CN116099031B - Degradable and absorbable magnesium alloy suture line and preparation method and application thereof - Google Patents
Degradable and absorbable magnesium alloy suture line and preparation method and application thereof Download PDFInfo
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- CN116099031B CN116099031B CN202310063209.1A CN202310063209A CN116099031B CN 116099031 B CN116099031 B CN 116099031B CN 202310063209 A CN202310063209 A CN 202310063209A CN 116099031 B CN116099031 B CN 116099031B
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
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- 239000003356 suture material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
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- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
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- 229910001424 calcium ion Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal 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
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/005—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters containing a biologically active substance, e.g. a medicament or a biocide
-
- 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
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable materials
-
- 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
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/14—Post-treatment to improve physical properties
- A61L17/145—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/10—Supplying or treating molten metal
- B22D11/11—Treating the molten metal
- B22D11/114—Treating the molten metal by using agitating or vibrating means
- B22D11/115—Treating the molten metal by using agitating or vibrating means by using magnetic fields
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium 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
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Vascular Medicine (AREA)
- Surgery (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a degradable and absorptive magnesium alloy suture line, which comprises the following elements in percentage by mass: 2.0-5.0% of Y, 1.0-3.0% of Nd, 0-2.0% of Gd, 0.01-1% of Zr and the balance of Mg. The invention also discloses a preparation method of the magnesium alloy suture line, which is prepared by smelting, electromagnetic continuous casting, back extrusion and hot drawing processes, wherein the tensile strength is more than or equal to 340MPa, the yield strength is more than or equal to 292MPa, the elongation is more than or equal to 20%, the corrosion rate in SBF simulated body fluid is less than or equal to 0.3mg cm ‑2·day‑1, and the magnesium alloy suture line has high biocompatibility and degradability and absorbability.
Description
Technical Field
The invention belongs to the technical field of biomedical materials, and particularly relates to a degradable and absorbable magnesium alloy suture, a preparation method of the suture and application of the suture in ligature hemostasis, suture hemostasis and tissue suturing in surgical operation or trauma treatment.
Background
At present, in surgical operations or trauma treatments, ligature hemostasis, suture hemostasis and tissue suturing are required, and the suturing is widely applied to operations such as plastic surgery, urology surgery, pediatrics, stomatology, otorhinolaryngology, ophthalmology and the like and suturing of intradermal soft tissues. In most of these surgical operations, non-degradable absorbable sutures are used, such as titanium alloy, stainless steel suture ligature suture hemostasis and internal tissue suture termination, and secondary surgery is required to remove the suture after body recovery, causing secondary injury to the human body and spirit. For example, congenital small ear deformity is a common congenital disease, and the treatment of small ear deformity is based on the reconstruction of the outer ear. Currently, the most commonly used auricular scaffolding material is autologous costal cartilage. In the preparation process of the auricle stent, rib cartilage strips are required to be built into a multi-layer structure, and cartilage at a special part also needs to be bent and shaped. In order to maintain the shape of the auricle stent, a titanium alloy suture line or an artificially synthesized macromolecule absorbable suture line is generally used for splicing and fixing a plurality of costal cartilage strips so as to obtain a stable three-dimensional structure. However, the titanium alloy suture cannot be degraded in the long-term retention body, and in daily activities, the titanium alloy suture can move, and the tip of the titanium alloy suture is easy to puncture the skin, so that the titanium wire and cartilage leak, and the postoperative infection risk is increased. In addition, the synthetic macromolecule absorbable suture has poor stress intensity, can not continuously fix cartilage form, has poor stability, can gradually deform a cartilage bracket, has slow degradation speed of the synthetic macromolecule absorbable suture, and generates acid metabolites in the degradation process to cause cartilage absorption and surrounding inflammatory reaction. Similar problems are involved in the operations of plastic surgery, urology surgery, pediatrics, stomatology, otorhinolaryngology, ophthalmology and the like and the operations of suturing soft tissues in the skin, so biomedical degradable absorbing magnesium alloy suture lines are required to be developed to replace non-degradable absorbing metal suture lines such as titanium alloy, stainless steel and the like, and the problems of insufficient strength, incomplete degradation, inflammation and the like of artificially synthesized high polymer suture lines are overcome.
The most used titanium alloy suture in the market at present is a titanium-nickel memory alloy suture, even if the titanium-nickel alloy has good biocompatibility, because of the nondegradability, the titanium-nickel memory alloy suture exists in a human body for a long time, and along with daily life, the suture tip punctures tissues, skin and the like to increase infection risks, a plurality of troubles are brought to patients, such as psychological problems, needle-like pain, secondary operation suture taking and the like. Patent publication No. CN103284771A discloses an antibacterial medical titanium-nickel memory alloy suture and a preparation method thereof. The method adopts a physical vapor deposition method to deposit an anion plating layer on the surface of the titanium-nickel memory alloy suture line, thereby playing a role in sterilization and bacteriostasis and achieving the purposes of preventing infection and resisting infection. But its non-degradable nature is not changeable, it is still an important issue limiting its application. Currently, absorbable polymer sutures are used in some procedures. The patent issued publication number CN208160632U discloses a PGA quick-absorption suture. The suture line can be rapidly degraded on the basis of maintaining the original performance by weaving 20-40 strands of the suture line and coating with polycaprolactone and calcium stearate, and can be degraded within 60-90 days after being implanted for two weeks, and the original tensile strength can be maintained. However, experiments show that part of the materials still cannot be degraded eventually, and inflammation can be triggered. The patent with publication number CN106039388A provides a preparation method of PLA-based surgical suture, and the polylactic acid is blended with various absorbable materials to achieve the effect of improving the mechanical property and the antibacterial rate of the suture. However, the polylactic acid has a slow degradation speed, so that the inside of the obtained suture line continuously maintains a relatively compact structure, and the ingrowth of tissues is limited, thereby prolonging the healing time and affecting the healing effect. The patent with publication number CN102406961B adds urea and glycerin into chitosan solution to increase the toughness of chitosan and adopts wet spinning technology to improve the preparation efficiency. However, since the chitosan has a high degradation rate, the mechanical strength of the chitosan is rapidly reduced in the actual use process, and the chitosan is difficult to maintain sufficient strength before the wound of a patient is recovered, and secondary cracking of the wound is easily caused, so that the recovery of the patient is affected.
