliferation of the outer wall of the blood vessel; when the heat treatment temperature was too high (comparative examples 7, 9, 11), the stent A f Above body temperature, radial supporting force is too low to realize due supporting effect at body temperature.
The wire of example 7 with a diameter of 0.05mm was the smallest diameter in examples 1, 7, 8. The smaller the grain size is, the faster the degradation rate is, the faster the mechanical strength loss of the woven implant is, and the support force of the support is insufficient in the later period of degradation. The preferred lower heat treatment temperature (375 ℃) allows the initial support force of the implant to be increased to compensate for the strength loss associated with too fast a degradation rate, achieving a balance between mechanical support requirements and ideal degradation rates.
TABLE 2 phase transition temperature and radial support force of copper-based shape memory alloy stents of different wire diameters under different heat treatment processes in examples 1, 7-14 and comparative examples 6-11
Different heat treatment times also have a certain effect on the transformation temperature of the copper-based shape memory alloy, as shown in table 3. The results show that too long (comparative example 12) or too short (comparative example 13) heat treatment results in too high a phase transition temperature, and the implant has no shape memory effect or superelasticity at the body temperature, and cannot realize self-expansion. When the heat treatment temperature is 3-15 min (examples 8, 15 and 16), the phase transition temperature of the implant is lower than the body temperature, and the implant has super-elasticity and shape memory effect.
TABLE 3 phase transition temperatures of copper-based shape memory alloys at different heat treatment times in examples 8, 15, 16 and comparative examples 12, 13
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 (5)
1. A degradable copper-based shape memory alloy medical implant, characterized in that the copper-based shape memory alloy is a Cu-Zn alloy and a Cu-Zn-Si alloy; wherein the Cu-Zn alloy comprises 43wt% to 50wt% Zn and the balance Cu; the Cu-Zn-Si alloy comprises 40wt% to 50wt% of Zn,2wt% to 10wt% of Si and the balance of Cu; the copper-based shape memory alloy medical implant is formed by weaving wires, and is subjected to heat treatment and ice water quenching, and is characterized in that the heat treatment temperature is 300-500 ℃ and the heat treatment time is 3-15 min.
2. A method of making a degradable copper-based shape memory alloy medical implant according to claim 1, comprising the steps of:
(1) Mixing selected metal particles or silicon powder according to mass percentage, placing the mixture into a high-purity graphite crucible, smelting the mixture in a vacuum smelting furnace, pouring the mixture into a cylindrical mold to form an alloy cast ingot, carrying out homogenization heat treatment at 800 ℃ for 2 hours, and cooling the alloy cast ingot along with the furnace;
(2) Preheating cast ingots and extruding to obtain bars;
(3) Carrying out multi-pass drawing and annealing treatment to obtain a copper-based shape memory alloy wire with the diameter of 0.05-0.2 mm;
(4) Weaving the alloy wires into the shape required by the implant, and then performing heat treatment;
(5) And finally, carrying out electrochemical polishing to obtain the medical implant.
3. The method for preparing a degradable copper-based shape memory alloy medical implant according to claim 2, wherein the heat treatment in the step (4) is performed at a temperature of 400-500 ℃ on a copper-based shape memory alloy wire with a diameter of 0.1-0.2 mm.
4. The method for preparing a degradable copper-based shape memory alloy medical implant according to claim 2, wherein the heat treatment in the step (4) is performed at a temperature of 350-450 ℃ on a copper-based shape memory alloy wire with a diameter of 0.07-0.17 mm.
5. The method for preparing a degradable copper-based shape memory alloy medical implant according to claim 2, wherein the heat treatment in the step (4) is performed at a temperature of 300-400 ℃ on a copper-based shape memory alloy wire with a diameter of 0.05-0.07 mm.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170128631A1 (en) * | 2013-10-25 | 2017-05-11 | Steriplate, LLC | Metal plated object with biocidal properties |
| CN109128064A (en) * | 2018-09-21 | 2019-01-04 | 北京科技大学 | A kind of biodegradable Zn-Na system kirsite and preparation method thereof |
| CN109602960A (en) * | 2018-12-17 | 2019-04-12 | 山东瑞安泰医疗技术有限公司 | One kind having superplastic medical Zinc alloy bar preparation method |
| CN110421173A (en) * | 2019-09-17 | 2019-11-08 | 湖南华耀百奥医疗科技有限公司 | A kind of Zinc-base compounded material of medical degradable and the preparation method and application thereof |
| CN111020254A (en) * | 2019-11-19 | 2020-04-17 | 河海大学 | Low-alloying high-toughness easily-woven degradable medical zinc alloy wire and preparation method thereof |
| CN111560540A (en) * | 2020-06-12 | 2020-08-21 | 长沙镁捷新材料科技有限公司 | Degradable medical implant material zinc-silicon series alloy and preparation method thereof |
| US20200385844A1 (en) * | 2015-08-19 | 2020-12-10 | Shanghai Jiao Tong University | Medical biodegradable zn-cu alloy and its preparation method as well as applications |
| CN112981179A (en) * | 2021-02-07 | 2021-06-18 | 广东省科学院材料与加工研究所 | Nickel-titanium shape memory alloy material, alloy wire material, and preparation method and application thereof |
| CN116983484A (en) * | 2023-09-26 | 2023-11-03 | 山东瑞安泰医疗技术有限公司 | Degradable copper-based shape memory alloy vascular stent and preparation method thereof |
-
2024
- 2024-02-26 CN CN202410206956.0A patent/CN117778801B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170128631A1 (en) * | 2013-10-25 | 2017-05-11 | Steriplate, LLC | Metal plated object with biocidal properties |
| US20200385844A1 (en) * | 2015-08-19 | 2020-12-10 | Shanghai Jiao Tong University | Medical biodegradable zn-cu alloy and its preparation method as well as applications |
| CN109128064A (en) * | 2018-09-21 | 2019-01-04 | 北京科技大学 | A kind of biodegradable Zn-Na system kirsite and preparation method thereof |
| CN109602960A (en) * | 2018-12-17 | 2019-04-12 | 山东瑞安泰医疗技术有限公司 | One kind having superplastic medical Zinc alloy bar preparation method |
| CN110421173A (en) * | 2019-09-17 | 2019-11-08 | 湖南华耀百奥医疗科技有限公司 | A kind of Zinc-base compounded material of medical degradable and the preparation method and application thereof |
| CN111020254A (en) * | 2019-11-19 | 2020-04-17 | 河海大学 | Low-alloying high-toughness easily-woven degradable medical zinc alloy wire and preparation method thereof |
| CN111560540A (en) * | 2020-06-12 | 2020-08-21 | 长沙镁捷新材料科技有限公司 | Degradable medical implant material zinc-silicon series alloy and preparation method thereof |
| CN112981179A (en) * | 2021-02-07 | 2021-06-18 | 广东省科学院材料与加工研究所 | Nickel-titanium shape memory alloy material, alloy wire material, and preparation method and application thereof |
| CN116983484A (en) * | 2023-09-26 | 2023-11-03 | 山东瑞安泰医疗技术有限公司 | Degradable copper-based shape memory alloy vascular stent and preparation method thereof |
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