CN116920180B - Degradable metal material and preparation method and application thereof - Google Patents

Degradable metal material and preparation method and application thereof Download PDF

Info

Publication number
CN116920180B
CN116920180B CN202311188138.4A CN202311188138A CN116920180B CN 116920180 B CN116920180 B CN 116920180B CN 202311188138 A CN202311188138 A CN 202311188138A CN 116920180 B CN116920180 B CN 116920180B
Authority
CN
China
Prior art keywords
degradable
metal
phase
acid
drug
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202311188138.4A
Other languages
Chinese (zh)
Other versions
CN116920180A (en
Inventor
宋亚欣
贺伟
施腾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lepu Medical Technology Beijing Co Ltd
Original Assignee
Lepu Medical Technology Beijing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lepu Medical Technology Beijing Co Ltd filed Critical Lepu Medical Technology Beijing Co Ltd
Priority to CN202311188138.4A priority Critical patent/CN116920180B/en
Publication of CN116920180A publication Critical patent/CN116920180A/en
Application granted granted Critical
Publication of CN116920180B publication Critical patent/CN116920180B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/02Inorganic materials
    • A61L31/022Metals or alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/08Materials for coatings
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/08Materials for coatings
    • A61L31/10Macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148Materials at least partially resorbable by the body
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials 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
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16Biologically active materials, e.g. therapeutic substances
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/04Making ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/20Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
    • A61L2300/216Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/416Anti-neoplastic or anti-proliferative or anti-restenosis or anti-angiogenic agents, e.g. paclitaxel, sirolimus
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/02Methods for coating medical devices
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/06Coatings containing a mixture of two or more compounds

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • Engineering & Computer Science (AREA)
  • Public Health (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Epidemiology (AREA)
  • General Health & Medical Sciences (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Molecular Biology (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention provides a degradable metal material, a preparation method and application thereof, and relates to the field of metals, wherein the degradable metal material comprises the following chemical components in percentage by mass: c:0.05% -0.55%; si:0.07% -0.37%; mn:0.50% -1.80%; cr is less than or equal to 0.5%; ni is less than or equal to 0.5%; cu is less than or equal to 0.5%; the balance being Fe and unavoidable impurities. The degradable metal is prepared by smelting and molding the raw materials at 1100-1600 ℃ according to the proportion, and can be applied to manufacturing vascular stents, intestinal implants and orthopedic implants. According to the invention, by introducing the second phase of the alloy element, the mechanical parameters of the degradable metal material are effectively controlled, so that the early mechanical properties of the degradable metal material can be maintained, the degradation can be gradually carried out in the later stage, and the controllable corrosion of the degradable metal material in a preset period is satisfied.

