CN109128064A - A kind of biodegradable Zn-Na system kirsite and preparation method thereof - Google Patents

A kind of biodegradable Zn-Na system kirsite and preparation method thereof Download PDF

Info

Publication number
CN109128064A
CN109128064A CN201811108848.0A CN201811108848A CN109128064A CN 109128064 A CN109128064 A CN 109128064A CN 201811108848 A CN201811108848 A CN 201811108848A CN 109128064 A CN109128064 A CN 109128064A
Authority
CN
China
Prior art keywords
kirsite
biodegradable
continuous casting
preparation
heat treatment
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.)
Granted
Application number
CN201811108848.0A
Other languages
Chinese (zh)
Other versions
CN109128064B (en
Inventor
石章智
刘雪峰
王鲁宁
于静
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.)
Beijing Shangning Kezhi Medical Instrument Co ltd
Original Assignee
University of Science and Technology Beijing USTB
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 University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to CN201811108848.0A priority Critical patent/CN109128064B/en
Publication of CN109128064A publication Critical patent/CN109128064A/en
Application granted granted Critical
Publication of CN109128064B publication Critical patent/CN109128064B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/11—Treating the molten metal
    • B22D11/114—Treating the molten metal by using agitating or vibrating means
    • B22D11/115—Treating the molten metal by using agitating or vibrating means by using magnetic fields
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/16—Biologically active materials, e.g. therapeutic substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/001—Continuous casting of metals, i.e. casting in indefinite lengths of specific alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
    • A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents

Landscapes

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

Abstract

A kind of biodegradable Zn-Na system kirsite, belongs to medical embedded material field.In alloy: Na is 0.01~0.97%.Reselection contains 27 kinds of harmless or beneficial at least one of elements.To reduce cost and obtaining excellent comprehensive performance, the total amount of the various alloying elements of optimal control addition is no more than 2.0%, surplus Zn.The kirsite prepares processing flow are as follows: continuous casting → hot extrusion → rolling, continuous casting → hot extrusion → solution heat treatment → drawing or continuous casting → homogenization heat treatment → hot extrusion → rolling.100~500MPa of yield strength of the kirsite, 150~700MPa of tensile strength, elongation percentage 1.5~100%；Degradation rate in simulated body fluid is no more than 0.8mm/；Cytotoxicity to L929 cell and human marrow mesenchymal stem cell is 0 grade or 1 grade, shows good biocompatibility, can be used for a variety of medical implants.