The high molecular suture has low mechanical strength, most of tensile strength is about 70MPa, the stability is poor, the degradation speed is slow, acidic metabolites are generated in the degradation process, and peripheral inflammatory reaction is caused. The existing macromolecule absorbable suture line can not completely meet the medical requirements of high biocompatibility and accurate controllable degradation rate.
The magnesium alloy has good biocompatibility and degradability, and has great potential and clinical application prospect as a novel biomedical metal material capable of replacing the traditional biomedical metal material.
Magnesium is one of the essential nutrient elements for human body, and a large amount of magnesium ions exist in the human body, and the content of magnesium ions is inferior to calcium ions, potassium ions and sodium ions. Magnesium is a necessary element for human bone growth, and can promote the formation of osteoblasts, promote the healing of bone cells and the growth of new bone cells, and prevent local osteoporosis. After the magnesium alloy is implanted into a human body, the concentration of released magnesium ions is far lower than the physiological concentration of blood (0.7-1.5 mmol/L), and the daily requirement of an adult is more than 350mg. The degradation of the magnesium alloy implant in the human body can cause the pH value of the environment near the implant to be increased, the alkaline environment is greatly improved, the living condition of bacteria is obviously destroyed, and the antibacterial effect is achieved. So that it has good biocompatibility.
The magnesium has high specific strength and specific rigidity, excellent electric conductivity and heat conductivity, shock absorption, shielding property, no magnetism, easy recovery and the like, and the Young modulus is 41-45GPa, which are similar to human bones, so that the stress shielding effect can be effectively avoided or weakened, the healing of bone tissues is facilitated, and the local osteoporosis can be prevented.
Compared with other biomedical metal implantation materials, the magnesium alloy can be automatically degraded in a human body, and is taken out without secondary operation, and compared with biomedical polymer implantation materials, the magnesium alloy has a degradation mechanism different from that of the polymer materials. The magnesium alloy combines with excellent biocompatibility of biomedical magnesium alloy, magnesium ions released during degradation are trace elements necessary for human body, bone growth and enzyme generation are promoted, excessive magnesium ions can be discharged along with urine, and the magnesium alloy is nontoxic and can ensure healthy growth of the body. The in vitro research and the in vivo research of the pure magnesium and the magnesium alloy show good biocompatibility and degradability, no obvious inflammatory reaction is observed in the animal in vivo experiment, and the in vivo implant can be completely degraded.
The patent application of the application publication number CN108950336A discloses a high-plasticity degradable biomedical Mg-Zn-Zr-Ca-Fe alloy wire and a preparation method thereof. The biomedical magnesium alloy wire with the diameter of 0.4-0.5mm under the service of biological fluid environment is obtained through smelting, casting, homogenization treatment, hot extrusion, drawing and artificial aging treatment. The alloy has no toxicity to human body after in vivo degradation, excellent mechanical property, good mechanical property and processing property and proper corrosion rate. The Mg-Zn-Zr-Ca-Fe alloy material has tensile strength of more than or equal to 297MPa, yield strength of more than or equal to 261MPa and elongation after fracture of more than or equal to 27 percent, and is suitable for preparing medical materials such as suture lines and the like. But their biocompatibility is not demonstrated in detail. The patent application of application publication No. CN115198155A discloses a high-performance degradable biological magnesium alloy material and a preparation method thereof. The degradable biological magnesium alloy material with high strength, good plasticity and uniform corrosion is obtained through smelting and casting, homogenizing heat treatment, hot extrusion and aging treatment, the tensile strength, yield strength and elongation after fracture reach 374MPa, 329MPa and 12.5 percent respectively, and the corrosion rate is more than 1.46 g.dm -2·h-1, so that the degradable biological magnesium alloy material can be widely applied to medical sutures. However, the method of making the suture filaments is not explained in detail in this patent and the corrosion rate is too fast to be beneficial for wound healing. The patent of application publication No. CN106917022A discloses that the magnesium-zinc alloy is subjected to severe plastic deformation treatment, when the strain amount is large enough, the original coarse second phase is broken into small particles, and meanwhile, crystal grains are obviously thinned and have a large number of crystal defects such as dislocation, vacancy and the like. The greater the number of phase interfaces per unit volume, the faster the diffusion speed and the shorter the distance that the solute atoms need to diffuse, the greater the number of grain defects in the material is very advantageous for the diffusion of zinc in the matrix. The material is heated to 300 ℃ in the subsequent drawing process and deformed, the grain size is maintained in a finer state under the action of dynamic recrystallization, the second phase is dissolved in the deformation process until the second phase is completely dissolved in the matrix, and when the wire drawing is completed, a single-phase supersaturated solid solution tissue is obtained, the strength and the elongation are higher than those of the wire obtained by directly drawing without equal channel extrusion, so that the requirements of strength and plasticity are met, and the corrosion resistance of the material is greatly improved. The yield strength, the tensile strength and the elongation of the Mg-Zn wire with the diameter of 0.3mm, which is manufactured by equal channel extrusion and drawing, are respectively 210MPa, 300MPa and 11 percent at room temperature.