Description

Degradable metal material and preparation method and application thereof
Technical Field
The invention relates to the field of metal materials, in particular to a degradable metal material and a preparation method and application thereof.
Background
The implant intervention is one of the important means for treating vascular diseases, bone diseases, injuries and other diseases, and the vascular stent and the bone internal fixation implant are key vascular implants and orthopedic implants and are used for assisting the repair and treatment of blood vessels and bones, so that the performance requirements are high and the functional requirements are diversified.
At present, the implant is mainly made of inert materials represented by titanium, alloys thereof, stainless steel and the like, although the materials are mature in clinical application, the materials can block and delay tissue healing in vivo after achieving the aim of treatment due to the characteristics of non-degradability and/or biocompatibility, rejection reaction can occur, medical examination and treatment can be influenced, and the permanent implant needs to be taken out by secondary operation after the temporary fixing and supporting functions are finished, so that research and development of degradable metal materials which can be automatically digested after the completion of service are new targets. The ideal degradable metallic implant should provide better physiological repair, local vascular remodeling, short-term longitudinal and radial straightening, the possibility of growth and post-revascularization, and be detectable by MRI and IVUS at follow-up without affecting vascular reshaping.
Magnesium alloys were first considered as degradable metallic material stents, whose main components are magnesium, aluminum or other alloying elements and small amounts of rare earth metals (Ce, pr, nd). The magnesium alloy can meet the requirements of biocompatibility, mechanical strength and degradation speed, and animal (pig) tests show that the inflammatory reaction is very small, no thrombus is formed, but obvious intimal cell proliferation is also observed. The more important problem of magnesium alloy is that the corrosion rate in human body is too fast, which results in limited application, as clinical data published by Biotronik corporation shows that bare magnesium alloy stents disappear in blood vessels for less than 2 months, which leads to restenosis of blood vessels.
Recent reports indicate that the iron stent is used for vascular stents, has good biocompatibility, is used as a trace nutrient element necessary for a human body, takes part in oxygen transmission and tissue respiration in the human body, has far less manufacturing difficulty than magnesium alloy, and does not have the problems of low strength, poor plasticity, too fast absorption and the like of the magnesium alloy. For example, the medical stainless steel vascular stent disclosed in the prior art has excellent mechanical properties, but is also more corrosion-resistant, i.e. does not have expected degradation characteristics, and cannot meet the requirement of controllable degradation rate of implant materials.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defect of slow degradation rate of the ferroalloy bracket in the prior art, thereby providing the degradable metal material with high mechanical strength and good degradation performance.
In one aspect, the present invention provides a degradable metallic material, comprising the chemical components in mass percent: c:0.05% -0.55%; si:0.07% -0.37%; mn:0.50% -1.80%; cr is less than or equal to 0.5%; ni is less than or equal to 0.5%; cu is less than or equal to 0.5%; p is less than or equal to 0.1 percent; s is less than or equal to 0.1 percent; the balance being Fe and unavoidable impurities.
Optionally, the degradable metallic material comprises the following chemical components: c:0.47% -0.55%; si:0.17% -0.37%; mn:0.50% -0.80%; cr:0.02% -0.25%; ni:0.02% -0.25%; cu:0.02% -0.25%; p:0.05% -0.035%; s:0.05% -0.040%; the balance being Fe and unavoidable impurities.
The structure of the degradable metal material comprises a two-phase alloy, wherein the two-phase alloy comprises a first phase and a second phase distributed on the surface of the first phase, the particle size of the second phase is 0.5-7.0 mu m, and the number of particles under the 2500X visual field of a metallographic microscope is 700-1500.
The particle size in the second phase is 1.5-3.5 mu m, and the number of particles is 200-400 under the 2500X field of a metallographic microscope.
The texture of the degradable metallic material further comprises a coating, and the coating is arranged on the surface of the second phase. The coating comprises a degradable carrier and a drug in a mass ratio of 1-4:1-4.
The degradable carrier is selected from polylactic acid, racemized polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate, polyacrylate, polyethylene succinate, polycarbonate and polyether ester.
The medicine is at least one of rapamycin and paclitaxel.
On the other hand, the invention also provides a preparation method of the degradable metal material. The preparation method of the degradable metal material comprises the following steps: s1, smelting and molding the raw materials at 1100-1600 ℃ according to the proportion.
Further comprising step S2: and (3) rolling the steel ingot prepared in the step (S1) into a plate, annealing at 400-700 ℃ for 1-5 h, and manufacturing the annealed plate into a required implant structure.
Further comprising step S3: and (3) tempering the implant structure prepared in the step (S2), wherein the tempering temperature is above 150 ℃ and the tempering time is 0.5-10 h.
Further comprising step S4: the implant structure produced in step S2 or step S3 is subjected to a polishing treatment.
The annealing temperature is 500-600 ℃. The tempering temperature is 550-650 ℃.
In the step S4, electrolytic polishing is adopted, and the polishing solution is prepared by mixing at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, hydrofluoric acid, citric acid, chromic acid and glacial acetic acid with at least one of ethylene glycol and pure water.
The temperature of the polishing solution is 40-90 ℃, and the polishing time is 10 s-10 min.
Further comprising step S5: coating the polished surface of the implant structure with a coating material.
In the step S4, the polishing solution used includes: the mass ratio is 6-8: 3-4: 4-6 parts of phosphoric acid, sulfuric acid and ethylene glycol; and/or coating the coating material in the step S5 by adopting a spraying mode, wherein the advancing speed of the spraying machine is 0.01-0.07 mL/min.
The coating material comprises a degradable carrier and a medicament in a mass ratio of 1-4:1-4, wherein the degradable carrier is at least one of polylactic acid, racemized polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate, polyacrylate, polyethylene succinate, polycarbonate and polyether ester, and the medicament is at least one of rapamycin and paclitaxel.
The degradable metal material or the degradable metal material prepared by the preparation method can be applied to the preparation of vascular stents, intestinal implants and orthopedic implants.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the invention provides a degradable metal material, which comprises the following chemical components in percentage by mass: c:0.05% -0.55%; si:0.07% -0.37%; mn:0.50% -1.80%; cr is less than or equal to 0.5%; ni is less than or equal to 0.5%; cu is less than or equal to 0.5%; the balance being Fe and unavoidable impurities. According to the invention, the alloy elements are introduced on the basis of the iron base material, and the content of the alloy elements is higher than the solubility of the alloy elements in the iron base material, so that the mechanical parameters of the degradable metal material can be effectively controlled, the early mechanical properties of the degradable metal material can be maintained, and the degradation of the degradable metal material can be gradually degraded in the later period, so that the controllable degradation of the degradable metal in a certain period is satisfied.
2. The structure of the degradable metal material provided by the invention comprises a two-phase alloy, wherein the two-phase alloy comprises a first phase and a second phase distributed on the surface of the first phase, the particle size of the second phase is 0.5-7.0 mu m, and the number of particles under the 2500X field of a metallographic microscope is 700-1500. According to the invention, the second phase of the alloy element is introduced into the surface of the iron element support structure, the size and the number of particles distributed on the second phase of the surface of the first phase are limited, the mechanical parameters of the degradable metal material are effectively controlled, the atomic arrangement on the formed two-phase alloy phase interface is not provided with lattice integrity, the phase interface can prevent dislocation from sliding, so that the material is reinforced, the integral strength and the integral hardness of the material are increased, the difference exists between crystal grains on the formed second phase and the components of the base material, the combination among the crystal grains can be destroyed under the action of the phase interface stress, and the corrosion rate of the degradable metal material is improved.
3. The degradable metal material provided by the invention can be provided with a coating on the surface, the coating comprises a carrier and a drug carried by the carrier, the drug carried by the carrier can be rapamycin or paclitaxel which can inhibit excessive proliferation of endothelium and prevent restenosis, and the drug carried by the carrier can not only realize the drug carrying function, but also improve the biocompatibility of the degradable metal material and promote the degradation of the degradable material. Wherein, the higher the drug content, the higher the degree of endothelialization (vascular tissue coating stent) in vivo, the thicker the endothelium, and the relatively slower the degradation; the larger the amount of carrier, the faster the scaffold degrades. The invention defines the mass ratio of the carrier to the drug carried, and further controls the degradation of the degradable metallic material. The amount of the drug and the carrier can be controlled by controlling the thickness variation ratio through the process, so that the degradation rate of the degradable metal material in the body can be cooperatively controlled.
4. The invention provides a preparation method of a degradable metal material, which comprises the steps of smelting and molding raw materials at 1100-1600 ℃ according to a proportion. The invention forms degradable metal with certain degradation rate and certain mechanical property by smelting elements with specific components and specific content, and forms two-phase alloy by annealing the formed iron-based alloy to generate crystal grains on the surface of the first phase. The degradable metal formed after annealing causes the internal local plastic deformation or local relaxation of the iron-based alloy to relax residual stress due to the change of the particle size, the number and the distribution of the formed second phase particles, so that part of internal stress is eliminated, the whole hardness is reduced, the possibility of partial stress corrosion is eliminated, and the corrosion resistance is restored to a certain extent; when the annealed degradable metal is tempered, particles are rapidly cooled after high-temperature tempering, the crystal grain structure is restored, and the crystal grains are distributed along the crystal boundary, so that the integral strength and plasticity of the material are comprehensively optimized by controlling the distribution of the microstructure of the second-phase crystal grains, the change of mechanical property and corrosion property is controlled, the balance of the strength and corrosion rate of the degradable metal material is realized, and good degradation rate can be provided while the strength is ensured.
5. According to the preparation method of the degradable metal material, the degradable metal material is polished after tempering to further control the corrosion rate of the matrix, and the prepared degradable metal material is polished to remove defects such as pits, protrusions, inclusions and cracks on the surface of the material, reduce the activation energy of the surface of the material, reduce the surface area, further reduce corrodible sites, reduce the tendency of pitting, ensure the strength in service and avoid the error of the corrosion rate caused by the pitting problem.
6. The degradable metal prepared by the invention can further control the degradation rate of the degradable metal by coating the surface of the implant structure and arranging the degradable carrier and the drug, so as to be matched with the service time of the implant structure, limit the advancing speed of the carrier and the drug-carried mixed solution sprayed on the degradable metal material, control the uniformity of the coating on the degradable metal, ensure the uniformity of each position of the degradable metal during degradation, control the finally sprayed carrier and drug quantity by the final wall thickness of the bracket, and observe and judge the uniformity of the carrier and the drug by means of a light mirror and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a microscopic view of the annealed degradable metallic stent of example 1 of the present invention at 2500X field of view;
FIG. 2 is a graph showing the mechanical properties of the annealed degradable sheet metal material of example 1 of the present invention;
FIG. 3 is a microscopic view of the degradable metallic stent of example 1 of the present invention at 2500X field of view after tempering;
FIG. 4 is an electrochemical polarity profile of a post-polishing degradable metal stent prepared in example 1 of the present invention;