Description

A kind of biodegradable Zn-Na system kirsite and preparation method thereof
Technical field
The present invention relates to a kind of designs of the ingredient of biodegradable Zn-Na system kirsite, preparation method and application field, belong to In medical embedded material field.
Background technique
Zinc in world's metal production and consumption ranking first five, be mainly used for coating, casting alloy, battery, brass etc. Containing zinc products, most important purposes is the anticorrosion of steel.Zinc is the essential trace elements of the human body, be can be used as biodegradable Metal uses.But the tensile strength of zinc is only 120MPa, is unable to reach a variety of Medical implants and wants to material mechanical performance It asks, strongly limits use scope of the zinc as biodegradable metal.Zinc and kirsite are extremely brittle in as cast condition, and room temperature elongation percentage is logical Often it is lower than 3%, seriously limits their application.
Sodium (Na) is nutrient needed by human, is mainly distributed on blood and extracellular fluid in vivo, to maintenance body fluid Balance plays an important role, and also assists in the normal operation of muscle, heart and nerve.Human body Na content is 105 grams, under normal circumstances blood Liquid amount containing Na is 3.15~3.40 grams per liters.Human body is perspired via epidermis daily, urine and excreta are lost about 115 milligrams of Na.It builds The adult every 2.3 grams of Na of daily ingestion of view, children and teenager are 1.5~2.2 grams, main to be taken in by diet, especially salt.
Patent document 1 is disclosed containing strontium and sodium high abrasion high thermal conductivity kirsite and its processing technology, and ingredient is with quality % Meter: Na:0.8~1.2%, Sr:0.2~0.3%, In:4.5~6.3%, Zr:0.8~1.2%, Si:0.4~0.8%, Sn: 2.4~3.6%, Yb:0.2~0.5%, Nd:0.1~0.2%, S:0.8~1.0%, surplus are zinc.The tension of the kirsite is strong Degree is 580~720MPa, but patent document 1 does not provide the yield strength and elongation percentage of the kirsite.Contain in the kirsite Have a Yb, the compound of this element can eyes to people and skin cause to stimulate and may cause monster.Therefore, which cannot As medical embedded material.
Patent document 2 discloses cold stamping without spangle Na-Er-Mo allumen used for hot dip galvanizing, and ingredient is in terms of quality %: Na:0.5~0.6%, Mg:3.0~4.0%, Ca:1.5~1.8%, Al:25.0~28.0%, Se:0.1~0.2%, Er: 0.2~0.4%, B:0.1~0.2%, Mo:0.3~0.5%, surplus are zinc.The highest element of additive amount is in the kirsite Al, it may result in the nervous system disease.Therefore, which is not suitable as medical embedded material.
Patent document 3 discloses one kind magnesium alloy of fast degradation containing Na and preparation method thereof, and ingredient is in terms of quality %: Al:3.0~12%, Zn:0.5~5%, Cu:0.5~3%, Na:0.1~1.0%, remaining for Mg and inevitably it is miscellaneous Matter.The solvable bridge plug used for magnesium alloy used in oil-gas field fracturing construction.
Patent document 4 discloses a kind of aluminium alloy and preparation method thereof, and ingredient is in terms of quality %: Mg:0.55~ 0.65%, Mn:0.25~0.3%, Cr:0.1~0.2%, Si:0.7~0.75%, Fe:0.1~0.25%, Cu:0.4~ 0.45%, Ti:0.02~0.06%, Na:0.15~0.20%, surplus Al.Aluminium alloy corrosion resistance height, mouldability and the weldering Connecing property is excellent.
Existing technical literature
Patent document 1:CN108004432A, containing strontium and sodium high abrasion high thermal conductivity kirsite and its processing technology
Patent document 2:CN108396196A, cold stamping is without spangle Na-Er-Mo allumen used for hot dip galvanizing
Patent document 3:CN107523732A, one kind magnesium alloy of fast degradation containing Na and preparation method thereof
Patent document 4:CN104178668B, a kind of aluminium alloy and preparation method thereof
Summary of the invention
The present invention towards the problem of
Pure zinc intensity is low, it is difficult to adapt to requirement of a variety of medical embedded devices to material mechanical performance.Alloying combines system The optimization design of standby processing technology is to propose the effective means of high purity zinc mechanical property, at present the biodegradable kirsite of high-performance Type is less, far from meeting the market requirement.Development of new, high performance biodegradable kirsite are urgent need to resolve at this stage The problem of.
A kind of biodegradable Zn-Na system kirsite, it is characterised in that alloy composition is in terms of quality %: Na 0.01 ~0.97%, NaZn in the kirsite13Volume fraction be 0.4~40%.
Further, at least one of following 27 kinds of elements: C:0.003~3.4%, Sn:0.01 are added in alloy selection ~10.2%, B:0.003~3.1%, Ge:0.007~7.6%, Se:0.004~4.1%, P:0.002~1.6%, Ag: 0.004~4.0%, Li:0.002~0.82%, Cu:0.018~6.0%, Mg:0.005~2.0%, Ce, Pr, Nd, Sm, Ho: 0.017~4.2%, Er, Gd, Lu:0.019~4.7%, K:0.004~1.0%, La:0.014~3.5%, Ca, Ti:0.005 ~1.1%, Fe, Mn, Mo:0.006~1.5%, Sr, Zr:0.009~2.3%.
A kind of preparation method of biodegradable Zn-Na system kirsite, processing flow are divided into three kinds:
(1) continuous casting → hot extrusion → rolling；
(2) continuous casting → hot extrusion → solution heat treatment → drawing；
(3) continuous casting → homogenization heat treatment → hot extrusion → rolling.
Further, the alloy raw material smelting temperature of step (1) described continuous casting is 580~880 DEG C, vacuumizes or lead to inertia Gas shield, heat preservation 5~start continuous casting after twenty minutes, heated mold make to being higher than 430~550 DEG C of the kirsite fusing point 5~27 DEG C of recirculated water being maintained except casting mold outlet with temperature to cool down continuous casting billet, drawing speed is 0.3~ 10cm/min。
Further, step (2) or (3) described hot extrusion are carried out at 150~300 DEG C, and extrusion speed is 1~8mm/min, Extrusion ratio is 9~81, refines the second phase size to less than 50 μm.
Further, step (3) or (4) described rolling are carried out in room temperature~320 DEG C, and rolling speed is 0.01~0.1m/s, is become Shape amount is 10~98%, refines zinc crystallite dimension to less than 10 μm.
Further, step (4) drawing is carried out in room temperature~280 DEG C, and deflection is 20~99.9%.
Further, step (3) solution heat treatment carries out under vacuum or inert gas shielding environment, 340~ 390 DEG C keep the temperature 1~25 hour, water quenching immediately after, by 10~100% coarseer AgZn3、LiZn4、CuZn5、Mg2Zn11 And MnZn13Second phase is dissolved into Zinc Matrix, improves the degradation safety in vivo of the kirsite.
Further, step (2) homogenization heat treatment point 2 steps under vacuum or inert gas shielding environment carry out, 200~300 DEG C first are warming up to 2~10 DEG C/min and keeps the temperature 1~4 hour, are then warming up to 350~380 DEG C with 1~5 DEG C/min Cooling after heat preservation 1~3 hour, the type of cooling includes furnace cooling and water quenching.
The gist of the invention is as described below.
When without illustrating, default % is mass fraction.
1. the present invention proposes in the biodegradable Zn-Na system kirsite, it is characterised in that chemical component is with quality % Meter: Na:0.01~0.97%.Determine that the foundation of Na content is as follows.
According to Zn-Na binary phase diagraml, at the end phasor richness Zn, Na generates the NaZn that fusing point is 548 DEG C in conjunction with Zn13Between metal Compound, its Na content are 2.6%.If Na content is more than 2.6%, enter the NaZn of low melting point13+ Na two-phase section, temperature Degree rises to 97.5 DEG C of fusings that Na just occurs, into NaZn13+ L (rich Na liquid phase) two-phase section causes the kirsite to occur molten Erosion significantly reduces alloy property.Therefore, the present invention proposes that Na content is lower than 2.6% in the kirsite.
Further, the present invention proposes control NaZn13Volume fraction in the kirsite is 0.4~40%, to institute It states the Na content in kirsite and makes and advanced optimize.Because of NaZn13The deformability of intermetallic compound is substantially less than Zn, when NaZn13Volume fraction when being more than 40%, the brittleness of the kirsite dramatically increases, cause its in plastic processing easily It cracks, fracture failure occurs when serious.The density of Zn is 7.14g/cm3, applicant is according to NaZn13Atomic structure calculate The density for obtaining it is 6.26g/cm3, and Na content and NaZn in the kirsite has been calculated with lever law13Body Functional relation between fraction.According to the calculated result of applicant, when to obtain Na content be 0.01~0.97%, NaZn13's Volume fraction is 0.4~40%.