The magnesium alloy wires mentioned in the above patents have been studied in a great deal in terms of toughness, but the degradation speed in human body is fast and the expected requirements are not met. The pH value in the human body is about 7.4, and the secondary acid liquor is excessive caused by the metabolism of the human body after operation, so that the pH value is reduced, and the corrosion and degradation of the magnesium alloy can be accelerated. During the gradual repair of damaged tissues, the ideal suture material should be capable of meeting the short-term supporting and low-invasive repair functions, and after the body tissues are healed, the suture material is completely degraded and absorbed. The rapid degradation rate of the magnesium alloy wire makes it unable to provide effective support during tissue healing and can result in a significant accumulation of magnesium ions and hydrogen. Thus, the research on the biomedical degradable absorbing magnesium alloy suture with high strength and high corrosion resistance is still in the situation that no suitable wire is available.
Therefore, a biomedical degradable absorbing magnesium alloy suture thread wire with high strength, high plasticity, high corrosion resistance and high biocompatibility and a preparation method thereof are needed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a degradable and absorbable magnesium alloy suture line which has short supporting and low-invasive repairing functions and can be completely degraded and absorbed after body tissues are healed.
In order to solve the technical problems, the invention provides the following technical scheme:
the degradable and absorbable magnesium alloy suture comprises the following elements in percentage by mass: 2.0-5.0% of Y, 1.0-3.0% of Nd, 0-2.0% of Gd, 0.01-1% of Zr and the balance of Mg.
Preferably, the diameter of the degradable absorption magnesium alloy suture is 0.1-0.3mm.
The preparation method of the degradable absorption magnesium alloy suture comprises the following steps:
(1) Pretreatment: weighing the required raw materials according to the content of each element, and polishing by using sand paper to remove an oxide layer on the metal surface;
(2) Electromagnetic continuous casting: placing the pretreated raw material into a melting furnace, heating and melting the raw material, and obtaining an ingot through medium-high frequency electromagnetic continuous casting;
(3) Homogenizing: air cooling is carried out after the ingot is insulated;
(4) And (3) back extrusion: performing back extrusion on the cast ingot to obtain an alloy bar;
(5) Hot drawing deformation: machining the alloy bar, annealing before drawing, and performing hot drawing at 200-400 ℃;
(6) Annealing after drawing: and drawing to obtain the wire material according to the final manufacturing requirement of the wire material, and annealing.
Preferably, the electromagnetic continuous casting process of the step (2) is as follows: firstly, adding a high-purity magnesium ingot into a melting furnace for melting, and then, at a volume ratio SF 6：CO2 =1: and (3) under the protection of 99 high-purity gas, sequentially adding Mg-Zr, mg-Y, mg-Nd and (Mg-Gd) intermediate alloy, heating to 730-750 ℃, preserving heat for 15-30min, cooling to 700-720 ℃, preserving heat for 20min, casting, flowing the molten metal into a crystallizer through a guide pipe below a melting furnace under the action of gas pressure, applying an intermediate frequency electromagnetic field of 2.5kHz and 10kW in the casting process, wherein the casting machine speed is 0.8mm/s, the stable pulling speed is 1.02mm/s, the cooling water strength is 1.0t/h, the final ingot size is 120mm in diameter and 500mm in height.
Preferably, the homogenization treatment in the step (3) is carried out, the heat preservation range is 200-500 ℃, the heat preservation time is 5-32 hours, and the air cooling is carried out to the room temperature after the heat preservation.
Preferably, the back extrusion process of step (4) is: the diameter of the cast ingot is 35-40mm, the length is 15-30mm, the extrusion temperature is 400-500 ℃, the extrusion speed is 1-8mm/s, the extrusion ratio is 16-25, and the bar with the diameter of 8-10mm is reversely extruded.
Preferably, the hot drawing process of step (5) is: machining the extruded alloy bar, taking out a round bar with the diameter of 6mm and the length of 200-500mm, annealing for 15-30min at the annealing temperature of 300-500 ℃, and performing hot drawing. The drawing temperature is 200-400 ℃, the drawing speed is 1-10m/min, the diameter of the wire is larger than 1.0mm, 10% -15% of pass deformation is adopted to accelerate the drawing speed, the diameter of the wire is smaller than 1.0mm, 5% of pass deformation is adopted to prevent wire breakage, a tubular heating furnace is clamped on a fixed head on a drawing machine, the tubular heating furnace is opened to set the experimental temperature to 200-400 ℃, the temperature in the drawing bar and the tubular heating furnace is measured by using thermocouple heat, and the drawing is carried out until the drawing bar reaches the experimental temperature. The pass deformation of the drawing experiment is changed by changing drawing dies with different sizes. The drawing temperature of the drawing experiment was changed by changing the temperature of the tube furnace.