FIG. 5 shows the surface morphology of the metal matrix after the degradable metallic material prepared in example 1 of the present invention is immersed in vitro for 28 days to produce corrosion products;
FIG. 6 is a surface morphology of a metal matrix after the drug-loaded degradable metal material prepared in example 1 of the present invention is immersed in vitro for 28 days to produce corrosion products;
FIG. 7 is a one month OCT scan of the drug-free degradable metallic stent prepared in example 1 of the present invention after implantation in pig right coronary artery LCX;
FIG. 8 is a one month OCT scan of the drug-loaded metal stent prepared in example 1 of the present invention after implantation in the right coronary artery RCA of a pig;
fig. 9 is a tissue section taken out after the drug-loaded metal stent prepared in example 1 of the present invention is implanted in an animal.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The invention discloses a degradable metal material, which enhances the integral strength by introducing a second phase, ensures that a matrix material can be controllably corroded within a preset period of time, and ensures that the matrix material can be gradually degraded in the later stage while keeping the early mechanical property under a specified scene. The degradable metal material can be manufactured into different forms such as wires, sheets, blocks, plates and the like to adapt to the use requirements of different scenes. Taking a plate as an example, the plate can be manufactured into a metal bracket with degradable property through mechanical mortise and tenon joint, welding and other processes so as to meet the treatment requirement.
By introducing alloying elements C, si, mn, cu, ni, cr, P and S in the material, a second phase particle dispersed phase is introduced at the metal surface. The alloying element is dissolved in the base metal atom, and at this ratio, a second phase occurs due to the high content so as to exceed its solubility, forming a two-phase alloy. The atomic arrangement at the interface between the two phases no longer has lattice integrity, and the phase interface can hinder dislocation slip, thereby strengthening the material and increasing the overall strength and hardness of the metallic material. While the presence of the second phase increases the tendency of intergranular corrosion thereof compared to the matrix material without alloying elements introduced. Due to the composition difference of the second phase particles and the matrix, the existence of internal stress of the phase interface damages the combination among the particles, and the corrosion, namely the degradation rate of the material is improved to a certain extent. By adjusting the processing and treatment processes of the degradable metal material and adjusting the morphology, distribution and size of the second phase particles, stable balance can be achieved between the overall strength and degradation speed of the material, so that good degradation speed is provided while the strength is ensured, and the requirements are met.
After the metal component is smelted into molten steel, the molten steel is cast into steel ingots, and the steel ingots are formed through different forming processes. Taking a rolling process as an example, under the action of external force of rolling, grains on the surface of the material are extruded and elongated to cause deformation and even crushing, so that the motion capability of dislocation is further hindered, the overall hardness and strength are greatly improved, the plasticity of the material is reduced, residual stress is generated in the material, the stress corrosion phenomenon is increased, the corrosion resistance of the material is reduced, and the later-stage processing or service period reduction is not easy.
Based on the above, the invention carries out annealing treatment on the rolled material, and the annealing temperature in the step is 500-650 ℃. In the temperature range, the partial plastic deformation or partial relaxation process inside the material relaxes the residual stress, so that partial internal stress is eliminated, the overall hardness is reduced, the possibility of partial stress corrosion is eliminated, and the corrosion resistance is restored to a certain extent. Before tempering, the second particles exist in the microstructure, but the size is larger, no obvious crystal grains are observed, at this time, the hardness and strength performance of the prepared material are lower, and after the structure (the structure can be a vascular stent, an intestinal implant or an orthopedic implant) with corresponding requirements is prepared, the structure is tempered. After tempering, the grain boundary is obvious, so that the integral strength is improved, and meanwhile, the second phase particles are finer and distributed along the grain boundary, so that dislocation movement is hindered, the integral strength is further improved, the elongation is reduced, the corrosion rate is increased to a certain extent by the obvious grain boundary, and the strength is improved to a larger extent. In the present invention, the tempering temperature is 400 to 700 ℃. After tempering, the second phase particles of the microstructure are refined and distributed along the grain boundary, so that the strength and plasticity of the whole material are comprehensively optimized. Meanwhile, by adjusting the tempering temperature, duration time and cooling mode, the microstructure distribution of the material can be controlled and regulated, so that the change of mechanical property and corrosion property is controlled, and the overall performance can meet the actual requirements of various different use scenes.
To further control the corrosion rate of the substrate, the present invention polishes the resulting structure, primarily by mechanical polishing, chemical polishing, electrolytic polishing, to remove surface defects such as pits, protrusions, inclusions, cracks, and the like. By removing the defects, the activation energy of the whole surface is reduced, meanwhile, the surface area is reduced, corrodible sites are reduced, the tendency of pitting corrosion is reduced, and the strength in service is ensured to a certain extent. The polishing time, the components of the polishing solution used in chemical and electrolytic polishing and the temperature are adjusted, so that the overall degradation corrosion performance is controllable and adjustable. The polishing solution can be prepared by mixing at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, hydrofluoric acid, citric acid, chromic acid and glacial acetic acid with at least one of ethylene glycol and purified water. Taking the prepared metal bracket as an example, the polishing effect can be controlled by the wall thickness of the prepared bracket, and the observation and judgment can be carried out by using means such as a light mirror and the like.
The degradable polymer coating has good biocompatibility, wherein the degradable polymer carrier can be at least one of polylactic acid, racemized polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate, polyacrylate, polyethylene succinate, polycarbonate and polyether ester. It can carry medicine, raise its biocompatibility and promote the degradation of metal structure. Taking the prepared metal stent as an example, the carried medicament can be rapamycin or taxol, can inhibit the excessive proliferation of endothelium and can prevent restenosis to a certain extent. The drug content and the carrier amount on the final stent can be regulated and controlled by adjusting the mixture ratio of the two, so that the degradation of the metal stent can be controlled. Meanwhile, the uniformity of the coating on the bracket can be controlled by adjusting the advancing speed of the spraying machine when the degradable polymer carrier and the carried medicine mixed solution are sprayed, so that the uniformity of each position in degradation is ensured. The final sprayed carrier and medicine amount can be controlled by the final wall thickness of the bracket, and the uniformity of the carrier and medicine amount can be judged by observing through means such as a light mirror.
The test methods in terms of mechanical properties, degradation and electrochemical properties, biocompatibility and the like of the materials used in the following examples are as follows;
1. the mechanical property-tensile strength and elongation test method comprises the following steps:
according to GB/T228.1-2010 section 1 Metal Material tensile test: in annex B, annex C and annex D in room temperature test method, annealed degradable sheet metal samples are manufactured into proper sizes. Taking a plate as an example, the annealed degradable metal plate is cut into a tensile sample with the width of 12.5mm, the original gauge length is 50mm, the tensile speed is set to be 5mm/min, and the tensile strength and the elongation rate of the degradable metal plate are measured.
2. The degradation and electrochemical performance test method comprises the following steps:
taking a metal bracket made of degradable metal as an example, the degradation performance test method comprises the following steps: the stent is ultrasonically cleaned by purified water for 5 to 10 minutes, the cleaning power is 500W, the absolute ethyl alcohol is used for ultrasonic cleaning for 5 to 10 minutes after impurities are washed off, the cleaning power is 500W, and then the air gun is used for drying residual ethyl alcohol on the surface for 3 to 5 minutes. After preparation, the cleaned stent is recorded with an initial mass M 0 Fully immersing the configured PBSSoaking and culturing in the solution at 37+ -1deg.C. Taking out the bracket according to different set time nodes, ultrasonically cleaning the bracket with 3wt% tartaric acid solution for 3-5 min to wash away corrosion products on the surface of the bracket, exposing the metal matrix, and recording the quality M after cleaning with purified water and absolute ethyl alcohol 1 And calculating the mass loss rate of the bracket, wherein the formula is as follows:
W=(M 0 -M 1 )/M 0 ×100%;
w is the mass loss rate of the bracket;
M 1 -the mass of the remaining non-corroding degraded metal stent matrix;
M 0 -initial mass of the metal stent matrix.
Regarding electrochemical performance, polarization curves of the degradable metallic materials in PBS solution at 37 ℃ were measured with a prinston P4000 electrochemical workstation. The test adopts a standard three-electrode system, a sample to be tested exposed in the solution is a working electrode, a saturated calomel electrode is a reference electrode, and a platinum electrode is a counter electrode. The test of the polarization curve is carried out under the open circuit potential, after the working electrode is soaked in PBS solution at 37 ℃ until the open circuit potential is stable, the potential test range is set to be plus or minus 600 and mV relative to the open circuit potential, and the potential scanning rate is set to be 0.1 mV/s. The exposed area of the working electrode is measured by using a Kihnshi VHX7000 ultra-depth-of-field microscope, and the test result is analyzed by using Origin software, so that the corrosion potential E of the degradable metal material in PBS solution at 37 ℃ can be obtained c And corrosion current density I c
3. Method for testing biocompatibility:
the biocompatibility of the application of the degradable metal material is mainly determined by implanting the prepared structure into an animal body for service and observing the endothelialization effect of the structure. After the structure with corresponding requirements is prepared (the structure can be a vascular stent, an intestinal implant or an orthopedic implant), the sterilization treatment is carried out to meet the sterile requirements, and the structure is implanted into the corresponding use position in the animal body. Taking a metal stent made of degradable metal material as an example, implanting the sterilized stent into a left anterior descending LAD, a left circumflex branch LCX or a right coronary artery RCA of an animal, performing Optical Coherence Tomography (OCT) scanning on a blood vessel implanted with the stent at different set time points, and observing endothelialization conditions of the blood vessel.
4. Wall thickness testing method:
the measurements were observed under a super depth of field microscope. The structure takes a metal bracket as an example, a measuring point is respectively selected at two ends and the middle section of the bracket, the wall thickness of the bracket is measured, and the average value is obtained for recording. For the stent with the degradable polymer drug-carrying coating, the selection mode of the measuring position is unchanged, the edge of the drug coating is required to be distinguished and clear during measurement, the error is avoided being larger, and the number of measuring points can be increased if necessary.
Example 1
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: c:0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. And smelting the metal component to form molten steel, and preparing a steel ingot after the smelting temperature is 1600 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 650 ℃ for 2 hours. After annealing, the microstructure of the plate at 2500X is observed, as shown in figure 1, the size of the second phase particles on the surface of the plate is 0.5-3.2 mu m, and the number of the second phase particles in the field of view is 900-1000. While no significant grains are observed in this field of view, possibly due to grain breakage after rolling. The performance was tested by the above test method, and the measured mechanical properties are shown in FIG. 2. The tensile strength of the component plate after annealing is 1237MPa, and the elongation is 1.33%. The performance is tested by the detection mode, the corrosion potential of the annealed component plate is-0.67V, and the corrosion current is 9.33 multiplied by 10 -5 A·cm -2 . Meanwhile, compared with pure iron, the plate manufactured by the embodiment improves the corrosion rate and the application possibility of the plate serving as a degradable metal material.
