CN107198796A - A kind of bio-medical Zn Mn Cu systems kirsite and preparation method thereof - Google Patents
A kind of bio-medical Zn Mn Cu systems kirsite and preparation method thereof Download PDFInfo
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- CN107198796A CN107198796A CN201710363125.4A CN201710363125A CN107198796A CN 107198796 A CN107198796 A CN 107198796A CN 201710363125 A CN201710363125 A CN 201710363125A CN 107198796 A CN107198796 A CN 107198796A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- 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
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/086—Phosphorus-containing materials, e.g. apatite
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- 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
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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- 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
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- 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
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Abstract
The invention discloses a kind of bio-medical Zn Mn Cu systems alloy and preparation method thereof.Belong to the design of medical degradable metal material composition and preparing technical field.This kirsite includes Cu of the mass percent for 0.1~5% Mn and 0.1~2%, and surplus is Zn.There is good mechanical property after vacuum induction melting and plastic working, the intensity and plasticity requirements of medical implant material is met.It is nontoxic, can degrade in vivo, possess good histocompatbility and blood compatibility, the metal ion of dissolution can be absorbed the reparation of promotion organization organ by organism or be excreted by metabolism.
Description
Technical field
The present invention relates to a kind of bio-medical Zn-Mn-Cu systems kirsite and preparation method thereof, and in particular to a kind of Zn-Mn-
The preparation method of Cu systems kirsite and its application in degradable medical implant, belong to medical degradable metal material composition
Design and preparing technical field.
Technical background
Metal material, inorganic material, high polymer material, composite and biomimetic material etc. are to be applied to clinical biochemical at present
Medical material, wherein medical metal material obtain widest application because mechanical property and processing characteristics are preferable, such as：
316L stainless steels, Co-Cr-Mo alloys, WE43 magnesium-rare earth alloys, Ti-6Al-4V alloys, Zn-Mg alloys, pure iron etc..These materials
Material can be divided into 2 classes, and a class is the material in people's degradable in vivo, and another kind of is the nondegradable material in human body.In human body
Interior nondegradable material, such as 316L stainless steels, Ti-6Al-4V alloys, Co-Cr-Mo alloys, are permanent implanted, work as plant
Entering after military service of the body in human body expires must be taken out by second operation, and physiology pain and financial burden are added to patient.
And in the material of people's degradable in vivo, such as pure iron, magnesium alloy, kirsite, suitable for needing the device being on active service, such as blood vessel branch temporarily
Frame, urethra rack, bone fracture fixation plate etc..These devices implantation human body plays a part of auxiliary and promotion organization is repaired, with group
Knit reparation gradually to complete, these devices are gradually degraded by body fluid, its catabolite part is absorbed by the body promotion organization reparation,
Another part is excreted by metabolism, is taken out without second operation, will not increase pain and financial burden to patient.Can
Medical bio metal material of degrading turns into the study hotspot of current international bio Material Field.
In recent years, degradable biological medical magnesium alloy material turns into one of focus of research, develops a series of biology
Medical degradable magnesium alloy, with the most Clinical practice prospect of the magnesium alloy containing rare earth element.German Biotronik companies Mg-
DREAMS 1G intravascular stents prepared by Re (rare earth) alloy, the tensile strength of material reaches 195MPa, but elongation percentage only has 2%, suction
The receipts cycle is 0.5 year.It can thus be appreciated that at present the subject matter that exists as degradable biological medical material of magnesium alloy be plasticity compared with
Speed that is low and being corroded in human body is too fast.