Preferably, the wire material with the diameter of 0.3mm to 0.1mm is obtained by drawing in the step (6), and then the wire material is annealed at the annealing temperature of 300-500 ℃ for 15-30min.
The degradable and absorbable magnesium alloy suture is applied to surgery or trauma treatment, and is preferably applied to surgery such as plastic surgery, urology surgery, pediatrics, stomatology, otorhinolaryngology, ophthalmology and the like and the suturing of intradermal soft tissues.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a degradable absorption Mg-Y-Nd- (Gd) -Zr magnesium alloy suture line, which is prepared by smelting, electromagnetic continuous casting, back extrusion and hot drawing processes, has the tensile strength of more than or equal to 340MPa, the yield strength of more than or equal to 292MPa, the elongation rate of more than or equal to 20 percent, and the corrosion rate of SBF simulated body fluid of less than or equal to 0.3Mg cm -2·day-1, and has high biocompatibility and degradable absorptivity.
(2) The biomedical degradable magnesium alloy suture prepared by the method can be independently compounded or compounded with other high polymer materials, and the high polymer coating material can further improve the corrosion resistance or biocompatibility of the material.
(3) The main alloying elements in Mg-Y-Nd- (Gd) -Zr have very low electrode potentials, the standard potentials for Y, nd and Gd (relative to standard hydrogen electrode SHE) are-2.37V, -2.44V and-2.40V, respectively, each lower than the standard potential for magnesium-2.34V, so the rare earth rich phases in Mg-Y-Nd- (Gd) -Zr (phase structure Mg 24RE5 phase and Mg 41Nd5 phase) may have lower potentials than α -Mg. Some studies have also shown that the rare earth-rich second phase in rare earth magnesium alloys has a potential close to that of the matrix. So that no significant galvanic corrosion occurs and the matrix dissolves rapidly. The main phase structure of the alloy is Mg 24RE5 phase and Mg 41Nd5 phase, the irregular island-shaped structure distributed around the grain boundary mainly consists of eutectic Mg 41Nd5 phase, and the room temperature mechanical property of the relative alloy is improved to a limited extent. The granular Mg 24RE5 phase is separated out along with the dynamic recrystallization process, and the short strip-shaped Mg-Y-Nd phase is discontinuously separated out at the grain boundary, and the granular Mg 24Y5 phase and the short strip-shaped Mg-Y-Nd phase act together at the moment, so that the strength of the alloy is greatly improved. Based on the principle of complex strengthening of multiple rare earth, the increase of the precipitation efficiency of alloy precipitated phases and the refinement of crystal grains are main reasons for improving the mechanical properties of Mg-Y-Nd- (Gd) -Zr alloy. The solid solution strengthening effect of Y is more obvious than that of the traditional Al and Zn, and meanwhile, the rare earth element also has excellent precipitation strengthening effect. Nd is believed to have the greatest effect on improving the performance of heavy rare earth magnesium alloy systems. The diffusion coefficient of Nd in magnesium is small, the recrystallization process can be slowed down, the thermal stability of desolventizing phase is increased, and meanwhile, the formed second phase can pin grain boundaries to block dislocation movement. The addition of Zr can produce remarkable refining effect on the extruded structure of the magnesium alloy. The addition of Gd brings the following benefits to the alloy: (1) enhanced phase density; (2) the microstructure is thinned to a certain degree; (3) a reduction in brittle eutectic phase; (4) The large-size sharp blocks are reduced, and the mechanical properties of the component modified alloy are obviously improved. Therefore, grains can be refined by regulating and controlling the Gd content, and meanwhile, the advanced precipitated intermetallic phases in the microstructure are finer, more in number and more uniform in distribution.
(4) Compared with the prior art adopting common continuous casting, the invention adopts electromagnetic continuous casting, and has the advantages mainly in the following aspects: the electromagnetic pressure, the metallostatic pressure and the additional pressure caused by the surface tension of the liquid metal can be balanced, and the non-contact casting is realized. The surface of the cast ingot is smooth, and the surface roughness can reach about 0.65 mu m. The surface of the common continuous casting ingot has obvious segregation tumor, and sometimes has defects of cold shut, strain and the like. The dendrite is easy to break along with the electromagnetic stirring effect in the electromagnetic casting process, so that a large number of new crystal nuclei are formed, and grains are refined. The casting speed is high, which is improved by 10-30% compared with the common continuous casting method, and the production efficiency is improved. In addition, as a plurality of ingot test bars can be machined from the existing electromagnetic continuous casting ingot at one time for the subsequent back extrusion process, compared with the common ingot cast at one time, the production efficiency is high.
(5) Compared with the alloy bar obtained by forward extrusion in the prior art, the invention adopts backward extrusion and has the advantages that: under the same extrusion condition, the cast ingot and the extrusion cylinder are free from friction, the required extrusion pressure is much smaller than the forward extrusion, and the extrusion force is irrelevant to the length of the cast ingot, so that the extrusion bar with longer length can be obtained, the backward extrusion speed is higher, and the production efficiency is high. Compared with forward extrusion, the extrusion bar obtained by backward extrusion can effectively refine grains, balance the flowability of the material, eliminate the defects of air holes, looseness and the like in a tissue, and improve the mechanical property and corrosion resistance of the material.