In example 1, a plate material was welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 700 ℃ and the tempering time is 1h. The microstructure of the treated metal stent surface at 2500X is shown in FIG. 3, and the second phase particles are observed on the surface, and the second phase particles are composed of metal carbide. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 1.5-2.2 mu m. The number of crystal grains in the view field is 300-400, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
The mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol is 6:3:4 preparing polishing solution, and carrying out electrolytic polishing on the metal bracket with the surface oxide removed at the temperature of 68 ℃ for 43s, wherein the wall thickness of the bracket is 66 mu m. Mechanical property detection is carried out on the polished degradable metal bracket, and the tensile strength of the metal bracket is 792MPa, and the elongation percentage is 5.69%. The performance is tested by the detection mode, the electrochemical polarization curve is shown in figure 4, the corrosion potential of the metal bracket is-0.75V, and the corrosion current is 1.72 multiplied by 10 -4 A·cm -2 . FIG. 5 shows the surface morphology of the metal matrix after 28 days of in vitro soaking degradation of the metal stent to remove corrosion products, and it can be observed that corrosion products adhere to a portion of the surface, and the rest of the stent is the corroded metal matrix, but no obvious corrosion products are found. FIG. 6 shows the surface morphology of the metal matrix after 28 days of in vitro soaking degradation to remove corrosion products. Compared with the bare stent of fig. 5 without drug, fig. 6 can observe that corrosion products are attached to the whole surface, which proves the effect of the carrier on the degradation rate of the matrix.
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug is rapamycin, and the mass ratio of the polymer carrier to the drug is 1:1, the propelling speed of the spraying machine is 0.030mL/min. The wall thickness of the sprayed drug stent is 73 μm. Fig. 7 shows OCT scan results one month after implantation of the drug-loaded metal stent into the right coronary artery RCA of a pig, and fig. 8 shows OCT scan results one month after implantation of the drug-free bare metal stent into the right coronary artery LCX of a pig. Compared with the polymer, the degradable polymer drug-loaded coating can promote endothelialization to a certain extent, and the biocompatibility is improved. From fig. 9, it was observed that tissue sections of the drug-loaded metal stent after degradation have good endothelialization at the degradation site, further indicating excellent biocompatibility of the degradation product.
Example 2
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: c:0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. And smelting the metal component to form molten steel, and preparing a steel ingot after the smelting temperature is 1600 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 650 ℃ for 1.5 hours. After annealing, the microstructure of the plate at 2500X is observed, the size of second phase particles on the surface of the plate is 0.9-3.8 mu m, the number of second phase particles in the field of view is 700-900, and meanwhile, no obvious crystal grains are observed in the field of view, which is probably caused by the breakage of the crystal grains after rolling. The mechanical properties measured by the test mode are as follows: the tensile strength was 1068MPa and the elongation was 2.01%. After the test mode is used for testing the performance and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is-0.52V and the corrosion current is 6.75X10 -5 A·cm -2
In this embodiment, the plate material is welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 700 ℃ and the tempering time is 1h. The microstructure of the surface of the treated metal stent at 2500X, and second phase particles can be observed on the surface. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 1.7-2.9 mu m. The number of crystal grains in the view field is 250-360, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
The mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol is 8:3: and 6, preparing a polishing solution, and electropolishing the metal bracket with the surface oxide removed at 67 ℃ for 50s. The wall thickness of the polished metal stent measured by the above-mentioned detection method was 69. Mu.m. The mechanical property curve of the metal bracket measured by the detection mode is as follows: the tensile strength was 715MPa and the elongation was 6.87%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the metal bracket is minus 0.69V, and the corrosion current is 1.24 multiplied by 10 -4 A·cm -2
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug is rapamycin, and the ratio of the polymer carrier to the drug is 1:1, the propelling speed of the spraying machine is 0.030mL/min. The wall thickness of the sprayed metal bracket measured by the detection mode is 74 mu m.
Example 3
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: c:0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. And smelting the metal component to form molten steel, and preparing a steel ingot after the smelting temperature is 1600 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 650 ℃ for 1h. After annealing, the microstructure of the plate at 2500X is observed, the size of second phase particles on the surface of the plate is 1.4-5.3 mu m, the number of second phase particles in the field of view is 600-850, and meanwhile, no obvious crystal grains are observed in the field of view, which is probably caused by the breakage of the crystal grains after rolling. The mechanical properties measured by the test mode are as follows: tensile strength of 994MPa and elongation of 2.74%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is-0.42V, and the corrosion current is 3.83 multiplied by 10 -5 A·cm -2
In this embodiment, the plate material is welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 700 ℃ and the tempering time is 2 hours. The microstructure of the surface of the treated metal stent at 2500X, and second phase particles can be observed on the surface. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 2.2-3.7 mu m. The number of crystal grains in the view field is 200-350, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
The mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol is 6:4: and 6, preparing a polishing solution, and electropolishing the metal bracket with the surface oxide removed at the temperature of 68 ℃ for 40 seconds. The wall thickness of the polished metal stent measured by the above-mentioned detection method was 68. Mu.m. The mechanical property curve of the metal bracket measured by the detection mode is as follows: the tensile strength was 667MPa and the elongation was 7.09%. After the performance is tested by the detection mode and the electrochemical polarization curve is converted, the corrosion potential of the metal bracket is minus 0.64V, and the corrosion current is 9.97X10 -5 A·cm -2
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug carried by the degradable polymer drug-carrying coating is rapamycin, and the ratio of the polymer carrier to the drug is 1:1, the propelling speed of the spraying machine is 0.030mL/min. The wall thickness of the sprayed metal stent is 71 mu m measured by the detection mode.
Example 4
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: 0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. And smelting the metal component to form molten steel, and preparing a steel ingot after the smelting temperature is 1600 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 500 ℃ for 2 hours. After annealing, the microstructure of the plate at 2500X is observed, the size of second phase particles on the surface of the plate is 0.5-3.2 mu m, the number of second phase particles in the field of view is 900-1000, and meanwhile, no obvious crystal grains are observed in the field of view, which is probably caused by the breakage of the crystal grains after rolling. The mechanical properties measured by the test mode are as follows: the tensile strength was 1237MPa and the elongation was 1.33%. After the test mode is used for testing the performance and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is minus 0.67V, and the corrosion current is 9.33 multiplied by 10 -5 A·cm -2
In this embodiment, the plate material is welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 600 ℃ and the tempering temperature is 1h. The microstructure of the surface of the treated metal stent at 2500X, and second phase particles can be observed on the surface. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 2.3-3.1 mu m. The number of crystal grains in the view field is 250-350, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
The mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol is 6:3:4 preparing polishing solution, and carrying out electrolytic polishing on the metal bracket after removing the surface oxide at the temperature of 68 ℃ for 45s. The polished metal bracket is measured by the detection modeThe wall thickness was 69. Mu.m. The mechanical property curve of the metal bracket measured by the detection mode is as follows: the tensile strength was 704MPa and the elongation was 6.11%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the metal bracket is minus 0.84V, and the corrosion current is 2.31 multiplied by 10 -4 A·cm -2
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug is rapamycin, and the ratio of the polymer carrier to the drug is 1:1, the propelling speed of the spraying machine is 0.030mL/min. The wall thickness of the sprayed metal bracket measured by the detection mode is 75 mu m.
Example 5
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: c:0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. And smelting the metal component to form molten steel, and preparing a steel ingot after the smelting temperature is 1600 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 500 ℃ for 1.5 hours. After annealing, the microstructure of the plate at 2500X is observed, the size of second phase particles on the surface of the plate is 0.5-3.2 mu m, the number of second phase particles in the field of view is 900-1000, and meanwhile, no obvious crystal grains are observed in the field of view, which is probably caused by the breakage of the crystal grains after rolling. The mechanical properties measured by the test mode are as follows: the tensile strength was 1237MPa and the elongation was 1.33%. After the test mode is used for testing the performance and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is minus 0.67V, and the corrosion current is 9.33 multiplied by 10 -5 A·cm -2
In this embodiment, the plate material is welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 600 ℃ and the tempering temperature is 1h. The microstructure of the surface of the treated metal stent at 2500X, and second phase particles can be observed on the surface. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 2.5-3.5 mu m. The number of crystal grains in the view field is 200-350, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
The mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol is 8:3:4 preparing polishing solution, and carrying out electrolytic polishing on the metal bracket with the surface oxide removed under the condition that the temperature of the polishing solution is 68 ℃ for 40s. The wall thickness of the polished metal stent measured by the above-mentioned detection method was 64. Mu.m. The mechanical property curve of the metal bracket measured by the detection mode is as follows: the tensile strength was 673MPa and the elongation was 6.83%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the metal bracket is minus 0.89V, and the corrosion current is 2.85 multiplied by 10 -4 A·cm -2
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug is rapamycin, and the ratio of the polymer carrier to the drug is 1:1, the propelling speed of the spraying machine is 0.030mL/min. The wall thickness of the sprayed metal bracket measured by the detection mode is 77 mu m.
Example 6
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: c:0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. And smelting the metal component to form molten steel, and preparing a steel ingot after the smelting temperature is 1600 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 500 ℃ for 1h. Back outThe microstructure of the plate at 2500X is observed after fire, the second phase particle size of the surface is 0.5-3.2 mu m, the number of the second phase particles in the field of view is 900-1000, and meanwhile, no obvious crystal grains are observed in the field of view, which is probably caused by the breakage of the crystal grains after rolling. The mechanical properties measured by the test mode are as follows: the tensile strength was 1237MPa and the elongation was 1.33%. After the test mode is used for testing the performance and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is minus 0.67V, and the corrosion current is 9.33 multiplied by 10 -5 A·cm -2
In this embodiment, the plate material is welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 600 ℃, and the tempering time is 2 hours. The microstructure of the surface of the treated metal stent at 2500X, and second phase particles can be observed on the surface. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 1.5-2.2 mu m. The number of crystal grains in the view field is 300-400, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