2. biodegradable Zn-Na system kirsite proposed by the present invention, it is characterised in that chemical component, can in terms of quality % Following 27 kinds at least one of elements nontoxic to the human body or beneficial: lithium (Li), potassium (K), carbon are further added in selection (C), germanium (Ge), cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), holmium (Ho), erbium (Er), gadolinium (Gd), lutetium (Lu), molybdenum (Mo), tin (Sn), phosphorus (P), boron (B), selenium (Se), zirconium (Zr), calcium (Ca), magnesium (Mg), iron (Fe), manganese (Mn), copper (Cu), silver (Ag), strontium (Sr), titanium (Ti).Determine that the foundation of above-mentioned element additive amount is as follows.
According to Material Thermodynamics theory and database, the present invention proposes the combination energy according to the addition element and Zn atom Power is grouped them, first as the addition is controlled to determine their volume fraction ranges in the kirsite The foundation of cellulose content optimizes the mechanical property of the kirsite, especially plasticity.The groups elements are as follows:
(1) group 1 includes 7 kinds of elements: C, Sn, B, Ge, Se, P and Ag.The atomic energy and 0~3 Zn original of single above-mentioned element Son, which combines, forms the second phase, and wherein C, Sn, B and Ge exist in Zn matrix with simple substance form, and Se, P and Ag are formed in conjunction with Zn ZnSe、Zn3P2And AgZn3。
(2) group 2 includes 3 kinds of elements: Li, Cu and Mg.The atomic energy of single above-mentioned element shape in conjunction with 4~6 Zn atoms At the second phase: LiZn4、CuZn5And Mg2Zn11。
(3) group 3 include 17 kinds of elements: Ce, Pr, Nd, Sm, Ho, Er, Gd, Lu, K, La, Ca, Fe, Mn, Sr, Zr, Ti and Mo.The atomic energy of single above-mentioned element forms the second phase: CeZn in conjunction with 11~22 Zn atoms11、PrZn11、NdZn11、 SmZn11~12、HoZn12、ErZn12、GdZn12、LuZn12、KZn13、LaZn13、CaZn13、FeZn13、MnZn13、SrZn13、ZrZn14、 TiZn15And MoZn22。
The present invention proposes the mechanical property that the kirsite is improved using above-mentioned second phase, by being formed in zinc intra-die Nano-scale mutually hinders dislocation to use with the second of micron-scale, improves the intensity of the kirsite；By in zinc crystal particle crystal boundary It is upper formed micron-scale the second phase promote zinc crystal grain recrystallization, refine crystal grain, while improve the kirsite intensity and Plasticity.
The present invention proposes that the volume fraction for the second phase that element is formed in control group 1 is 0.01~10%；In control group 2 The volume fraction for the second phase that element is formed is 0.1~35%；The volume fraction for the second phase that element is formed in control group 3 exists 0.1~25%.The volume fraction upper limit for the second phase that element is formed in group 1~3 is no more than the second phase of Na element formation The volume fraction upper limit.It is calculated when individually adding one of described 27 kinds of elements accordingly, their content range: C: 0.003~3.4%, Sn:0.01~10.2%, B:0.003~3.1%, Ge:0.007~7.6%, Se:0.004~4.1%, P:0.002~1.6%, Ag:0.004~4.0%, Li:0.002~0.82%, Cu:0.018~6.0%, Mg:0.005~ 2.0%, Ce, Pr, Nd, Sm, Ho:0.017~4.2%, Er, Gd, Lu:0.019~4.7%, K:0.004~1.0%, La: 0.014~3.5%, Ca, Ti:0.005~1.1%, Fe, Mn, Mo:0.006~1.5%, Sr, Zr:0.009~2.3%.
3. the present invention proposes, influence of the interaction to the kirsite comprehensive performance between element is comprehensively considered, and examine Consider cost of alloy and processing performance, the total amount for controlling the various alloying elements of addition be no more than 2.0% (in actual production process, If not considering cost of alloy, the simple comprehensive performance for considering alloy, the total amount of the various alloying elements of addition is to be more than 2%), surplus Zn.Obtain the biodegradable Zn-Na system kirsite of low cost, low alloying.The mechanical property of the kirsite Pure zinc can be significantly higher than.
4. the present invention propose the kirsite prepare processing flow and technological parameter is:
(1) continuous casting → hot extrusion → rolling；
(2) continuous casting → hot extrusion → solution heat treatment → drawing；
(3) continuous casting → homogenization heat treatment → hot extrusion → rolling.
The alloy smelting of the continuous casting carries out in graphite or ceramic crucible, and smelting temperature is 580~880 DEG C, vacuumizes Or logical inert gas shielding, to temperature after heat preservation 5~start continuous casting after twenty minutes, use inner wall polish graphite casting mould, heating casting Type uses steel or copper as dummy bar, maintains 5~27 DEG C using temperature to being higher than 430~550 DEG C of the kirsite fusing point Recirculated water casting mold outlet except continuous casting billet is cooled down, drawing speed be 0.3~10cm/min.By adjusting casting mold plus The temperature field of hot temperature, drawing speed and intensity of cooling control continuous casting billet, the solid liquid interface of the kirsite continuous casting billet is controlled Within casting mold exports at 0.2~3cm, the effect that the continuous casting reaches is: (1) preventing that leakage thing occurs in continuous casting process Therefore prevent security risk；(2) friction between continuous casting billet and mould wall is reduced, not only reduces throwing power, and obtain surface matter Excellent continuous casting billet is measured, its surface-brightening, not thick oxide skin can be directly used for subsequent hot extrusion processing.And with pass The kirsite ingot casting of system method preparation, needs to remove the oxide skin of ingot casting surface, increases manufacturing procedure before hot extrusion, improves Production cost, reduces production efficiency；(3) orientation heterogeneous structure is obtained, wherein zinc crystal grain is in the form of a column (column crystal), on crystal boundary The second phase is distributed with, the angle of the length direction of the distribution and continuous casting billet of the long axis direction of column crystal and the second phase is 0 °~15 °, This orientation heterogeneous structure has better plastic forming ability.
The hot extrusion is carried out at 150~300 DEG C, and extrusion speed is 1~8mm/min, and extrusion ratio is 9~81, refinement the Two-phase is to size less than 50 μm.
The rolling is carried out in room temperature~320 DEG C, and rolling speed is 0.01~0.1m/s, and deflection is 10~98%, refines zinc Crystal grain is to size less than 10 μm.
The drawing is carried out in room temperature~280 DEG C, and deflection is 20~99.9%.
The solution heat treatment carries out under vacuum or inert gas shielding environment, small in 340~390 DEG C of heat preservations 1~25 When, (water quenching) is quenched in water immediately after, water temperature is 0~40 DEG C.The solution heat treatment by 10~100% it is coarseer AgZn3、LiZn4、CuZn5、Mg2Zn11And MnZn13Second phase is dissolved into Zinc Matrix, plays the adjustment kirsite microstructure Purpose, improve the kirsite in the intracorporal degradation safety of people.
Homogenization heat treatment point 2 steps under vacuum or inert gas shielding environment carry out, first with 2~10 DEG C/min liter Temperature to 200~300 DEG C keep the temperature 1~4 hour, then with 1~5 DEG C/min be warming up to 350~380 DEG C heat preservation 1~3 hour after it is cold But.The type of cooling includes furnace cooling and water quenching, and water temperature is 0~40 DEG C.The step 1 of the heat treatment is institute in order to prevent The low melting point fusing in kirsite is stated, crystal boundary ablation is caused, makes material scrap.The step 2 of the heat treatment is to make Microsegregation homogenization, improves the plastic forming ability and effect of the kirsite.
5. the room temperature tensile mechanical property of biodegradable Zn-Na system kirsite of the invention are as follows: yield strength 100~ 500MPa, 150~700MPa of tensile strength, elongation percentage 1.5~100%.By adjusting the ingredient and preparation work of the kirsite Skill can meet requirement of a variety of medical embedded devices to material mechanical performance in a wide range of interior adjustment mechanical property.