(6) Compared with cold drawing in the prior art, the invention adopts hot drawing, and has the advantages that: in the cold drawing process, with the increase of the pass deformation, the work hardening effect of the alloy wire is enhanced, the position density in the internal deformation structure is increased, so that the shaping and toughness of the alloy wire are reduced, and frequent intermediate annealing is required to promote the deformation structure to recover and recrystallize to adjust the strength and the toughness, so as to ensure continuous wire breakage in the drawing process. The alloy wire prepared by cold drawing is difficult to process, easy to break, low in production efficiency and low in elongation. The forming temperature of the hot drawing process is higher, so that the plastic deformation capacity of the magnesium alloy is increased, intermediate annealing is not needed, and cracks are not easy to generate in the drawing process, thereby greatly improving the production efficiency. The alloy wire prepared by hot drawing has better surface quality and higher elongation, so that the wire has better corrosion resistance and knotting performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a Mg-4Y-2Nd-1Gd-0.5Zr magnesium alloy suture with a diameter of 0.2mm prepared in example 1.
FIG. 2 shows the microstructure of the Mg-4Y-2Nd-1Gd-0.5Zr alloy after being drawn in example 1.
FIG. 3 is a polarization curve of the Mg-4Y-2Nd-1Gd-0.5Zr alloy prepared in example 1 in SBF simulated body fluid.
FIG. 4 shows the expression of the genes related to inflammation of the Mg-4Y-2Nd-1Gd-0.5Zr alloy wire leaching solution prepared in example 1.
FIG. 5 is a knotted pattern of Mg-4Y-3Nd-0.5Zr magnesium alloy suture lines with a diameter of 0.2mm prepared in example 2.
FIG. 6 shows the microstructure of the Mg-4Y-3Nd-0.5Zr alloy after being drawn in example 2.
FIG. 7 is a polarization curve of the Mg-4Y-3Nd-0.5Zr alloy prepared in example 2 in SBF simulated body fluid
FIG. 8 shows the cartilage related gene expression of the Mg-4Y-3Nd-0.5Zr alloy wire leaching solution prepared in example 2.
Detailed Description
The technical solutions and the technical problems to be solved in the embodiments of the present invention will be described below in conjunction with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, of the embodiments of the present patent.
Example 1: mg-4Y-2Nd-1Gd-0.5Zr
(1) The required alloy components are weighed according to the weight percentage of 4wt.% of Y,2wt.% of Nd,1wt.% of Gd,0.5wt.% of Zr and the balance of Mg, wherein the purity of magnesium ingots is more than or equal to 99.99%, the purity of Mg-Y master alloy is more than or equal to 99.99%, the purity of Mg-Nd master alloy is more than or equal to 99.99%, and the purity of Mg-Gd master alloy is more than or equal to 99.99%. The purity of the Mg-Zr intermediate alloy is more than or equal to 99.99 percent.
(2) After the surface of the raw material is polished clean, firstly adding a high-purity magnesium ingot into a melting furnace for melting, and then, in the volume ratio SF 6：CO2 =1: and (3) under the protection of 99 high-purity gas, sequentially adding Mg-Zr, mg-Y, mg-Nd and Mg-Gd intermediate alloy, heating to 730-750 ℃, preserving heat for 15-30min, cooling to 700-720 ℃, preserving heat for 20min, casting, flowing the molten metal into a crystallizer through a guide pipe below a melting furnace under the action of gas pressure, applying an intermediate frequency electromagnetic field of 2.5kHz and 10kW in the casting process, wherein the speed of a casting machine is 0.8mm/s, the stable pulling speed is 1.02mm/s, the strength of cooling water is 1.0t/h, the size of a final cast ingot is 120mm in diameter, and the height is 500mm.
(3) And homogenizing the cast ingot, wherein the heat preservation temperature is 450 ℃, the heat preservation time is 24 hours, and air cooling is performed to room temperature after heat preservation. And processing the homogenized cast ingot into a cast ingot with the diameter of 40mm and the length of 20mm, performing back extrusion processing, wherein the extrusion temperature is 460 ℃, the extrusion speed is 10mm/s, the extrusion ratio is 25, back extruding a bar with the diameter of 8mm, and performing hot drawing after machining into a bar with the diameter of 6mm and the length of 300 mm.
(4) Annealing is carried out at 350 ℃/15min before hot drawing, the drawing speed is 3m/min, and the drawing temperature is 300 ℃. The wire diameter is larger than 1.0mm, the drawing speed is accelerated by adopting 10% pass deformation, the wire diameter is smaller than 1.0mm, the wire breakage is prevented by adopting 5% pass deformation, and the annealing is performed at 425 ℃/30min after the wire diameter of 0.2mm is finally obtained.
FIG. 1 shows the morphology of the prepared Mg-4Y-2Nd-1Gd-0.5Zr biomedical degradable absorption magnesium alloy suture. The Mg-4Y-2Nd-1Gd-0.5Zr alloy obtained by the steps is tested to obtain the alloy with room temperature tensile strength of not less than 340MPa, yield strength of not less than 292MPa, elongation of not less than 20 percent and corrosion rate of not less than 0.3Mg cm -2·day-1 in 37 ℃/SBF simulated body fluid. FIG. 2 shows the microstructure of the Mg-4Y-2Nd-1Gd-0.5Zr alloy after being drawn. FIG. 3 is a polarization curve of the prepared Mg-4Y-2Nd-1Gd-0.5Zr wire in SBF simulated body fluid, the corrosion potential E corr of the alloy wire is 1.53V, the corrosion current I corr is on the order of 10 -4, and the alloy wire has smaller corrosion tendency in SBF simulated body fluid.
FIG. 4 shows the expression of the genes related to the inflammation of the prepared Mg-4Y-2Nd-1Gd-0.5Zr biomedical degradable absorption magnesium alloy suture line extract. The experiments were divided into three groups, namely normal P2 generation pig Chondrocyte (CHON), inflammatory chondrocyte model (LPS+CHON), and inflammatory chondrocyte (Mg+LPS+CHON) after adding Mg-4Y-2Nd-1Gd-0.5Zr alloy wire leaching solution for 48 hours. Experimental results show that the relative expression level of the TNF-alpha and IL-1 beta inflammatory genes of the pig chondrocyte added with LPS is obviously higher than that of a normal pig chondrocyte; the relative expression quantity of inflammatory chondrocyte TNF-alpha and IL-1 beta inflammatory genes after the treatment of the Mg-4Y-2Nd-1Gd-0.5Zr alloy wire leaching solution is obviously reduced. The result shows that the leaching solution of the Mg-4Y-2Nd-1Gd-0.5Zr alloy wire can reduce the inflammatory reaction of P2 generation pig chondrocytes.
Example 2: mg-4Y-3Nd-0.5Zr
(1) The required alloy components are weighed according to the weight percentage content of 4wt.% of Y,3wt.% of Nd,0.5wt.% of Zr and the balance of Mg, wherein the purity of magnesium ingots is more than or equal to 99.99%, the purity of Mg-Y intermediate alloy is more than or equal to 99.99%, and the purity of Mg-Nd intermediate alloy is more than or equal to 99.99%. The purity of the Mg-Zr intermediate alloy is more than or equal to 99.99 percent.
(2) After the surface of the raw material is polished clean, firstly adding a high-purity magnesium ingot into a melting furnace for melting, and then, in the volume ratio SF 6：CO2 =1: and (3) sequentially adding Mg-Zr and Mg-Y, mg-Nd intermediate alloy under the protection of high-purity gas, heating to 730-750 ℃, preserving heat for 15-30min, cooling to 700-720 ℃, preserving heat for 20min, casting, enabling molten metal to flow into a crystallizer through a guide pipe below a melting furnace under the action of gas pressure, applying an intermediate frequency electromagnetic field of 2.5kHz and 10kW in the casting process of the crystallizer, wherein the speed of a casting machine is 0.8mm/s, the stable pulling speed is 1.02mm/s, the cooling water strength is 1.0t/h, the final ingot size is 120mm in diameter and the height is 500mm.
(3) And homogenizing the cast ingot, wherein the heat preservation temperature is 450 ℃, the heat preservation time is 24 hours, and air cooling is performed to room temperature after heat preservation. And processing the homogenized cast ingot into a cast ingot with the diameter of 40mm and the length of 20mm, performing back extrusion processing, wherein the extrusion temperature is 460 ℃, the extrusion speed is 10mm/s, the extrusion ratio is 25, back extruding a bar with the diameter of 8mm, and performing hot drawing after machining into a bar with the diameter of 6mm and the length of 300 mm.
(4) Annealing is carried out at 350 ℃/15min before hot drawing, the drawing speed is 3m/min, and the drawing temperature is 300 ℃. The wire diameter is larger than 1.0mm, the drawing speed is accelerated by adopting 10% pass deformation, the wire diameter is smaller than 1.0mm, the wire breakage is prevented by adopting 5% pass deformation, and the annealing is performed at 425 ℃/30min after the wire diameter of 0.2mm is finally obtained.
FIG. 5 shows the knotted morphology of the prepared Mg-4Y-3Nd-0.5Zr biomedical degradable absorbing magnesium alloy suture. The Mg-4Y-3Nd-0.5Zr alloy obtained by the steps is tested to obtain the alloy with room temperature tensile strength of not less than 326Mpa, yield strength of not less than 287Mpa and elongation of not less than 20%. In example 2, the strength was decreased compared with example 1, since Gd element was not added. FIG. 6 shows the microstructure of the Mg-4Y-3Nd-0.5Zr alloy after being drawn. FIG. 7 is a polarization curve of a prepared Mg-4Y-3Nd-0.5Zr wire in SBF simulated body fluid, the corrosion potential E corr of the alloy wire is 1.55V, the corrosion current I corr is on the order of 10 -4, and the corrosion rate in 37 ℃/SBF simulated body fluid is less than or equal to 0.35Mg cm -2·day-1.
FIG. 8 shows the cartilage related gene expression of Mg-4Y-3Nd-0.5Zr alloy suture extract. The relative expression quantity of the pig chondrocyte COL2 added with LPS and the MMP13 cartilage related genes is obviously higher than that of normal pig chondrocyte, and the cartilage matrix destruction can lead to the increase of the expression of the chondrocyte COL2 genes, the MMP13 is matrix metalloproteinase, and the increase of the gene expression indicates the increase of the cartilage matrix destruction; the relative expression level of inflammatory chondrocyte COL2 and MMP13 cartilage related genes after the treatment of the Mg-4Y-3Nd-0.5Zr alloy wire leaching solution is obviously reduced. The result shows that the leaching solution of the Mg-4Y-3Nd-0.5Zr alloy wire can effectively protect cartilage stromal cells.