Preparing polishing solution according to the mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol of 6:3:4, and carrying out electrolytic polishing on the metal bracket with the surface oxide removed for 54s when the temperature of the polishing solution is 60 ℃. The wall thickness of the polished metal stent measured by the above-mentioned detection method was 61. Mu.m. The mechanical property curve of the metal bracket measured by the detection mode is as follows: the tensile strength was 786MPa and the elongation was 5.57%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the metal bracket is minus 0.81V, and the corrosion current is 1.99X10 -4 A·cm -2
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug is rapamycin, and the ratio of the polymer carrier to the drug is 1:1, the propelling speed of the spraying machine is 0.030mL/min. The wall thickness of the sprayed metal bracket measured by the detection mode is 68 mu m.
Example 7
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: c:0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. And smelting the metal component to form molten steel, and preparing a steel ingot after the smelting temperature is 1600 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 550 ℃ for 2 hours. After annealing, the microstructure of the plate at 2500X is observed, the size of second phase particles on the surface of the plate is 0.5-3.2 mu m, the number of second phase particles in the field of view is 900-1000, and meanwhile, no obvious crystal grains are observed in the field of view, which is probably caused by the breakage of the crystal grains after rolling. The mechanical properties measured by the test mode are as follows: the tensile strength was 1237MPa and the elongation was 1.33%. After the test mode is used for testing the performance and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is minus 0.67V, and the corrosion current is 9.33 multiplied by 10 -5 A·cm -2
In this embodiment, the plate material is welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 500 ℃, and the tempering time is 1h. The microstructure of the surface of the treated metal stent at 2500X, and second phase particles can be observed on the surface. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 1.5-2.2 mu m. The number of crystal grains in the view field is 300-400, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
The mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol is 8:3:4 preparing polishing solution, and carrying out electrolytic polishing on the metal bracket with the surface oxide removed for 120s when the temperature of the polishing solution is 60 ℃. The wall thickness of the polished metal stent measured by the above-mentioned detection method was 53. Mu.m. The mechanical property curve of the metal bracket measured by the detection mode is as follows: the tensile strength was 739MPa and the elongation was 5.86%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the metal bracket is minus 0.94V, and the corrosion current is 2.51 multiplied by 10 -4 A·cm -2
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug is rapamycin, and the ratio of the polymer carrier to the drug is 1:1, the propelling speed of the spraying machine is 0.030mL/min. The wall thickness of the sprayed metal stent is 59 μm measured by the detection method.
Experimental example 8
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: c:0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. The metal component is smelted to form molten steel, and a steel ingot is prepared after the smelting temperature is 1100 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 400 ℃ for 5 hours. After annealing, the microstructure of the plate at 2500X is observed, the size of second phase particles on the surface of the plate is 0.5-3.2 mu m, the number of second phase particles in the field of view is 900-1000, and meanwhile, no obvious crystal grains are observed in the field of view, which is probably caused by the breakage of the crystal grains after rolling. The mechanical properties measured by the test mode are as follows: the tensile strength was 1237MPa and the elongation was 1.33%. Testing performance by the detection mode, and obtaining the corrosion electricity after annealing the component plate after the electrochemical polarization curve conversion data bit-0.67V, corrosion current 9.33X10 -5 A·cm -2
In this embodiment, the plate material is welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 250 ℃, and the tempering time is 6 hours. The microstructure of the surface of the treated metal stent at 2500X, and second phase particles can be observed on the surface. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 1.5-2.2 mu m. The number of crystal grains in the view field is 300-400, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
Preparing polishing solution according to the mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol of 8:4:4, and carrying out electrolytic polishing on the metal bracket with the surface oxide removed for 5min when the temperature of the polishing solution is 40 ℃. The wall thickness of the polished metal stent measured by the above-mentioned detection method was 68. Mu.m. The mechanical property curve of the metal bracket measured by the detection mode is as follows: the tensile strength was 786MPa and the elongation was 5.57%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the metal bracket is minus 0.81V, and the corrosion current is 1.99X10 -4 A·cm -2
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug is rapamycin, and the ratio of the polymer carrier to the drug is 2:1, the propelling speed of the spraying machine is 0.070mL/min. The wall thickness of the sprayed metal bracket measured by the detection mode is 74 mu m. And in vitro degradation tests observe that the generation of stent corrosion products is accelerated, and the whole surface of the matrix is coated in the vicinity of 21 days.
Example 9
The embodiment provides a preparation method of a degradable metal material, which comprises the following specific steps and parameters:
the degradable metal material comprises the following components: c:0.51%; si:0.27%; mn:0.60%; p: 0.022; s:0.030%; cr:0.20%; ni:0.23%; cu:0.19%; fe and unavoidable impurities. The metal component is smelted to form molten steel, and steel ingot is prepared after the smelting temperature is 1400 ℃. And (3) rolling to form a plate, rolling to form a steel strip, and simultaneously annealing at 700 ℃ for 3 hours. After annealing, the microstructure of the plate at 2500X is observed, the size of second phase particles on the surface of the plate is 0.5-3.2 mu m, the number of second phase particles in the field of view is 900-1000, and meanwhile, no obvious crystal grains are observed in the field of view, which is probably caused by the breakage of the crystal grains after rolling. The mechanical properties measured by the test mode are as follows: the tensile strength was 1237MPa and the elongation was 1.33%. After the test mode is used for testing the performance and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is minus 0.67V, and the corrosion current is 9.33 multiplied by 10 -5 A·cm -2
In this embodiment, the plate material is welded into a metal bracket. 5 metal brackets are manufactured by adopting the same material and the same process, and tempering heat treatment is carried out on the metal brackets. The tempering heat treatment temperature is 150 ℃ and the tempering time is 10 hours. The microstructure of the surface of the treated metal stent at 2500X, and second phase particles can be observed on the surface. The second phase particles are more uniformly distributed and have smaller size differences than the annealed sheet, while distinct grains are observed. It is analyzed that the grain refinement is due to rapid cooling after high temperature tempering, and at the same time, the grain structure morphology is recovered, which illustrates that tempering can control the second phase distribution, size and grain size to some extent. The size of the structural grains is 1.5-2.2 mu m. The number of crystal grains in the view field is 300-400, and the recovery of the crystal boundary is favorable for improving the integral mechanical strength.
The mass ratio of phosphoric acid, hydrochloric acid and ethylene glycol is 6:4: and 6, preparing polishing solution, and carrying out electrolytic polishing on the metal bracket after removing the surface oxide for 10min when the temperature of the polishing solution is 90 ℃. The wall thickness of the polished metal stent measured by the above-mentioned detection method was 72. Mu.m. The metal bracket is detected by the detection modeThe measured mechanical properties were as follows: the tensile strength was 786MPa and the elongation was 5.57%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the metal bracket is minus 0.81V, and the corrosion current is 1.99X10 -4 A·cm -2
In this example, the post-polishing metal stent is drug-sprayed. The degradable polymer carrier in the degradable polymer drug-carrying coating is polylactic acid, the drug is rapamycin, and the ratio of the polymer carrier to the drug is 3:1, the propelling speed of the spraying machine is 0.010mL/min. The wall thickness of the sprayed metal bracket measured by the detection mode is 79 mu m. And in vitro degradation tests observe that the generation of stent corrosion products is accelerated, and the whole surface of the matrix is coated in the vicinity of 18 days.
Comparative example 1
The comparative example provides a metal stent having substantially the same preparation method as in example 1, except that the stent is made of pure iron. The pure iron ingot is rolled to form a plate, then curled into a strip, and simultaneously annealed at 500 ℃. After annealing the microstructure of the plate was observed at 2500X, the surface of which was free of second phase particles. While no significant grains are observed in this field of view, possibly due to grain breakage after rolling. The mechanical properties measured by the test mode are as follows: the tensile strength was 258MPa and the elongation was 31%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is minus 0.59V, and the corrosion current is 8.26 multiplied by 10 -5 A·cm -2 . Therefore, compared with the degradable metal material, the pure iron has the advantages of improved corrosion resistance, greatly reduced strength and incapability of meeting the use requirement.
Comparative example 2
The comparative example provides a metal stent that is prepared in substantially the same manner as in example 1, except that the stent annealing temperature is 750 ℃. After annealing, the microstructure of the plate at 2500X is observed, the second phase particles on the surface of the plate are rapidly reduced to less than 100, and obvious particles are observed in the field of viewLarge grains and smaller grains, probably due to annealing reaching the recrystallization temperature, cause the grains originally broken by rolling to re-nucleate and grow to produce new recrystallized grains. The larger inter-grain gap may be due to the fact that the original second phase grains promote recrystallization, so that the second phase grains are preferentially nucleated and have a higher speed, and the size difference exists among the grains. The mechanical properties measured by the test mode are as follows: the tensile strength was 542MPa and the elongation was 0.96%. After the test mode is used for testing the performance and the data is converted by the electrochemical polarization curve, the corrosion potential of the annealed component plate is-0.62V, and the corrosion current is 8.94 multiplied by 10 -5 A·cm -2 . Therefore, when the annealing temperature is too high for the same degradable metal material, the recrystallization process occurs, so that the second phase particles can be reduced to further enhance the corrosion resistance, but the strength and the elongation are greatly reduced due to the enlarged crystal grains, and the use requirement cannot be met.
Comparative example 3
The comparative example provides a metal stent having substantially the same preparation as example 1, except that the stent has a tempering temperature of 100 c, and the microstructure of the surface of the metal stent after tempering at 2500X is such that particles of the second phase are observed on the surface. The second phase particles are more uniformly distributed and more numerous than the annealed sheet, and the analysis is due to the increased degree of grain refinement after tempering. However, the low-temperature tempering leads to higher overall hardness, the elongation is lower than 3.64%, and the welded part is likely to be broken more easily, which is not beneficial to the subsequent practical use. And (3) removing surface oxides, and then electropolishing the metal stent, wherein the wall thickness of the polished metal stent is 71 mu m. The metal bracket manufactured by the method has the advantages that the cracking condition of the welding part is obviously increased when the metal bracket is used, and the defect of low-temperature tempering is further verified.
Comparative example 4
The comparative example provides a metal stent having substantially the same preparation method as in example 1, except that the stent polishing time was 5s. The wall thickness of the polished metal stent measured by the above-mentioned detection method was 98. Mu.m. Warp-up of metal supportThe mechanical property curve measured by the detection mode is as follows: the tensile strength was 729MPa and the elongation was 4.11%. After the performance is tested by the detection mode and the data is converted by the electrochemical polarization curve, the corrosion potential of the metal bracket is minus 0.89V, and the corrosion current is 2.31 multiplied by 10 -4 A·cm -2 . The polishing mode shortens the polishing time, so that the overall thickness of the support is increased, the final mechanical strength is improved, but burrs on the overall surface are more, the polishing is not carried out, and the follow-up use cannot be met.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (13)