6. the degradation rate of biodegradable Zn-Na system kirsite of the invention in simulated body fluid is no more than 0.8mm/ Year.
7. biodegradable Zn-Na system kirsite of the invention is to the cell of L929 cell and human marrow mesenchymal stem cell Toxicity is 0 grade or 1 grade, shows good biocompatibility.
8. biodegradable Zn-Na system kirsite of the invention is suitable for but is not limited to manufacture following medical implant: the heart Dirty coronary artery and other intravascular stents, urethra rack, biliary tract rack, intracranial stent, trachea bracket, esophageal stents, intestinal stent etc. Intraluminal stent, bone tissue reparation bracket, bone nail, spicule, band line holdfast, screw, bone plate, bone set, intramedullary needle, bowel anastomosis device, The staplers such as blood vessel anastomat or dialyneury device.
The features of the present invention and advantage are as follows:
1. the good biocompatibility of Zn-Na system kirsite, mechanical property, biodegradation rate and anti-microbial property can By adjusting alloying component and processing flow and parameter are prepared in a wide range of interior adjustment, can satisfy a variety of medical embedded devices pair The demand of material property, applicability are wide.
2. the total amount of the various alloying elements added in Zn-Na system kirsite be no more than 2.0%, mechanical property and Anti-fatigue performance is substantially better than pure zinc.
3. the cost of Zn-Na system kirsite is low, preparation process flow and parameter are easy to real with existing industrial equipment It is existing, it is very suitable to industrialization promotion.
Specific embodiment
Embodiments of the present invention are described in detail below.
The present invention relates to a kind of biodegradable Zn-Na system kirsites and preparation method thereof.
In the following, clearly illustrating effect of the invention by embodiment.In addition, the invention is not limited to below Embodiment can appropriately be changed in the range of not changing main idea and is implemented.
Embodiment 1:
Ingredient, preparation and the performance test of biodegradable Zn-Na binary kirsite.
For the chemical component of 4 examples of the kirsite as shown in table 1-1, the Na of addition is 0.01~0.72%, remaining Amount is Zn.NaZn in the kirsite13The volume fraction of second phase is 0.4~30%.
The kirsite prepares processing flow are as follows: continuous casting → hot extrusion → rolling.The raw material of the continuous casting is by table 1-1 The metal Zn and Na of proportion, place them into the graphite crucible of continuous casting installation for casting, high-purity argon gas protection are passed through after vacuumizing, then Graphite crucible is warming up to 620 DEG C by induction heating, heat preservation 10 minutes to melting sources and sufficiently mixed under electromagnetic force stirring It closes.The temperature of graphite casting mould is heated to 450 DEG C, continuous casting billet is slowly pulled out graphite casting mould by starting drawing device, and circulating water temperature is protected It holds at 20 ± 1 DEG C, obtains the continuous casting billet of surface-brightening, wherein zinc crystal grain is column crystal, the length of long axis direction and continuous casting billet The angle in direction is 0 °~10 °.
The hot extrusion is carried out at 220 DEG C, extrusion speed 2mm/min, extrusion ratio 16.
The rolling is carried out at 60 DEG C, and rolling speed is 0.04m/s, and deflection is 60~98%, and the kirsite stocking is made, Wherein the average grain size of zinc crystal grain is less than 10 μm, NaZn13The size of second phase is less than 1 μm.
Sample is cut from the kirsite stocking carries out electrochemical corrosion, immersion corrosion, cytotoxicity and room temperature tensile The test of mechanical property.The sample for preparing above-mentioned performance test according to the method in relevant criterion, is marked according to ASTM-G102-89 Standard calculates Electrochemical corrosion rate, according to ASTM-G102-89 criterion calculation immersion corrosion rate, according to national standard GB/T 16886.5-2003 evaluating cytotoxicity, room temperature tensile mechanical property is evaluated according to national standard GB/T 228.1-2010.
Measure the room temperature tensile mechanical property of 4 example kirsites in table 1-1 are as follows: 100~180MPa of yield strength resists 150~220MPa of tensile strength, elongation percentage 40~100%.
Measuring Electrochemical corrosion rate of 4 example kirsites in simulated body fluid in table 1-1 is 0.05~0.10mm/ Year.
Measuring immersion corrosion rate of 4 example kirsites in simulated body fluid in table 1-1 is 0.04~0.08mm/ Year.
The cytotoxicity for measuring 4 example kirsites in table 1-1 is 0 grade or 1 grade, shows good bio-compatible Property.
Table 1-1
Example Na (quality %) NaZn13(volume %)
Alloy 1 0.01 0.4
Alloy 2 0.23 10
Alloy 3 0.35 15
Alloy 4 0.72 30
Embodiment 2:
Ingredient, preparation and the performance test of biodegradable Zn-Na system ternary kirsite.
The chemical component of 8 examples of the kirsite as shown in table 2-1, the alloying element total amount of addition is 0.25~ 0.98%, surplus Zn belong to low alloying kirsite, at low cost.
The kirsite prepares processing flow are as follows: continuous casting → hot extrusion → rolling.It is used by the content of element in table 2-1 High pure raw material carries out ingredient, places them into the graphite crucible of continuous casting installation for casting, high-purity argon gas protection is passed through after vacuumizing, then Graphite crucible is warming up to 650 DEG C by induction heating, heat preservation 8 minutes to melting sources and sufficiently mixed under electromagnetic force stirring It closes.The temperature of graphite casting mould is heated to 430 DEG C, continuous casting billet is slowly pulled out graphite casting mould by starting drawing device, and circulating water temperature is protected It holds at 25 ± 1 DEG C, obtains the continuous casting billet of surface-brightening, wherein zinc crystal grain is column crystal, the length of long axis direction and continuous casting billet The angle in direction is 0 °~10 °.
The hot extrusion is carried out at 200 DEG C, extrusion speed 1mm/min, extrusion ratio 25.
The rolling is carried out in room temperature, and rolling speed is 0.07m/s, and deflection is 60~80%, and the kirsite stocking is made, Wherein the average grain size of zinc crystal grain is 1~5 μm, and the size of a variety of second phases is less than 2 μm.
Sample is cut from the kirsite stocking carries out electrochemical corrosion, cytotoxicity and room temperature tensile mechanical property Test.The preparation of said sample and test method are carried out according to the method that embodiment 1 provides.
Measure the room temperature tensile mechanical property of 8 example kirsites in table 2-1 are as follows: 120~450MPa of yield strength resists 180~590MPa of tensile strength, elongation percentage 5~60%.
Measuring Electrochemical corrosion rate of 8 example kirsites in simulated body fluid in table 2-1 is 0.05~0.23mm/ Year.
The cytotoxicity for measuring 8 example kirsites in table 2-1 is 0 grade or 1 grade, shows good cytocompatibility Property.
Table 2-1
Embodiment 3:
Ingredient, preparation and the performance test of biodegradable Zn-Na system quaternary kirsite.
The kirsite contains 4 kinds of alloying elements, wherein 2 kinds are the alloying elements that must contain: Zn and Na, and the 3rd~4 kind It is the alloy element further added.The chemical component of 18 embodiments of the kirsite is as shown in table 3-1, the conjunction of addition Gold element total amount is 0.46~1.40%, surplus Zn, belongs to low alloying kirsite, at low cost.
The kirsite prepares processing flow are as follows: continuous casting → homogenization heat treatment → hot extrusion → rolling.By in table 3-1 The content of element carries out ingredient using high pure raw material, places them into the graphite crucible of continuous casting installation for casting, is passed through height after vacuumizing Then graphite crucible is warming up to 700 DEG C by induction heating, keeps the temperature 5 minutes to melting sources and in electromagnetism by straight argon gas shielded It is sufficiently mixed under power stirring.The temperature of graphite casting mould is heated to 440 DEG C, continuous casting billet is slowly pulled out graphite casting by starting drawing device Type, circulating water temperature are maintained at 18 ± 1 DEG C, obtain the continuous casting billet of surface-brightening, wherein zinc crystal grain be column crystal, long axis direction with The angle of the length direction of continuous casting billet is 0 °~10 °.