Comparative example 1Mg-4Y-2Nd-1Gd-0.5Zr
The alloy composition and preparation process are the same as in example 1, except that the electromagnetic casting in step (2) is changed into common resistance furnace smelting:
(2) Firstly, adding a high-purity magnesium ingot into a high-purity graphite crucible for melting, and then, at a volume ratio SF 6：CO2 =1: and adding Mg-Zr, mg-Y, mg-Nd and Mg-Gd intermediate alloy one by one under the protection of 99 high-purity gas, heating to 730-750 ℃, preserving heat for 15-30min, cooling to 700-720 ℃ and preserving heat for 20min for casting, wherein a water-cooling stainless steel die or a water-cooling copper die is adopted as a casting die, and SF 6+CO2 mixed gas is used for protecting melt in the smelting and casting process.
The Mg-4Y-2Nd-1Gd-0.5Zr alloy obtained by the steps is tested to obtain the alloy with room temperature tensile strength of equal to or greater than 297MPa, yield strength of equal to or greater than 245MPa, elongation of equal to or greater than 16%, and corrosion rate in 37 ℃/SBF simulated body fluid of equal to or less than 0.83Mg cm -2·day-1. The method shows that the suture obtained by smelting the magnesium alloy through a common resistance furnace and finally through the procedures of back extrusion, hot drawing and the like has lower strength and elongation, and the corrosion resistance of the obtained suture is much lower than that of the suture through an electromagnetic continuous casting technology, and the electromagnetic continuous casting technology can refine grains to a great extent and eliminate the tissue defects such as looseness, shrinkage cavity and the like. Can also reduce impurities and improve the surface quality, so that the alloy material is more suitable for the medical field.
Comparative example 2Mg-4Y-2Nd-1Gd-0.5Zr
The alloy composition and preparation process were the same as in example 1, except that step (3) was forward extruded:
(3) And homogenizing the cast ingot, wherein the heat preservation temperature is 450 ℃, the heat preservation time is 24 hours, and air cooling is performed to room temperature after heat preservation. And processing the homogenized cast ingot into a cast ingot with the diameter of 40mm and the length of 20mm, then performing forward extrusion processing, wherein the extrusion temperature is 460 ℃, the extrusion speed is 10mm/s, the extrusion ratio is 25, the rod with the diameter of 8mm is forward extruded, and the rod with the diameter of 6mm and the length of 300mm is subjected to hot drawing after being machined.
The Mg-4Y-2Nd-1Gd-0.5Zr alloy obtained by the steps is tested to obtain the alloy with room temperature tensile strength of not less than 316MPa, yield strength of not less than 279MPa, elongation of not less than 16 percent and corrosion rate of not less than 0.67Mg cm -2·day-1 in 37 ℃/SBF simulated body fluid. The suture obtained through forward extrusion has lower tensile strength than that obtained through backward extrusion, has smaller influence on yield strength, and has lower elongation and corrosion resistance, because the backward extrusion can refine grains more effectively than the forward extrusion, balance the fluidity of the material, eliminate the defects of air holes, looseness and the like in the tissue, and further improve the mechanical property and the corrosion resistance of the material.
Comparative example 3Mg-4Y-2Nd-1Gd-0.5Zr
The alloy composition and preparation process were the same as in example 1, except that step (4) was cold drawn:
(4) Annealing at a speed of 350 ℃/15min before cold drawing, wherein the drawing speed is 3m/min. The wire diameter is larger than 1.0mm, the drawing speed is increased by adopting 10% pass deformation, the wire diameter is smaller than 1.0mm, the wire breakage is prevented by adopting 5% pass deformation, the stress relief annealing is carried out at 350 ℃/15min after each 3 passes of drawing, and the annealing is carried out at 425 ℃/30min after the wire diameter of 0.2mm is finally obtained.
The Mg-4Y-2Nd-1Gd-0.5Zr alloy obtained by the steps is tested to obtain the alloy with room temperature tensile strength of not less than 350MPa, yield strength of not less than 314MPa, elongation of not less than 10%, and corrosion rate in 37 ℃/SBF simulated body fluid of not less than 0.23Mg cm -2·day-1. It is explained that by cold drawing, a higher tensile and yield strength than hot drawing can be obtained, but the final elongation is far lower than that of a suture obtained by a hot drawing process, because the forming temperature of the hot drawing process is higher, the plastic deformation capability of the magnesium alloy is increased, and cracks are not easy to generate in the drawing process.
Comparative example 4Mg-4Y-2Nd-1Gd
The alloy composition preparation process was the same as in example 1, except that the alloy composition of step (1) was changed:
(1) The required alloy components are weighed according to the weight percentage of 4wt.% of Y,2wt.% of Nd,1wt.% of Gd and the balance of Mg, wherein the purity of magnesium ingots is more than or equal to 99.99%, the purity of Mg-Y intermediate alloy is more than or equal to 99.99%, the purity of Mg-Nd intermediate alloy is more than or equal to 99.99%, and the purity of Mg-Gd intermediate alloy is more than or equal to 99.99%.
The Mg-4Y-2Nd-1Gd alloy obtained by the steps is tested to obtain the alloy with the room temperature tensile strength of not less than 313MPa, the yield strength of not less than 277MPa, the elongation of not less than 18%, and the corrosion rate of 37 ℃ per SBF simulated body fluid of not less than 0.89Mg cm -2·day-1. The method shows that the strength and the elongation of the suture line obtained after the Zr content in the alloy is changed are reduced, the corrosion resistance of the suture line is greatly influenced, and the corrosion rate is increased.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (5)
1. The degradable and absorbable magnesium alloy suture is characterized in that the element composition of the suture is Mg-Y-Nd-Gd-Zr, gd is selectively added, and the mass percentage of each element is as follows: 2.0-5.0% of Y, 1.0-3.0% of Nd, 0-2.0% of Gd, 0.01-1% of Zr and the balance of Mg;
The preparation method of the degradable and absorbable magnesium alloy suture comprises the following steps:
(1) Pretreatment: weighing the required raw materials according to the content of each element, and polishing by using sand paper to remove an oxide layer on the metal surface;
(2) Electromagnetic continuous casting: placing the pretreated raw material into a melting furnace, heating and melting the raw material, and obtaining an ingot through medium-high frequency electromagnetic continuous casting;
(3) Homogenizing: air cooling is carried out after the ingot is insulated;
(4) And (3) back extrusion: performing back extrusion on the cast ingot to obtain an alloy bar;
(5) Hot drawing deformation: machining the alloy bar, annealing before drawing, and performing hot drawing at 200-400 ℃;
(6) Annealing after drawing: drawing to obtain a wire material according to the final manufacturing requirement of the wire material, and annealing;
The electromagnetic continuous casting process of the step (2) comprises the following steps: firstly, adding a high-purity magnesium ingot into a melting furnace for melting, and then, at a volume ratio SF 6：CO2 =1: 99, sequentially adding Mg-Zr, mg-Y, mg-Nd and Mg-Gd intermediate alloy under the protection of high-purity gas, heating to 730-750 ℃, preserving heat for 15-30min, cooling to 700-720 ℃, preserving heat for 20min, casting, flowing molten metal into a crystallizer through a guide pipe below a melting furnace under the action of gas pressure, applying an intermediate frequency electromagnetic field of 2.5kHz and 10kW in the casting process of the crystallizer, wherein the speed of a casting machine is 0.8mm/s, the stable pulling speed is 1.02mm/s, the strength of cooling water is 1.0t/h, the size of a final cast ingot is 120mm in diameter and 500mm in height;
The hot drawing process in the step (5) is as follows: machining the extruded alloy bar, taking out a round bar with the diameter of 6mm and the length of 200-500mm, annealing for 15-30min at the annealing temperature of 300-500 ℃, carrying out hot drawing, wherein the drawing temperature is 200-400 ℃, the drawing speed is 1-10m/min, the wire diameter is larger than 1.0mm, the 10% -15% pass deformation is adopted to accelerate the drawing speed, the wire diameter is smaller than 1.0mm, the 5% pass deformation is adopted to prevent wire breakage, a tubular heating furnace is clamped on a fixed head on a drawing machine, the tubular heating furnace is opened, the experimental temperature is set to be 200-400 ℃, the temperature in the drawing bar and the tubular heating furnace is measured by using thermocouple heat, and drawing is carried out until the drawn bar reaches the experimental temperature.
2. The degradable absorbing magnesium alloy suture of claim 1, wherein the diameter is 0.1-0.3mm.
3. The degradable and absorbable magnesium alloy suture line according to claim 1, wherein the homogenization treatment in the step (3) has a heat preservation range of 200-500 ℃ and a heat preservation time of 5-32 hours, and is air-cooled to room temperature after heat preservation.
4. The degradable absorbing magnesium alloy suture of claim 1, wherein the back extrusion process of step (4) is: the diameter of the cast ingot is 35-40mm, the length is 15-30mm, the extrusion temperature is 400-500 ℃, the extrusion speed is 1-8mm/s, the extrusion ratio is 16-25, and the bar with the diameter of 8-10mm is reversely extruded.
5. The degradable absorbing magnesium alloy suture line according to claim 1, wherein the annealing is performed after the wire material with the diameter of 0.3mm to 0.1mm is drawn in the step (6), the annealing temperature is 300-500 ℃, and the annealing time is 15-30min.
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| CN104451303A (en) * | 2014-12-03 | 2015-03-25 | 东南大学 | Biomedical magnesium alloy and preparation method and application of biomedical magnesium alloy wire |
| CN104480330A (en) * | 2014-12-11 | 2015-04-01 | 江阴宝易德医疗科技有限公司 | Ultrafine twin-crystal deformed magnesium alloy profile as well as preparation method and application of ultrafine twin-crystal deformed magnesium alloy profile |
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| CN106086563A (en) * | 2016-08-05 | 2016-11-09 | 沈阳明腾科技有限公司 | A kind of high-strength temperature-resistant cast magnesium alloy and preparation method thereof |
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| CN104451303A (en) * | 2014-12-03 | 2015-03-25 | 东南大学 | Biomedical magnesium alloy and preparation method and application of biomedical magnesium alloy wire |
| CN104480330A (en) * | 2014-12-11 | 2015-04-01 | 江阴宝易德医疗科技有限公司 | Ultrafine twin-crystal deformed magnesium alloy profile as well as preparation method and application of ultrafine twin-crystal deformed magnesium alloy profile |
| CN112322948A (en) * | 2020-10-14 | 2021-02-05 | 中国兵器科学研究院宁波分院 | Magnesium alloy and preparation method thereof |
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