1. A degradable metallic material, characterized in that the chemical composition of the degradable metallic material comprises, in mass percent:
c:0.05% -0.55%; si:0.07% -0.37%; mn:0.50% -1.80%; cr is less than or equal to 0.5%; ni is less than or equal to 0.5%; cu is less than or equal to 0.5%; p is less than or equal to 0.1 percent; s is less than or equal to 0.1 percent; the balance of Fe and unavoidable impurities;
the structure of the degradable metal material comprises a two-phase alloy, wherein the two-phase alloy comprises a first phase and a second phase distributed on the surface of the first phase, the particle size of the second phase is 0.5-7.0 mu m, and the number of particles under the 2500X visual field of a metallographic microscope is 700-1500.
2. The degradable metallic material according to claim 1, comprising the following chemical composition: c:0.47% -0.55%; si:0.17% -0.37%; mn:0.50% -0.80%; cr:0.02% -0.25%; ni:0.02% -0.25%; cu:0.02% -0.25%; p:0.05% -0.035%; s:0.05% -0.040%; the balance being Fe and unavoidable impurities.
3. The degradable metallic material according to claim 2, wherein the particle size in the second phase is 1.5 μm to 3.5 μm, and the number of particles is 200 to 400 under a 2500X field of a metallographic microscope.
4. The degradable metallic material according to claim 3, wherein the texture of the degradable metallic material further comprises a coating layer provided on the surface of the second phase.
5. The degradable metallic material according to claim 4, wherein the coating comprises a degradable carrier and a drug in a mass ratio of 1-4:1-4.
6. The degradable metallic material according to claim 5, wherein the degradable carrier is at least one of polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate, polyacrylate, polyethylene succinate, polycarbonate, polyether ester; and/or, the number of the groups,
the medicine is at least one of rapamycin and paclitaxel.
7. The method for preparing the degradable metal material according to any one of claims 1 to 6, comprising the steps of:
s1, smelting and molding the raw materials at 1100-1600 ℃ according to the proportion.
8. The method according to claim 7, further comprising step S2: and (3) rolling the steel ingot prepared in the step (S1) into a plate, annealing at 400-700 ℃ for 1-5 h, and manufacturing the annealed plate into a required implant structure.
9. The method of claim 8, further comprising step S3: tempering the implant structure prepared in the step S2, wherein the tempering temperature is above 150 ℃ and the tempering time is 0.5-10 h; and/or the number of the groups of groups,
Further comprising step S4: the implant structure produced in step S2 or step S3 is subjected to a polishing treatment.
10. The method according to claim 9, wherein the annealing temperature is 500-600 ℃; and/or, the tempering temperature is 550-650 ℃.
11. The method according to claim 10, wherein the step S4 is performed by electropolishing, and the polishing solution is prepared by mixing at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, perchloric acid, hydrofluoric acid, citric acid, chromic acid, glacial acetic acid, and at least one of ethylene glycol and pure water;
and/or the temperature of the polishing solution is 40-90 ℃, and the polishing time is 10 s-10 min; and/or the number of the groups of groups,
further comprising step S5: coating the polished surface of the implant structure with a coating material.
12. The method according to claim 11, wherein in the step S4, the composition of the polishing liquid used includes: the mass ratio is 6-8: 3-4: 4-6 parts of phosphoric acid, sulfuric acid and ethylene glycol; and/or coating the coating material in the step S5 in a spraying manner, wherein the propelling speed of the spraying machine is 0.01-0.07 mL/min; and/or the number of the groups of groups,
the coating material comprises a degradable carrier and a drug, wherein the mass ratio of the degradable carrier to the drug is 1-4:1-4, the degradable carrier is at least one of polylactic acid, polyglycolic acid, polycaprolactone, polyhydroxyalkanoate, polyacrylate, polyethylene succinate, polycarbonate and polyether ester, and the drug is at least one of rapamycin and paclitaxel.
13. Use of the degradable metallic material according to any one of claims 1 to 6 or the degradable metallic material produced by the production method according to any one of claims 7 to 12 for the production of vascular stents, intestinal implants, orthopedic implants.
CN202311188138.4A 2023-09-14 2023-09-14 Degradable metal material and preparation method and application thereof Active CN116920180B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311188138.4A CN116920180B (en) 2023-09-14 2023-09-14 Degradable metal material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311188138.4A CN116920180B (en) 2023-09-14 2023-09-14 Degradable metal material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN116920180A CN116920180A (en) 2023-10-24
CN116920180B true CN116920180B (en) 2023-12-15