The homogenization heat treatment carries out in vacuum heat treatment furnace, after vacuumizing, is first warming up to 200 DEG C with 2 DEG C/min Then heat preservation 4 hours is warming up to 360 DEG C with 1 DEG C/min and keeps the temperature 2 hours, then furnace cooling.
The hot extrusion is carried out at 250 DEG C, extrusion speed 4mm/min, extrusion ratio 16.
The rolling is carried out in room temperature, and rolling speed is 0.03m/s, and deflection is 82~93%, and the kirsite stocking is made, Wherein the average grain size of zinc crystal grain is 1~5 μm, and the size of a variety of second phases is less than 1 μm.
Sample is cut from the kirsite stocking carries out electrochemical corrosion, cytotoxicity and room temperature tensile mechanical property Test.The preparation of said sample and test method are carried out according to the method that embodiment 1 provides.
The test that sample carries out anti-microbial property is cut from the kirsite stocking.Sample is cut into 10 × 2mm of Φ first Disk disk is put into alcohol and is cleaned by ultrasonic 20~40 minutes, clearly after polishing disk obtains the surface with metallic luster It is spare with drying up after the completion of washing.The test of antibiotic property is carried out to alloy using spread plate, and is calculated and is resisted according to following formula Bacterium rate: antibiotic rate (%)=(negative control group average colony number-sample sets average colony number)/negative control group average colony number × 100%.Testing the bacterium used is Escherichia coli.
Measure the room temperature tensile mechanical property of 18 example kirsites in table 3-1 are as follows: 200~420MPa of yield strength, 260~550MPa of tensile strength, elongation percentage 3~55%.
Measure in table 3-1 Electrochemical corrosion rate of 18 example kirsites in simulated body fluid be 0.08~ 0.30mm/.
The cytotoxicity for measuring 18 example kirsites in table 3-1 is 0 grade or 1 grade, shows good cytocompatibility Property.
The antibiotic rate of example alloy 14,19,20,23,24,26~28 in table 3-1 is measured 90% or more, is had anti- Bacterium property.
Table 3-1
Embodiment 4:
Ingredient, preparation and the performance test of biodegradable five yuan of kirsites of Zn-Na system.
The kirsite contains 5 kinds of alloying elements, wherein 2 kinds are the alloying elements that must contain: Zn and Na, and the 3rd~5 kind It is the alloy element further added.The chemical component of 15 embodiments of the kirsite is as shown in table 4-1, the conjunction of addition Gold element total amount is 0.44~1.37%, surplus Zn, belongs to low alloying kirsite, at low cost.
The kirsite prepares processing flow are as follows: continuous casting → homogenization heat treatment → hot extrusion → rolling.By in table 4-1 The content of element carries out ingredient using high pure raw material, places them into the graphite crucible of continuous casting installation for casting, is passed through height after vacuumizing Then graphite crucible is warming up to 750 DEG C by induction heating, keeps the temperature 5 minutes to melting sources and in electromagnetism by straight argon gas shielded It is sufficiently mixed under power stirring.The temperature of graphite casting mould is heated to 500 DEG C, continuous casting billet is slowly pulled out graphite casting by starting drawing device Type, circulating water temperature are maintained at 15 ± 1 DEG C, obtain the continuous casting billet of surface-brightening, wherein zinc crystal grain be column crystal, long axis direction with The angle of the length direction of continuous casting billet is 0 °~8 °.
The homogenization heat treatment carries out in vacuum heat treatment furnace, after vacuumizing, is first warming up to 250 DEG C with 4 DEG C/min Heat preservation 3 hours, is then warming up to 375 DEG C with 2 DEG C/min and keeps the temperature 1.5 hours, is placed in the water that temperature is 0 DEG C and carries out immediately after Water quenching.
The hot extrusion is carried out at 225 DEG C, extrusion speed 2mm/min, extrusion ratio 16.
The rolling is carried out in room temperature, and rolling speed is 0.05m/s, and deflection is 83~98%, and the kirsite stocking is made, Wherein the average grain size of zinc crystal grain is 1~5 μm, and the size of a variety of second phases is less than 1 μm.
Sample is cut from the extruding stocking of the kirsite carries out electrochemical corrosion, cytotoxicity and room temperature tensile mechanics The test of performance.The preparation of said sample and test method are carried out according to the method that embodiment 1 provides.
Measure the room temperature tensile mechanical property of 15 example kirsites in table 4-1 are as follows: 260~500MPa of yield strength, 320~700MPa of tensile strength, elongation percentage 2~46%.
Measure in table 4-1 Electrochemical corrosion rate of 15 example kirsites in simulated body fluid be 0.24~ 0.43mm/.
The cytotoxicity for measuring 15 example kirsites in table 4-1 is 0 grade or 1 grade, shows good cytocompatibility Property.
Table 4-1
Embodiment 5:
Ingredient, preparation and the performance test of the biodegradable hexa-atomic kirsite of Zn-Na system.
The kirsite contains 6 kinds of alloying elements, wherein 2 kinds are the alloying elements that must contain: Zn and Na, and the 3rd~6 kind It is the alloy element further added.The chemical component of 10 embodiments of the kirsite is as shown in Table 5-1, the conjunction of addition Gold element total amount is 0.79~1.41%, surplus Zn, belongs to low alloying kirsite, at low cost.
The kirsite prepares processing flow are as follows: continuous casting → hot extrusion → solution heat treatment → drawing.By first in table 5-1 The content of element carries out ingredient using high pure raw material, places them into the graphite crucible of continuous casting installation for casting, is passed through after vacuumizing high-purity Then graphite crucible is warming up to 780 DEG C by induction heating, keeps the temperature 8 minutes to melting sources and in electromagnetic force by argon gas protection It is sufficiently mixed under stirring.The temperature of graphite casting mould is heated to 460 DEG C, continuous casting billet is slowly pulled out graphite casting by starting drawing device Type, circulating water temperature are maintained at 20 ± 1 DEG C, obtain the continuous casting billet of surface-brightening, wherein zinc crystal grain be column crystal, long axis direction with The angle of the length direction of continuous casting billet is 0 °~10 °.
The hot extrusion is carried out at 190 DEG C, extrusion speed 1mm/min, extrusion ratio 16.
It is carried out in the solution heat treatment vacuum heat treatment furnace, keeps the temperature 5~8 hours at 378 DEG C, be placed in temperature immediately after To carry out water quenching in the water of room temperature.By the solution heat treatment by the coarseer LiZn in table 5-1 in example alloy4、 CuZn5、Mg2Zn11Or MnZn13Part is dissolved into Zn matrix, reaches following tissue modulation effect: (1) discharging Li, Cu, Mg or Mn Atom enters Zn matrix, forms substitution solid solution, improves alloy strength；(2) it in subsequent plastic processing, is precipitated and receives again The LiZn of meter ruler cun4、CuZn5、Mg2Zn11Or MnZn13Second phase improves the comprehensive performance of alloy.
The drawing is carried out at 60~100 DEG C, and deflection is 85~96%, and the kirsite wire rod is made, and wherein zinc is brilliant The average grain size of grain is less than 3 μm, and the size of a variety of second phases is less than 1 μm.
Sample is cut from the kirsite wire rod carries out electrochemical corrosion, cytotoxicity and room temperature tensile mechanical property Test.The preparation of said sample and test method are carried out according to the method that embodiment 1 provides.
Measure the room temperature tensile mechanical property of 10 example kirsites in table 5-1 are as follows: 330~500MPa of yield strength, 380~700MPa of tensile strength, elongation percentage 10~37%.
Measure in table 5-1 Electrochemical corrosion rate of 10 example kirsites in simulated body fluid be 0.20~ 0.52mm/.
The cytotoxicity for measuring 10 example kirsites in table 5-1 is 0 grade or 1 grade, shows good cytocompatibility Property.
Table 5-1

Claims (10)

1. a kind of biodegradable Zn-Na system kirsite, it is characterised in that chemical component is in terms of quality %: Na be 0.01~ 0.97%, NaZn in kirsite13Volume fraction be 0.4~40%.
2. biodegradable Zn-Na system kirsite as described in claim 1, it is characterised in that selected in the kirsite into At least one of following 27 kinds of elements of one step addition: C:0.003~3.4%, Sn:0.01~10.2%, B:0.003~ 3.1%, Ge:0.007~7.6%, Se:0.004~4.1%, P:0.002~1.6%, Ag:0.004~4.0%, Li:0.002 ~0.82%, Cu:0.018~6.0%, Mg:0.005~2.0%, Ce, Pr, Nd, Sm, Ho:0.017~4.2%, Er, Gd and Lu:0.019~4.7%, K:0.004~1.0%, La:0.014~3.5%, Ca, Ti:0.005~1.1%, Fe, Mn and Mo: 0.006~1.5%, Sr, Zr:0.009~2.3%.
3. biodegradable Zn-Na system as described in claim 2 kirsite, it is characterised in that comprehensively consider the phase between element Influence of the interaction to the kirsite comprehensive performance, and consider cost of alloy and processing performance, control the various alloys of addition The total amount of element is no more than 2.0%, surplus Zn, obtains the biodegradable Zn-Na system kirsite of low cost, low alloying, Its mechanical property is significantly higher than pure zinc.
4. the preparation method of biodegradable Zn-Na system as described in claim 2 kirsite, it is characterised in that processing flow It is divided into three kinds:
(1) continuous casting → hot extrusion → rolling；
(2) continuous casting → hot extrusion → solution heat treatment → drawing；
(3) continuous casting → homogenization heat treatment → hot extrusion → rolling.
5. the preparation method of biodegradable Zn-Na system as described in claim 4 kirsite, it is characterised in that step (1) The alloy raw material smelting temperature of the continuous casting is 580~880 DEG C, vacuumizes or lead to inert gas shielding, heat preservation 5~after twenty minutes Start continuous casting, heated mold maintains 5~27 DEG C of circulation using temperature to being higher than 430~550 DEG C of the kirsite fusing point Water cools down continuous casting billet except casting mold outlet, and drawing speed is 0.3~10cm/min.
6. the preparation method of biodegradable Zn-Na system as described in claim 4 kirsite, it is characterised in that step (2) Or (3) described hot extrusion is carried out at 150~300 DEG C, extrusion speed is 1~8mm/min, and extrusion ratio is 9~81, refines the second phase Size to less than 50 μm.
7. the preparation method of biodegradable Zn-Na system as described in claim 4 kirsite, it is characterised in that step (3) Or (4) described rolling is carried out in room temperature~320 DEG C, rolling speed is 0.01~0.1m/s, and deflection is 10~98%, refines zinc crystal grain Size to less than 10 μm.
8. the preparation method of biodegradable Zn-Na system as described in claim 4 kirsite, it is characterised in that step (4) The drawing is carried out in room temperature~280 DEG C, and deflection is 20~99.9%.
9. the preparation method of biodegradable Zn-Na system as described in claim 4 kirsite, it is characterised in that step (3) The solution heat treatment carries out under vacuum or inert gas shielding environment, keeps the temperature 1~25 hour at 340~390 DEG C, then stands That is water quenching, by 10~100% coarseer AgZn3、LiZn4、CuZn5、Mg2Zn11And MnZn13Second phase is dissolved into Zinc Matrix, Improve the degradation safety in vivo of the kirsite.
10. the preparation method of biodegradable Zn-Na system as described in claim 4 kirsite, it is characterised in that step (2) Homogenization heat treatment point 2 steps under vacuum or inert gas shielding environment carry out, and are first warming up to 200 with 2~10 DEG C/min ~300 DEG C keep the temperature 1~4 hour, cooling after being then warming up to 350~380 DEG C of heat preservations 1~3 hour with 1~5 DEG C/min, described The type of cooling includes furnace cooling and water quenching.
CN201811108848.0A 2018-09-21 2018-09-21 Biodegradable Zn-Na series zinc alloy and preparation method thereof Active CN109128064B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811108848.0A CN109128064B (en) 2018-09-21 2018-09-21 Biodegradable Zn-Na series zinc alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811108848.0A CN109128064B (en) 2018-09-21 2018-09-21 Biodegradable Zn-Na series zinc alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109128064A true CN109128064A (en) 2019-01-04
CN109128064B CN109128064B (en) 2020-04-28

Family

ID=64823206

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811108848.0A Active CN109128064B (en) 2018-09-21 2018-09-21 Biodegradable Zn-Na series zinc alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109128064B (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109847113A (en) * 2019-03-04 2019-06-07 苏州越众生物科技有限公司 Pltine biodegradable angiocarpy bracket and preparation method thereof
CN109966568A (en) * 2019-04-11 2019-07-05 湘潭大学 A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof
CN110241453A (en) * 2019-04-25 2019-09-17 西南大学 A kind of release fluoride and the degradable kirsite bone nail of cerium and preparation method thereof
CN110317973A (en) * 2019-07-03 2019-10-11 北京科技大学 A kind of biodegradable LiZn4- Zn composite diphase material and preparation method thereof
CN111020295A (en) * 2020-01-03 2020-04-17 北京科技大学 High-performance biodegradable Zn-Cu-Li-X alloy and preparation and application methods thereof
CN111529761A (en) * 2020-05-12 2020-08-14 浙江工贸职业技术学院 Degradable Zn-Ti binary biomedical material and preparation method thereof
CN112899527A (en) * 2021-01-20 2021-06-04 湖南华锐科技集团股份有限公司 Degradable zinc alloy bar and preparation method thereof
CN113416867A (en) * 2021-06-16 2021-09-21 东北大学 Preparation method of zinc alloy pipe capable of being used for degradable cardiovascular stent
CN114042898A (en) * 2021-11-10 2022-02-15 温州医科大学附属口腔医院 Preparation method of biomedical degradable metal skeleton reinforced Zn-based composite material with large-area galvanic corrosion structure
CN117137543A (en) * 2023-11-01 2023-12-01 山东瑞安泰医疗技术有限公司 Degradable plugging device and preparation method and application thereof
CN117778801A (en) * 2024-02-26 2024-03-29 山东瑞安泰医疗技术有限公司 Degradable copper-based shape memory alloy medical implant and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021243398A1 (en) * 2020-06-01 2021-12-09 Deakin University Zinc-based alloys for bioresorbable medical implants

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1130934A (en) * 1965-10-08 1968-10-16 Nat Distillers Chem Corp Novel zinc composition and preparation thereof
US3641081A (en) * 1969-01-21 1972-02-08 Int Lead Zinc Res Process for preparing dialkylzinc compounds from alkylbromide
JPS56112452A (en) * 1980-02-06 1981-09-04 Mitsui Mining & Smelting Co Ltd Galvanized material
JPH04167942A (en) * 1990-11-01 1992-06-16 Hitachi Cable Ltd Manufacture of corrosion resistant zinc alloy-coated steel wire
JPH07278707A (en) * 1994-04-08 1995-10-24 Mitsui Mining & Smelting Co Ltd Zinc alloy
WO2005030285A1 (en) * 2003-09-28 2005-04-07 Guido Schnyder Biodegradable and/or bioabsorbable member for vascular sealing
CN104857570A (en) * 2015-05-05 2015-08-26 乐普（北京）医疗器械股份有限公司 Degradable zinc-based alloy bracket and preparation method thereof
CN107456610A (en) * 2016-06-02 2017-12-12 北京大学 A kind of Zn-Ag systems kirsite and preparation method and application
CN108004432A (en) * 2017-12-22 2018-05-08 广州宇智科技有限公司 Containing strontium and sodium high abrasion high heat conduction kirsite and its processing technology

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1130934A (en) * 1965-10-08 1968-10-16 Nat Distillers Chem Corp Novel zinc composition and preparation thereof
US3641081A (en) * 1969-01-21 1972-02-08 Int Lead Zinc Res Process for preparing dialkylzinc compounds from alkylbromide
JPS56112452A (en) * 1980-02-06 1981-09-04 Mitsui Mining & Smelting Co Ltd Galvanized material
JPH04167942A (en) * 1990-11-01 1992-06-16 Hitachi Cable Ltd Manufacture of corrosion resistant zinc alloy-coated steel wire
JPH07278707A (en) * 1994-04-08 1995-10-24 Mitsui Mining & Smelting Co Ltd Zinc alloy
WO2005030285A1 (en) * 2003-09-28 2005-04-07 Guido Schnyder Biodegradable and/or bioabsorbable member for vascular sealing
CN104857570A (en) * 2015-05-05 2015-08-26 乐普（北京）医疗器械股份有限公司 Degradable zinc-based alloy bracket and preparation method thereof
CN107456610A (en) * 2016-06-02 2017-12-12 北京大学 A kind of Zn-Ag systems kirsite and preparation method and application
CN108004432A (en) * 2017-12-22 2018-05-08 广州宇智科技有限公司 Containing strontium and sodium high abrasion high heat conduction kirsite and its processing technology