Recently, kirsite has obtained the concern of people, correlative study Shang Qi steps as degradable biological medical material
Section.In Traditional project application, metal Zn plays anti-corrosion protection effect to parent metal frequently as sacrificial anode material coating,
Such as, galvanizing steel.But in bio-medical field, compared with magnesium, metallic zinc and its alloy have higher corrosion potential, therefore
Corrosion rate than magnesium is slow, more conforms to clinical demand, is expected to turn into new bio medical degradable implantation material.Chinese invention
A kind of Zn-Mg systems kirsite and preparation method and application, Chinese invention patent CN are disclosed in the A of patent CN 104212998
A kind of Zn-Ca systems kirsite and preparation method and application, Chinese invention patent CN are disclosed in 104195369 B
A kind of zipper tooth belt Zn-Cu-Al-Mg systems alloy and preparation method thereof is disclosed in 102011029 A.
Zinc, manganese and copper are the metallic elements that human body needs.Zinc acts on very big in human body, lived spark plug it
Claim.Human normal zinc content is 2~3 grams, and adult needs 13-15 milligrams of zinc daily, and it is the main component of a variety of enzymes in human body.
Zinc is distributed in most tissues organ, and wherein liver, muscle and bone content are higher.Human body zinc-deficiency will visual degradation,
Wound and wound healing are slowed, body and intelligence development are bad, and nanism is caused when serious.Effect of the manganese in human body
Not small, in the safety for the manganese that Chinese Soclety of Nutrition formulates and suitable intake reference index, each age level crowd is corresponding
Index difference, wherein more than 11 years old each age group crowd is 2~3 milligrams daily.Human body manganese deficiency can influence bone just
It is frequently grown and develops, influence the metabolism of sugar, trigger neurasthenia syndrome, accelerates the serious consequences such as human senility.Copper
It is element needed by human, World Health Organization's suggestion adult's per kilogram of body weight should take in 0.03 milligram of copper, pregnant woman and baby daily
Youngster should double.Copper is the component of human body multiple protein, and Central nervous, immune system, brain, liver and heart etc. are multiple
The development of internal organs and function have a major impact.Copper, in about 100~150 milligrams of people's in-vivo content, is that content occupies second in human body
Required minor metallic element.Scarce copper can trigger sclerotin loose, cause anaemia, coronary heart disease, infertility etc..
The preparation side for the Zn-Mn-Cu systems kirsite also invented both at home and abroad without document and patent report this patent at present
Method and performance, and propose this Zn-Mn-Cu systems kirsite being used as degradable biological medical material.
The content of the invention
It is an object of the invention to provide a kind of Zn-Mn-Cu systems kirsite and its preparation and application method, it is related to a kind of Zn-
The preparation method of Mn-Cu systems kirsite and its application in degradable medical implant.Kirsite prepared by the present invention has
Excellent comprehensive mechanical property, permanently effective support force can be provided in vivo, with excellent cell compatibility, blood
Liquid phase capacitive and tissue, organ compatibility, the preparation available for biomedical implant.
The Zn-Mn-Cu systems kirsite that the present invention is provided, including Zn elements, Mn elements and Cu elements.Alloy element component model
Enclose be 0.1~5% Mn, 0.1~2% Cu, surplus is Zn, and mentioned component is calculated by percentage to the quality, the Zn-Mn-Cu
Mn mass percent scope is 0.1~5% in alloy；Cu percentage ranges are 0.1~2%.
Zn-Mn-Cu systems as described above kirsite, alloying element is count by weight percentage：
(1) by 98.5%~99.6% Zn, 0.3%~0.8% Mn and 0.1%~0.7%Cu composition；
(2) it is made up of 98.8% Zn, 0.8% Mn and 0.4% Cu；
(3) it is made up of 99.2% Zn, 0.4% Mn and 0.4% Cu.
Zn-Mn-Cu systems kirsite prepared by the present invention is compact texture, possesses good histocompatbility, is that one kind can
The biological and medicinal implant material leaned on.
The preparation method of Zn-Mn-Cu systems as described above kirsite, specific preparation process is as follows：
1) cast：Using pure Zn, pure Mn and pure Cu as raw material, in the vacuum induction melting furnace that argon gas atmosphere is protected, 750
~800 DEG C refine 3~7 minutes, then pour into mould and are air-cooled to room temperature；
2) plastic working：Plastic processing method includes at least one of rolling, extruding and drawing.