Family

ID=88375666

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311188138.4A Active CN116920180B (en) 2023-09-14 2023-09-14 Degradable metal material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116920180B (en)

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5435824A (en) * 1993-09-27 1995-07-25 Crucible Materials Corporation Hot-isostatically-compacted martensitic mold and die block article and method of manufacture
JP2003193206A (en) * 2002-12-02 2003-07-09 Sumitomo Metal Ind Ltd Stainless steel for separator of polymer electrolyte fuel cell and polymer electrolyte fuel cell
JP2004011017A (en) * 2002-06-11 2004-01-15 Jfe Steel Kk Hot rolled steel sheet for rotary ironing, method for producing the same and automobile parts
CN101024870A (en) * 2006-02-24 2007-08-29 南阳二机石油装备(集团)有限公司 Low-temperature high-strength, high-toughness steel and preparing method therefor
JP2012097308A (en) * 2010-10-29 2012-05-24 Jx Nippon Mining & Metals Corp Copper alloy, copper rolled product, electronic component and connector
US8246767B1 (en) * 2005-09-15 2012-08-21 The United States Of America, As Represented By The United States Department Of Energy Heat treated 9 Cr-1 Mo steel material for high temperature application
JP2013064172A (en) * 2011-09-16 2013-04-11 Jfe Steel Corp Cold rolled high tensile strength steel sheet excellent in resistance to surface distortion, bake hardenability, and stretch flange formability, and method for producing the same
CN103210105A (en) * 2010-11-12 2013-07-17 杰富意钢铁株式会社 High-strength hot-dip galvanized steel sheet having excellent uniform elongation and plating properties, and method for manufacturing same
JP2013249501A (en) * 2012-05-31 2013-12-12 Kobe Steel Ltd High-strength cold-rolled steel plate with minimized dispersion of mechanical characteristics, and method for manufacturing the same
JP2016074965A (en) * 2014-10-09 2016-05-12 Jfeスチール株式会社 High strength cold rolled steel sheet, high strength plated steel sheet and manufacturing method for them
CN106668952A (en) * 2015-11-06 2017-05-17 万瑞飞鸿(北京)医疗器材有限公司 Multi-coating bio-degradable metal support and preparation method thereof
CN107778446A (en) * 2017-10-18 2018-03-09 圆容生物医药无锡有限公司 Degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break
WO2019045001A1 (en) * 2017-08-30 2019-03-07 新日鐵住金株式会社 Alloy plate and gasket
CN109717992A (en) * 2014-11-28 2019-05-07 先健科技(深圳)有限公司 Intraluminal stent prefabricated component and the intraluminal stent prepared by intraluminal stent prefabricated component
CN112891640A (en) * 2021-01-20 2021-06-04 湖南华锐科技集团股份有限公司 Zn-Mg series zinc alloy intravascular stent and preparation method thereof
CN115181917A (en) * 2021-04-02 2022-10-14 宝山钢铁股份有限公司 780 MPa-grade low-carbon low-alloy high-formability dual-phase steel and rapid heat treatment manufacturing method
WO2023109005A1 (en) * 2021-12-13 2023-06-22 莱芜钢铁集团银山型钢有限公司 56 kg-grade low-yield-ratio ultrahigh-strength maritime work steel plate and preparation method therefor
CN116688254A (en) * 2023-07-04 2023-09-05 苏州恒瑞宏远医疗科技有限公司 Degradable cavity support