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109847113A (en) * 2019-03-04 2019-06-07 苏州越众生物科技有限公司 Pltine biodegradable angiocarpy bracket and preparation method thereof
CN109966568A (en) * 2019-04-11 2019-07-05 湘潭大学 A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof
CN109966568B (en) * 2019-04-11 2021-08-06 湘潭大学 Zn-Ge-X ternary biomedical material and preparation method thereof
CN110241453A (en) * 2019-04-25 2019-09-17 西南大学 A kind of release fluoride and the degradable kirsite bone nail of cerium and preparation method thereof
CN110317973A (en) * 2019-07-03 2019-10-11 北京科技大学 A kind of biodegradable LiZn4- Zn composite diphase material and preparation method thereof
CN111020295A (en) * 2020-01-03 2020-04-17 北京科技大学 High-performance biodegradable Zn-Cu-Li-X alloy and preparation and application methods thereof
CN111529761A (en) * 2020-05-12 2020-08-14 浙江工贸职业技术学院 Degradable Zn-Ti binary biomedical material and preparation method thereof
CN112899527B (en) * 2021-01-20 2022-04-08 湖南华锐科技集团股份有限公司 Degradable zinc alloy bar and preparation method thereof
CN112899527A (en) * 2021-01-20 2021-06-04 湖南华锐科技集团股份有限公司 Degradable zinc alloy bar and preparation method thereof
CN113416867A (en) * 2021-06-16 2021-09-21 东北大学 Preparation method of zinc alloy pipe capable of being used for degradable cardiovascular stent
CN114042898A (en) * 2021-11-10 2022-02-15 温州医科大学附属口腔医院 Preparation method of biomedical degradable metal skeleton reinforced Zn-based composite material with large-area galvanic corrosion structure
CN114042898B (en) * 2021-11-10 2023-02-28 温州医科大学附属口腔医院 Preparation method of biomedical degradable metal skeleton reinforced Zn-based composite material with large-area galvanic corrosion structure
CN117137543A (en) * 2023-11-01 2023-12-01 山东瑞安泰医疗技术有限公司 Degradable plugging device and preparation method and application thereof
CN117137543B (en) * 2023-11-01 2024-02-02 山东瑞安泰医疗技术有限公司 Degradable plugging device and preparation method and application thereof
CN117778801A (en) * 2024-02-26 2024-03-29 山东瑞安泰医疗技术有限公司 Degradable copper-based shape memory alloy medical implant and preparation method thereof
CN117778801B (en) * 2024-02-26 2024-05-24 山东瑞安泰医疗技术有限公司 Degradable copper-based shape memory alloy medical implant and preparation method thereof

Also Published As

Publication number Publication date
CN109128064B (en) 2020-04-28

Similar Documents

Publication Publication Date Title
CN109128064A (en) A kind of biodegradable Zn-Na system kirsite and preparation method thereof
Zhang et al. Investigation on the microstructure, mechanical properties, in vitro degradation behavior and biocompatibility of newly developed Zn-0.8% Li-(Mg, Ag) alloys for guided bone regeneration
CN109097629B (en) Biodegradable Zn-Mo series zinc alloy and preparation method thereof
Jiang et al. Effect of Sn addition on the mechanical properties and bio-corrosion behavior of cytocompatible Mg–4Zn based alloys
EP2764130B1 (en) Biodegradable metal alloys
CN107557632B (en) Degradable biomedical Mg-Zn-Zr-Nd alloy material and preparation method thereof
CN108588484A (en) High-strength high-plastic biodegradable Zn-Mn-Mg systems kirsite of one kind and preparation method thereof
CN108754232B (en) High-strength high-plasticity biodegradable Zn-Mn-Li series zinc alloy and application thereof
CN105986146B (en) A kind of degradable medical is metal material embedded and preparation method thereof
CN109966568B (en) Zn-Ge-X ternary biomedical material and preparation method thereof
CN104120320A (en) Degradable rare earth magnesium alloy medical biomaterial and preparation method thereof
CN104328318A (en) Preparation method of high-corrosion-resistance biodegradable magnesium alloy
CN111187943A (en) Biomedical Zn-Cu-Mg alloy and preparation method thereof
CN102258806B (en) Degradable magnesium-base biomedical material for implantation in orthopaedics, and preparation method thereof
CN109602960B (en) Preparation method of medical zinc alloy bar with superplasticity
CN108486408A (en) A kind of low elastic modulus dental filling beta titanium alloy and its manufacturing method
CN114318187B (en) Biomedical high-purity high-strength corrosion-resistant Mg-Zn-Mn magnesium alloy wire and preparation method thereof
CN108425051A (en) A kind of bio-medical Mg-Sn-Zn-Ca magnesium alloys and preparation method thereof
CN110241330A (en) A kind of degradable Zn-Ag system kirsite and the preparation method and application thereof
CN110117743A (en) A kind of corrosion-proof and high-strength tough magnesium alloy tubing and preparation process
CN108677074A (en) A kind of medical degradable corrosion-resistant magnesium alloy bracket and preparation method thereof of implantation heart
CN110317973A (en) A kind of biodegradable LiZn4- Zn composite diphase material and preparation method thereof
CN108165782B (en) Medical zinc-based alloy strip and preparation method thereof
Niu et al. The effects of Cu and Mn on the microstructure, mechanical, corrosion properties and biocompatibility of Zn–4Ag alloy
CN111187957A (en) Biodegradable magnesium alloy and preparation method 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
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230317

Address after: Room 110, Building 6, Yard 26, Yongwang West Road, Daxing Biomedical Industry Base, Zhongguancun Science Park, Daxing District, Beijing 102629 (cluster registration)

Patentee after: Beijing shangning Kezhi Medical Instrument Co.,Ltd.

Address before: 100083 No. 30, Haidian District, Beijing, Xueyuan Road

Patentee before: University OF SCIENCE AND TECHNOLOGY BEIJING