Rolling described in Zn-Mn-Cu systems as described above kirsite is divided into 2 kinds of rolling mill practice routes, by this 2 kinds of process routes
It is any all can finished product sheet material：
(1) hot rolling：Temperature is 250~380 DEG C；
(2) hot rolling → cold rolling：Hot-rolled temperature is 250~380 DEG C, and cold rolling temperature is room temperature；Above-mentioned hot rolling and cold rolling change
Shape amount is 20~95%.
Further, the extrusion temperature is 200~350 DEG C of progress, and extrusion ratio is 10~90.
Further, the drawing temperature be room temperature to 250 DEG C, drawing reduction of area is 5~95%.
The surface of kirsite as described above can also coat degradable macromolecule coating, ceramic coating or medication coat.
The thickness of the degradable macromolecule coating, the ceramic coating and the medication coat can be 0.01~5mm.
The material for preparing of the degradable macromolecule coating can be following at least one：PLA (PLA), PLLA
(PLLA), polyglycolic acid (PGA), poly- acetic acid lactones (PCL), paracyanogen base acrylate (PACA), poly- to dioxane
Ketone (poly- (p-dioxanone)).
The material for preparing of the ceramic coating can be following at least one：Hydroxyapatite (hydroxyapatite), phosphorus
Sour DFP (TCP) or tetracalcium phosphate (TTCP).
The medication coat can be following at least one：Rapamycin (RAPA) and its derivative coating, such as ethoxy spread out
Biological everolimus (everolimus) coating.
The characteristics of present invention can be degraded in vivo using Zn and Zn alloys, selects the Mn element and Cu beneficial to human body
Element improves pure Zn mechanical property as alloying element.The mechanical property of the Zn-Mn-Cu systems alloy of the present invention meets medical plant
Enter the intensity and plasticity requirements of body material, while can degrade in vivo again, can both overcome Mg and Mg alloy degradation rates are too fast to lead
The shortcoming of mechanical property rapid loss of implanting is caused, Ti and Ti alloys, stainless steel, Co-Cr-Mo alloys etc. are not present again medical
The problem of metal material non-degradable.The Zn-Mn-Cu systems kirsite of the present invention has biodegradable and permanently effective spy concurrently
Point.
The Zn-Mn-Cu systems kirsite that the present invention is provided can be used for preparing following medical implant：Cardiac stent, urethra branch
Frame, intestinal stent, trachea bracket, biliary tract rack, bone tissue reparation support, bone fracture device, fixing line, fixed screw, fixed pin, folder
Hone lamella, dental pulp pin or tooth filling material.
The invention has the advantages that：
(1) the Zn-Mn-Cu systems kirsite that the present invention is designed, the most alloying element of content uses the Mn elements of low cost,
And alloying element total content is low, the cost of alloy is low, suitable for promoting the use of on a large scale；
(2) mechanical property of Zn-Mn-Cu systems kirsite prepared by the present invention meets intensity and the modeling of medical implant material
Property require, while can degrade in vivo, with suitable internal degradation speed, it is possible to provide permanently effective support effect；
(3) when the Zn-Mn-Cu systems kirsite that the present invention is designed is used for degradable medical implant, in implantation a period of time
Interior energy plays the advantage of metal material high intensity, completes the function of implant.It is implanted into behind human lesion position, with diseased region
Reparation, it is finally completely degraded by human body fluid gradually corrosion degradation.The Mn ions discharged in degradation process can promote
The growth of histoorgan is restored, and with many benefits such as fat content, promotion cholesterol biosynthesis in reduction liver.Degraded
The Cu ions discharged in journey constitute copper enzyme and copper-binding protein, participate in metabolism and the RBC acceptor garland rate of iron.Fail to be inhaled by human body
Zn, Mn and Cu of receipts can be excreted by human metabolism.
Brief description of the drawings
Fig. 1 is the tensile stress-strain curve of casting Zn-Mn-Cu systems kirsite prepared by embodiment 1.
Wherein Fig. 1 a are the tensile stress-strain curve of casting Zn-0.8Mn-0.4Cu systems kirsite,
Fig. 1 b are the tensile stress-strain curve of casting Zn-0.4Mn-0.4Cu systems kirsite；
Fig. 2 is the tensile stress-strain curve of hot rolling Zn-Mn-Cu systems kirsite prepared by embodiment 2.
The wherein tensile stress-strain curve of Fig. 2 a hot rollings Zn-0.8Mn-0.4Cu systems kirsite,
The tensile stress-strain curve of Fig. 2 b hot rolling Zn-0.4Mn-0.4Cu systems kirsite,
Fig. 3 is electrochemical corrosion polarization of the hot rolling Zn-0.4Mn-0.4Cu alloys of the preparation of embodiment 2 in simulated body fluid
Curve.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise instructed.
Material, reagent used etc., unless otherwise instructed, are commercially obtained in following embodiments.
Percentage composition used, is weight/mass percentage composition unless otherwise instructed in following embodiments.
Embodiment 1：
Prepare casting Zn-Mn-Cu system's alloys and measure the mechanical property of material.
Using pure Zn (99.99%), pure Mn (99.9%), pure Cu (99.9%) as raw material, by following 2 kinds of mass percents
Mixing, is put into the Al in vacuum induction melting furnace2O3In crucible：(1) 98.8% Zn, 0.8% Mn and 0.4% Cu；(2)
99.2% Zn, 0.4% Mn and 0.4% Cu.First vacuumize, be passed through after after the near 30Pa of air pressure in vacuum induction melting furnace
Argon gas, makes argon pressure reach 0.04MPa.Then heating is equipped with the Al of raw material under argon gas protection2O3Crucible, 5 are refined at 760 DEG C
Minute, then alloy melt is poured into diameter 75mm cylindrical high purity graphite mould, room temperature is air-cooled to, Zn- is made
0.8Mn-0.4Cu and Zn-0.4Mn-0.4Cu alloy cast ingots.
According to GB/T 228.1-2010《Metal material stretching test part 1, room temperature test method》Prepare pole stretching
Test specimen, tension test is carried out using universal material mechanics machine at room temperature, and tensile strain rate is 10-3/s.Casting
The stretching engineering stress strain curve of Zn-Mn-Cu systems kirsite by Fig. 1 a as shown in figure 1, can must cast Zn-0.8Mn-0.4Cu
The tensile yield strength of alloy is 113.2MPa, and tensile strength is 120.1MPa, and elongation percentage is 0.44%；It must can be cast by Fig. 1 b
The tensile strength of Zn-0.4Mn-0.4Cu alloys is 83.9MPa, and elongation percentage is 0.25%, is difficult to use work because elongation percentage is too low
Cheng Changyong Rp0.2As yield strength, therefore take Rp0.1As yield strength, its value is 76.7MPa.
Embodiment 2：
Prepare hot rolling Zn-Mn-Cu system's sheet alloys and measure the mechanics and corrosive nature of material.
Zn-Mn-Cu systems alloy cast ingot is prepared according to the method provided in embodiment 1, thickness is cut from ingot casting for 30mm
Sheet material.First sheet material is preheated before hot rolling, process system is 320 DEG C and is incubated 1 hour.Then sheet material is taken from heating furnace
Go out to send into hot-rolling mill, its thickness is reduced into 5mm by 5 passage hot rollings, hot rolling deformation amount is up to 83.3%.
According to GB/T 228.1-2010《Metal material stretching test part 1, room temperature test method》Prepare plate stretching examination
Sample is tested, tension test is carried out using universal material mechanics machine at room temperature, tensile strain rate is 10-3/s.Hot rolling Zn-
Stretching engineering stress-strain curve of Mn-Cu systems alloy by Fig. 2 a as shown in Fig. 2 can obtain hot rolling Zn-0.8Mn-0.4Cu alloys
Tensile yield strength be 195.5MPa, tensile strength is 277.5MPa, and elongation percentage is 15.3%；Hot rolling Zn- can be obtained by Fig. 2 b
The tensile yield strength of 0.4Mn-0.4Cu alloys is 198.4MPa, and tensile strength is 292.4MPa, and elongation percentage is 29.6%.
The sample that size is 2mm (thickness) × 10mm × 10mm is cut from hot rolling Zn-0.4Mn-0.4Cu alloys, 800# is used
To 2000# SiC sand paper polishing sample surfaces, then mechanically polish.After sample clean drying, the mould that pH value is 7.40 is immersed in
Intend body fluid and (add following material in order in 1000ml simulated body fluid：8.035g NaCl, 0.355g NaHCO3,
0.225g KCl, 0.231g Na2HPO4·3H2O, 0.311g MgCl2·6H2O, 39ml 1.0MHCl, 0.292g CaCl2,
0.072g NaSO4, 6.118g Tris, 0~5ml 1.0MHCl in), the temperature for keeping simulated body fluid is 37 DEG C, is soaked wherein
Bubble starts to measure electrochemical corrosion polarization curve after 5 minutes, and sweep speed is 1mV/s.Fig. 3 is measurement result, and therefrom calculating can
The corrosion rate for obtaining hot rolling Zn-0.4Mn-0.4Cu alloys is 0.056mm/.
Embodiment 3：
Prepare cold rolling Zn-Mn-Cu systems sheet alloy.
The method provided by embodiment 1 prepares Zn-Mn-Cu systems alloy cast ingot, and the plate that thickness is 30mm is cut from ingot casting
Material.Hot rolling is first carried out, first sheet material is preheated before hot rolling, process system is 320 DEG C and is incubated 1 hour.Then from heating furnace
Sheet material is taken out into feeding hot-rolling mill, its thickness 15mm is reduced into by 2 passage hot rollings, hot rolling deformation amount is 50%.Treat hot rolled plate
The temperature of material is reduced to room temperature, is sent to cold-rolling mill, its thickness is reduced into 3mm by 4 passages, cold rolling reduction is 80%.
Embodiment 4：
Prepare extruding Zn-Mn-Cu systems alloy bar material.
The method provided by embodiment 1 prepares Zn-Mn-Cu systems alloy cast ingot, and a diameter of 40mm rod is cut from ingot casting
Material.Bar is preheated before extruding, process system is 300 DEG C and is incubated 2 hours.Then bar is taken out from heating furnace to be put into just
Into extruder, a diameter of 8mm bar is extruded by 1 passage, extrusion ratio is 25.
Embodiment 5：
Prepare drawing Zn-Mn-Cu systems alloy wire.
The method provided by embodiment 1 prepares Zn-Mn-Cu systems alloy cast ingot, and a diameter of 30mm rod is cut from ingot casting
Material.Bar is preheated before extruding, process system is 300 DEG C and is incubated 2 hours.Then from heating furnace take out bar be put into it is crowded
In press, a diameter of 5mm bar is extruded by 1 passage, extrusion ratio is 36.A diameter of 5mm bar is passed through 3 in room temperature
The cold drawn wire rod for pulling into a diameter of 2mm of passage, the total reduction of area of drawing is 84%.
Embodiment 6：
In Zn-Mn-Cu systems alloy surface coating curative drug rapamycin (RAPA) and degradable polymer PLA
(PLA)。
Sample is taken from hot rolling Zn-Mn-Cu systems sheet alloy prepared by embodiment 2, with 800# to 2000# SiC sand paper
Then polishing sample surfaces, mechanical polishing cleaned 15 minutes with supersonic wave cleaning machine in deionized water, takes out drying.By sample
Product, which are placed in Ultrasonic spraying machine, carries out spray treatment, and PLA-chloroform that carrying rapamycin is held in propeller is equal
Even solution, wherein chloroform are organic solvent.The ratio of rapamycin and PLA is 1:8, the volume ratio of PLA and chloroform is
1:15.The thickness of coat is 50 μm.Sample after coating is put into vacuum drying chamber, dried 18 hours at 37 DEG C, is removed
Remaining chloroform.
Claims (10)
1. a kind of bio-medical Zn-Mn-Cu systems kirsite, it is characterised in that alloy element component scope is 0.1~5% Mn,
0.1~2% Cu, surplus is Zn, and mentioned component is calculated by percentage to the quality.
2. Zn-Mn-Cu systems as claimed in claim 1 kirsite, it is characterised in that alloying element is count by weight percentage：
(1) by 98.5%~99.6% Zn, 0.3%~0.8% Mn and 0.1%~0.7%Cu composition；
(2) it is made up of 98.8% Zn, 0.8% Mn and 0.4% Cu；
(3) it is made up of 99.2% Zn, 0.4% Mn and 0.4% Cu.
3. the preparation method of Zn-Mn-Cu systems as claimed in claim 1 or 2 kirsite, it is characterised in that specific preparation process is such as
Under：
(1) cast：Using pure Zn, pure Mn and pure Cu as raw material, in the vacuum induction melting furnace that argon gas atmosphere is protected, 750~
800 DEG C refine 3~7 minutes, then pour into mould and are air-cooled to room temperature；
(2) plastic working：Plastic processing method includes at least one of rolling, extruding and drawing.
4. the preparation method of Zn-Mn-Cu systems as described in claim 3 kirsite, it is characterised in that the rolling is divided into 2 kinds
Rolling mill practice route, can finished product sheet material by any one of this 2 kinds of process routes：
(1) hot rolling：Temperature is 250~380 DEG C；
(2) hot rolling → cold rolling：Hot-rolled temperature is 250~380 DEG C, and cold rolling temperature is room temperature；Above-mentioned hot rolling and cold rolling deflection
For 20~95%.
5. such as the preparation method of the Zn-Mn-Cu systems kirsite in claim 3, it is characterised in that the extrusion temperature is 200~
350 DEG C of progress, extrusion ratio is 10~90.
6. the preparation method of Zn-Mn-Cu systems as described in claim 3 kirsite, it is characterised in that the drawing temperature is
Room temperature is to 250 DEG C, and drawing reduction of area is 5~95%.
7. such as any one of claim 1-2 Zn-Mn-Cu systems kirsite, it is characterised in that the surface of the kirsite is also applied
It is covered with degradable macromolecule coating, ceramic coating or medication coat；Three kinds of coating layer thicknesses are 0.01~5mm.
8. Zn-Mn-Cu systems as claimed in claim 7 kirsite, it is characterised in that the degradable macromolecule coating prepares material
Expect for following at least one：It is PLA, PLLA, polyglycolic acid, poly- acetic acid lactones, paracyanogen base acrylate, poly- to two
Oxa- cyclohexane ketone.
9. Zn-Mn-Cu systems as claimed in claim 7 kirsite, it is characterised in that the material for preparing of the ceramic coating is following
It is at least one：Hydroxyapatite, tricalcium phosphate or tetracalcium phosphate.
10. Zn-Mn-Cu systems as claimed in claim 7 kirsite, it is characterised in that the medication coat is following at least one：
Rapamycin and its derivative coating.
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Effective date of registration: 20220119 Address after: 102629 room 409-172, 4th floor, building 1, No. 38 Yongda Road, Daxing biomedical industry base, Zhongguancun Science Park, Daxing District, Beijing (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 |