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7294214B2 (en) * 2003-01-08 2007-11-13 Scimed Life Systems, Inc. Medical devices
US20070068605A1 (en) * 2005-09-23 2007-03-29 U.I.T., Llc Method of metal performance improvement and protection against degradation and suppression thereof by ultrasonic impact
DE102008002601A1 (en) * 2008-02-05 2009-08-06 Biotronik Vi Patent Ag Implant with a body made of a biocorrodible iron alloy
US20100217370A1 (en) * 2009-02-20 2010-08-26 Boston Scientific Scimed, Inc. Bioerodible Endoprosthesis
EP2399620B1 (en) * 2010-06-28 2016-08-10 Biotronik AG Implant and method for producing the same
JP5018935B2 (en) * 2010-06-29 2012-09-05 Jfeスチール株式会社 High-strength hot-dip galvanized steel sheet excellent in workability and manufacturing method thereof
WO2013059715A2 (en) * 2011-10-20 2013-04-25 Medtronic Vascular Inc. Iron based alloys for bioabsorbable stent
US20130243699A1 (en) * 2011-12-07 2013-09-19 Regents Of The University Of Minnesota Biodegradable Magnetic Nanoparticles and Related Methods
US9339401B2 (en) * 2013-03-08 2016-05-17 Abbott Laboratories Medical device utilizing a nickel-titanium ternary alloy having high elastic modulus
US10865465B2 (en) * 2017-07-27 2020-12-15 Terves, Llc Degradable metal matrix composite
CN106367714A (en) * 2015-07-24 2017-02-01 先健科技(深圳)有限公司 Iron-based absorbent implanting medical instrument, prefabricated tube, and production methods of medical instrument and prefabricated tube
US11969368B2 (en) * 2017-05-12 2024-04-30 Biotyx Medical (Shenzhen) Co., Ltd. Lumen stent and preform thereof, and methods for preparing the lumen stent and preform thereof
US20200232079A1 (en) * 2017-10-06 2020-07-23 Bio Dg, Inc. Fe-mn absorbable implant alloys with increased degradation rate
US20200254140A1 (en) * 2019-02-11 2020-08-13 Mirus Llc Alloy For Medical Device
TWI719767B (en) * 2019-12-19 2021-02-21 財團法人工業技術研究院 Biodegradable iron-based alloy composition, medical implant applying the same, and manufactruing method thereof
WO2021218089A1 (en) * 2020-04-30 2021-11-04 中科益安医疗科技(北京)股份有限公司 High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube
US20230113716A1 (en) * 2021-10-08 2023-04-13 Bio Dg, Inc. Alloy for inhibiting activity of bacterial collagenase and/or matrix metalloproteinase

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5435824A (en) * 1993-09-27 1995-07-25 Crucible Materials Corporation Hot-isostatically-compacted martensitic mold and die block article and method of manufacture
JP2004011017A (en) * 2002-06-11 2004-01-15 Jfe Steel Kk Hot rolled steel sheet for rotary ironing, method for producing the same and automobile parts
JP2003193206A (en) * 2002-12-02 2003-07-09 Sumitomo Metal Ind Ltd Stainless steel for separator of polymer electrolyte fuel cell and polymer electrolyte fuel cell
US8246767B1 (en) * 2005-09-15 2012-08-21 The United States Of America, As Represented By The United States Department Of Energy Heat treated 9 Cr-1 Mo steel material for high temperature application
CN101024870A (en) * 2006-02-24 2007-08-29 南阳二机石油装备(集团)有限公司 Low-temperature high-strength, high-toughness steel and preparing method therefor
JP2012097308A (en) * 2010-10-29 2012-05-24 Jx Nippon Mining & Metals Corp Copper alloy, copper rolled product, electronic component and connector
CN103210105A (en) * 2010-11-12 2013-07-17 杰富意钢铁株式会社 High-strength hot-dip galvanized steel sheet having excellent uniform elongation and plating properties, and method for manufacturing same
JP2013064172A (en) * 2011-09-16 2013-04-11 Jfe Steel Corp Cold rolled high tensile strength steel sheet excellent in resistance to surface distortion, bake hardenability, and stretch flange formability, and method for producing the same
JP2013249501A (en) * 2012-05-31 2013-12-12 Kobe Steel Ltd High-strength cold-rolled steel plate with minimized dispersion of mechanical characteristics, and method for manufacturing the same
JP2016074965A (en) * 2014-10-09 2016-05-12 Jfeスチール株式会社 High strength cold rolled steel sheet, high strength plated steel sheet and manufacturing method for them
CN109717992A (en) * 2014-11-28 2019-05-07 先健科技(深圳)有限公司 Intraluminal stent prefabricated component and the intraluminal stent prepared by intraluminal stent prefabricated component
CN106668952A (en) * 2015-11-06 2017-05-17 万瑞飞鸿(北京)医疗器材有限公司 Multi-coating bio-degradable metal support and preparation method thereof
WO2019045001A1 (en) * 2017-08-30 2019-03-07 新日鐵住金株式会社 Alloy plate and gasket
CN107778446A (en) * 2017-10-18 2018-03-09 圆容生物医药无锡有限公司 Degradation time is controllable, the adjustable medical degradable polyurethane of elongation at break
CN112891640A (en) * 2021-01-20 2021-06-04 湖南华锐科技集团股份有限公司 Zn-Mg series zinc alloy intravascular stent and preparation method thereof
CN115181917A (en) * 2021-04-02 2022-10-14 宝山钢铁股份有限公司 780 MPa-grade low-carbon low-alloy high-formability dual-phase steel and rapid heat treatment manufacturing method
WO2023109005A1 (en) * 2021-12-13 2023-06-22 莱芜钢铁集团银山型钢有限公司 56 kg-grade low-yield-ratio ultrahigh-strength maritime work steel plate and preparation method therefor
CN116688254A (en) * 2023-07-04 2023-09-05 苏州恒瑞宏远医疗科技有限公司 Degradable cavity support

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
影响新型低碳马氏体合金钢奥氏体晶粒的因素;赵艳君;孟庆雪;任学平;陈锡璋;冀红彦;;塑性工程学报(02);全文 *

Also Published As

Publication number Publication date
CN116920180A (en) 2023-10-24

Similar Documents

Publication Publication Date Title
US8137614B2 (en) Medical devices and method for making the same
Shih et al. Effect of surface oxide properties on corrosion resistance of 316L stainless steel for biomedical applications
O'Brien et al. A platinum–chromium steel for cardiovascular stents
US8372144B2 (en) Implant with a base body of a biocorrodible iron alloy
Moravej et al. Effect of electrodeposition current density on the microstructure and the degradation of electroformed iron for degradable stents
JP5153634B2 (en) Medical device having an alloy composition
CN110234366B (en) High-function bioabsorbable stent
CN102220529B (en) Mg-Zn-Y-Nd alloy for novel biodegradable vascular stents and preparation method thereof
Fakhar et al. A good combination of ductility, strength, and corrosion resistance of fine-grained ZK60 magnesium alloy produced by repeated upsetting process for biodegradable applications
EP1604691B1 (en) Biocompatible alloy for implantable medical devices
CN109602960B (en) Preparation method of medical zinc alloy bar with superplasticity
EP1604692B1 (en) Cobalt-nickel-chromium biocompatible alloy for implantable medical devices
Trepanier et al. Improvement of the corrosion resistance of NiTi stents by surface treatments
CA2526038A1 (en) A cobalt-chromium-molybdenum fatigue resistant alloy for intravascular medical devices
EP1657318A1 (en) Quaternary cobalt-nickel-chromium-molybdenum fatigue resistant alloy for intravascular medical devices
CN116920180B (en) Degradable metal material and preparation method and application thereof
CN111571128B (en) Preparation method of biodegradable superfine crystal magnesium alloy intravascular stent
EP3395971B1 (en) Alloy material and application thereof
Kao et al. Surface processing technology for 316LVM stainless steel stents
CN110042335A (en) It is a kind of for obtaining the treatment process of the low titanium-zirconium alloy of amount containing zirconium perfect recrystallization tissue
Yuan et al. Cold deformation behavior and microstructure evolution of biomedical Cu-containing L605 alloy
WO2023027012A1 (en) Cobalt-chromium alloy member, and method for producing same and device using same
CN117867325A (en) Degradable biomedical zinc alloy and preparation method and application thereof
CN117797328A (en) Degradable magnesium scandium shape memory alloy vascular stent and preparation method thereof
CN117165795A (en) Biomedical degradable Mn-based alloy and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant