CN107460371A - A kind of Zn-Li systems kirsite and preparation method and application - Google Patents
A kind of Zn-Li systems kirsite and preparation method and application Download PDFInfo
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- 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
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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
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable 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
- 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
- A61L27/50—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
- 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
- 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
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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
- 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
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- 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
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- Vascular Medicine (AREA)
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- Heart & Thoracic Surgery (AREA)
- Dermatology (AREA)
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Abstract
The invention discloses a kind of Zn Li systems kirsite and preparation method and application.Zn Li systems kirsite of the present invention includes Zn and Li；By weight percentage, Li weight/mass percentage composition is 0~30% in the kirsite, but does not include 0.Its preparation method, comprise the following steps：(1) the Zn and Li is mixed, obtains mixture；(2) by the mixture according to following a) or b) step is handled, and is then cooled down, that is, obtains the kirsite；A) in CO2And SF6Under atmosphere protection, the mixture is subjected to melting or sintering；B) under vacuum atmosphere protection, hydrogen is dissolved in the mixture and carries out the melting.Kirsite excellent in mechanical performance prepared by the present invention, permanently effective support force can be provided in vivo, there is excellent cell compatibility, blood compatibility and tissue, organ compatibility, can be used for the preparation of biological and medicinal implant material.
Description
Technical field
The present invention relates to a kind of Zn-Li systems kirsite and preparation method and application, belong to medical metal material prepare and
Technical field.
Background technology
Currently used for clinic bio-medical material mainly have biomedical metallic material, inorganic material, high polymer material,
Composite and biomimetic material etc..Biomedical metallic material is the metal or alloy for being used as bio-medical material, this kind of
Material has high mechanical strength and anti-fatigue performance, is the widest load implantation material of clinical practice.Such material
Application it is very extensive, throughout various aspects such as sclerous tissues, soft tissue, artificial organs and shell auxiliary appliances.Except
It is required that this kind of material has outside the physical property of good mechanical property and correlation, excellent antibiosis reason corrosivity and biology
Compatibility is also its prerequisite condition.Subject matter in medical metal material application is due to the corruption of physiological environment
Erosion and caused by metal ion the regression of material self property is spread and is implanted into surrounding tissue, the former may cause malicious pair
Effect, the latter frequently result in the failure of implantation.Have been used to clinic medical metal material mainly have simple metal (titanium,
Tantalum, niobium, zirconium etc.), and stainless steel, cobalt-base alloys and titanium-base alloy etc..These materials non-degradable in human body,
To be permanent implanted, after military service of the implant in human body expires, it is necessary to taken out by second operation, so as to trouble
Person brings unnecessary physiology pain and financial burden.
Degradable metal is the new class medical metal material using magnesium alloy and iron as representative for starting the beginning of this century to develop rapidly
Material, this kind of new medical metal material have abandoned the biography that people generally use metal implant as bio-inert material
System thought, and the spy of corrosion (degraded) dexterously easily occurs in human body environment's (chloride ion-containing) using magnesium and iron
Property, expectation can realize the repair function of metal implant in vivo with controlled manner, and finally complete weight in tissue
Build/function is degradable for harmless metal ion and other products after repairing.In view of ferrous alloy is in human body
Inside degraded slow, and catabolite can produce certain toxic side effect to human body, research medical degradable gold in recent years
The study hotspot of category is mainly on medical degradable magnesium alloy, such as AZ31, WE43, Mg-Ca, although magnesium alloy
There is tempting application prospect as biomaterial, but study that to find that magnesium alloy has a corrosion rate too fast, organizing
For organ without before fully healing, implant just can lose its mechanical integrity quickly, thus be necessary to develop new
Degradable alloy has met clinical demand.
Zinc is one of micronutrient element most abundant in human body, and 85% zinc is present in muscle and bone in human body, 11%
It is present in skin and liver, remaining zinc is present in tissue everywhere.Normal Zn content (24h) in the cleer and peaceful urine of blood in human body in
It is 800 ± 200 μ g/dL and 109-130 μ g/dL respectively.In multicellular tissue, almost all of zinc is present in cell
Interior, 30%-40% is present in nucleus, and 50% is present in cytoplasm, in organelle and vesica, it is remaining be present in it is thin
In after birth.For human body, daily zinc intake is about 15mg/d.Zinc is for the structure of numerous macromoleculars and super
Cross the effect that key is played in more than 300 kinds of enzymatic reaction.The substructure of many protein and DNA or other protein
The rack platform that zinc fingers offer need to be depended on during reaction is carried out.Zinc ion in vivo mainly with protein and core
The composite form of acid exists and participates in various intermediate supersessions, propagation and the expression of gene information, storage and synthesis,
Meanwhile also act as the effect of stable chromatin and biofilm structure.In bone environment, the zinc ion in Gegenbaur's cell leads to
Activation tRNA synzyme and stimulated gene expression are crossed to promote the synthesis of protein, while also increases intracellular DNA
Quantity, so as to promote Gegenbaur's cell New born formation and mineralising.Meanwhile zinc ion is by regulating and controlling Calcium Signal path,
Promote the apoptosis of osteoclast.Zinc ion is by facilitating bone and suppression bone information finally to increase bone mass, with other
Trace element is compared, and toxicity of the zinc ion in the metabolism of bone is minimum.In cardiovascular environment, by supplementing zinc
Ion can protect cardiac muscle cell not reduced stress damage by Acute oxidative, while the inflammation for preventing myocardial damage initiation is anti-
Should.Zinc ion also plays vital effect in regulating blood pressure, the serum of hyperpietic, lymphocyte and
The Zn content of bone can reduce and heart, liver, and Zn content raises in the tissue such as kidney.Experiment shows inside zinc support, zinc
(6.5 months) can suppress local smooth muscle cell proliferation so as to effectively suppress endometrial hyperplasia in being chronically implanted.Lack
Zinc can cause epidermis, and enteron aisle, nervous centralis, immune system, bone and reproductive system produce a series of relevant issues.
Lithium is also the necessary trace element of life, and Environmental Protection in America mechanism was in the adult for being proposed for a 70kg in 1985
The daily lithium intake of people is about 650-3100 μ g.Human body about 66%-90% lithium intake comes from vegetables and cereal,
Remaining lithium comes from animal food.Human body absorbs the soluble salt containing lithium by the sodium-ion channel of small intestine, by kidney
Discharge, absorbed lithium ion is evenly distributed in body fluid, little with extracellular lithium ion content difference into the cell.Lithium
Ion is most in cerebellum distribution, next to that brain and kidney.Lithium in Serum content is directly proportional to the intake of lithium ion,
The adult human serum lithium content for taking in 385-1540 μ g/day is about 7-28 μ g/L.In the case of identical lithium intake,
Height and body weight are inversely proportional with lithium intake.Scarce lithium ion normally behaves as exception in gentle behavior rather than spirit is different
Often, scarce lithium ion may there is also relation with kidney trouble.Low concentration lithium agent is suitable for prophylactic treatment, can be effectively pre-
Anti- depressive psychopathia.Monoamine oxidase (MAO) activity can be improved by supplementing appropriate lithium ion, stimulate vitamin
Transported to brain cell, can make one happy, play antidepressant effect.Because the atomic radius of lithium is small, Ke Yicong
The reaction site of biomembrane and enzyme displacement sodium, potassium, magnesium, calcium plasma, can also be with aluminium, manganese, vanadium reaction.
Synthesis also without document and patent report Zn-Li systems alloy and performance, and propose Zn-Li both at home and abroad at present
It is that alloy is used as degradable biological medical materials'use.
The content of the invention
It is an object of the invention to provide zinc prepared by a kind of Zn-Li systems kirsite and preparation method and application, the present invention
Alloy mechanical property is excellent, can provide permanently effective support force in vivo, has excellent cell compatibility, blood
Liquid phase capacitive and tissue, organ compatibility, can be used for the preparation of biological and medicinal implant material.
Zn-Li systems provided by the invention kirsite, the kirsite include Zn and Li；
By weight percentage, Li weight/mass percentage composition is 0~30% in the kirsite, but does not include 0.
Zn-Li systems provided by the invention kirsite is specially following 1) -10) in it is any, with percentage by weight：
1) it is made up of 99.9~99% Zn and 0.1%~1% Li；
2) it is made up of 99% Zn and 1% Li；
3) it is made up of 99.2% Zn and 0.8% Li；
4) it is made up of 99.4% Zn and 0.6% Li；
5) it is made up of 99.5% Zn and 0.5% Li；
6) it is made up of 99.65% Zn and 0.35% Li；
7) it is made up of 99.7% Zn and 0.3% Li；
8) it is made up of 99.75% Zn and 0.25% Li；
9) it is made up of 99.8% Zn and 0.2% Li；
10) it is made up of 99.85% Zn and 0.15% Li；
11) it is made up of 99.9% Zn and 0.1% Li.
In above-mentioned kirsite, in the kirsite also include trace element, it is described trace element for magnesium, calcium, strontium,
At least one of silicon, phosphorus, manganese, silver, copper, tin, iron and rare earth element；
In the kirsite, the micro- weight/mass percentage composition is 0~3%, but does not include 0.
In above-mentioned kirsite, the surface of the kirsite is also coated with coating；
The thickness of the coating is 0.01~5mm；
The coating is degradable macromolecule coating, ceramic coating, chemical conversion film layer, differential arc oxidation film layer and medicine
At least one of coating, specifically, the degradable macromolecule coating prepare material for it is following 1) and 2) in extremely
Few one kind：1) PCL, PLA, polyglycolic acid, PLLA, polybutylcyanoacrylate, condensing model,
At least one of poly phosphazene, poly- para-dioxane ketone, poly- butyric ester and poly- hydroxyl valerate；2) gather
Lactic acid, PCL, polyglycolic acid, PLLA, polybutylcyanoacrylate and poly- para-dioxane ketone
In at least two composition copolymers；The molecular weight for preparing material of the degradable macromolecule coating is
5000~100000；
The ceramic coating prepares material as hydroxyapatite, tricalcium phosphate, the calcium of phosphoric acid oxygen four, calcium monohydrogen phosphate, nothing
At least one of water calcium monohydrogen phosphate, calcium octahate phosphate, fluor-apatite, magnesium hydroxide and strontium phosphide；
The chemical conversion film layer is fluorinated film and/or phosphate film layer, and the material for preparing of the fluorinated film is hydrogen fluorine
At least one of acid, sodium fluoride, potassium fluoride and ammonium fluoride；The material for preparing of the phosphate film layer is biphosphate
Salt；
The differential arc oxidation film layer prepares material to add at least one in sodium hydroxide and/or potassium hydroxide electrolyte
Following compositions：Phosphate, silicate, meta-aluminate, fluoride, zirconates and permanganate；
The medication coat can be anticoagulation medicine, rapamycin and its derivative coating, taxol coating, actinomyces
Plain D, endothelial growth factor, everolimus coating, sirolimus coating, mitomycin coating and antimicrobial coating
At least one of, specifically, the anticoagulation medicine is heparin, hirudin and a receptor antagonists of II b/ of GP III.
Present invention also offers a kind of preparation method of above-mentioned kirsite, comprise the following steps：(1) by the Zn
Mixed with the Li, obtain mixture；
(2) by the mixture according to following a) or b) step is handled, and is then cooled down, that is, obtains the zinc
Alloy；
A) in CO2And SF6Under atmosphere protection, the mixture is subjected to melting or sintering；
B) under vacuum atmosphere protection, hydrogen is dissolved in the mixture and carries out the melting.
In the present invention, in methods described, the hydrogen injects the mixture in the case where its air pressure is 1MPa, makes melting
Metal liquid reaches saturation, then pouring into water cooled copper mould makes alloy liquid cool down from top to bottom；It is obtained under the conditions of this
The porosity 20-30% of the kirsite, 150-200 μm of aperture.
In above-mentioned preparation method, step (1) also includes adding the step of trace element mixes.
Also include coating in above-mentioned preparation method, after cooling down described in step (2) the degradable macromolecule coating,
The step of ceramic coating, the chemical conversion film layer, the differential arc oxidation film layer or medication coat.
In the present invention, the method for coating the Biodegradable high-molecular coating is that the kirsite is carried out into pickling, so
Its material for preparing in the Biodegradable high molecular coating is dissolved in dip-coating 10~30 in the colloid of trichloroethanes preparation afterwards
After minute, at the uniform velocity pull out and carry out the kirsite that centrifugal treating obtains being coated with Biodegradable high-molecular coating, can also
Prepared using the methods of electrostatic spinning, spin coating；
The method for coating the ceramic coating can be chemical deposition, Biomimetic, sol-gal process, Hydrothermal Synthesiss
It is any in method；
The chemical deposition be in the solution containing certain density calcium ion and phosphate anion, by control calcium/
Phosphorus ratio, reaction time, reaction temperature and pH value make insoluble CaP mineralizations in zinc alloy surface.Solution is selected
Ca (NO3) 2, Ca-EDTA and CaCl2 etc. provide calcium ion, from K2HPO4, NaH2PO4 and Na3PO4
Phosphate anion is provided.Between 27~90 DEG C, the time is solution chemistry reaction temperature general control：2~24h, pH
It is worth for 5.9~11.9.Resulting coating layer thickness is generally several microns to more than ten microns；
The Biomimetic is that kirsite is soaked in into temperature for 37 DEG C, pH=7.4 supersaturated calcium microcosmic salt solution,
That is certain time in simulated body fluid (such as SBF, Hank ' s balanced salt solution), the process of active HA coatings is generated；
The sol-gal process is：3.94g Ca (NO3) 24H2O and 0.71g P2O5 is dissolved separately in
In 10mL ethanol solution.The presoma of calcium instills in the presoma of phosphorus dropwise, obtains Ca/P than the calcium for 1.67
Phosphorus collosol suspension liquid, this suspension is placed in closing beaker, at 26 DEG C, mixing speed is to stir 5h under 400rpm,
Then use pulling machine that kirsite sample is dipped vertically into suspension into certain time and then lifted out with certain speed
Come, the thickness of film layer is obtained according to plan, so lifted repeatedly for several times；Then 24h is placed at room temperature to complete at timeliness
Reason, sample is gradually heated to 60 DEG C of holding 24h afterwards, finally sinters 6h at 300 DEG C；
The anodic oxidation and Hydrothermal Synthesiss with reference to method be that the kirsite is being contained into 0.01~0.5mol/L β-sweet
In the electrolyte of oleophosphoric acid sodium and 0.1~2mol/L calcium acetates, 10~30min is aoxidized under 200~500V, then by institute
State kirsite and 1~4h is handled at 200~400 DEG C；
The preparation method for coating fluorinated film in the chemical composition coating be by kirsite be soaked in fluoride ion (hydrofluoric acid,
Sodium fluoride, potassium fluoride or ammonium fluoride) solution in be that chemical reaction generation MgF occurs for matrix surface and solution2；Phosphoric acid
The preparation method of salt film layer is that metal is soaked in containing in phosphatic solution, and metal chemically reacts with phosphate
Yuan Wei generates low solubility or insoluble phosphatization salt, the presoma typically using dihydric phosphate as chemical conversion reaction.
The preparation method for coating the differential arc oxidation film layer is entered for that will first pass through cerate, lf or chemical deposition
Row pretreatment, then kirsite is immersed in the electrolyte that basis is sodium hydroxide/potassium hydroxide, generally use electric current
Control model, direct current, exchange and pulse current may be selected.Pulse frequency can be 10Hz to 2000Hz, and processing is certain
Progress sealing of hole and post processing after time, usable polymers sealing of hole, self-assembled multilayer film, phosphate and silicate sealing of hole,
Collosol and gel sealing of hole and LBL self-assembly film sealing of hole.Post processing includes hydro-thermal process, high energy pulse electron beam treatment and moved back
Burning hot processing；
The method for coating the medication coat is physics and chemical method；The physical method coating process is mainly using leaching
Bubble, spraying method；The immersion process is to be configured to active medicine and controlled release carrier (or single active medicine)
Solution, specific concentration can the drug dose with needed for be different and different because of solution viscosity, then soaks the medical implant
Steep in solution, then by necessary last handling process, be such as crosslinked, dry, solidification step, medicine painting is made
Layer；The spraying method is that active medicine and controlled release carrier (or single active medicine) are configured into solution, then
In 0.01~0.50ml/min of flow velocity, 1~10W of ultrasonic power, 1~50wt.% of concentration of polymer solution, cycle-index 10~100
Solution is spread evenly across the medical implant surface using Spray painting tool under secondary process conditions, through drying, solidification
Medication coat is made afterwards Deng post-processing step；The chemical method is mainly electroplated with electrochemical principle, institute
It is that electricity occurs in the electrode by the medical embedded making using active medicine and (or) controlled release carrier to state chemical method
Redox reaction, the medical embedded surface is set to form the stable medication coat by being chemically bonded.
In above-mentioned preparation method, the temperature of the melting can be 600~850 DEG C；
The sintering uses element powders mixed-sintering method, prealloy powder sintering process or self-propagating high-temperature synthesis.
In the present invention, the element powders mixed-sintering method is to be well mixed the mixture, is pressed into base, then
In vacuum sintering furnace, with 2~4 DEG C/min be warming up to 100~200 DEG C at a slow speed followed by with 30 DEG C/min be rapidly heated to
200~300 DEG C of sintering, then cool, obtain into the Zn-Li systems alloy of loose structure；
The prealloy powder sintering process is that the mixture is carried out into high-energy ball milling, type is then pressed into, at 250~350 DEG C
Carry out heat treatment 10~20 hours, obtain the Zn-Li systems alloy of loose structure；
The self-propagating high-temperature synthesis is that the mixture is pressed into base, and under inert gas shielding, pressure is
1×103~1 × 105Pa, temperature are at 250~350 DEG C, and Zn-Li systems alloy blank then is lighted into carry out self propagating high temperature
Synthesis, obtains the Zn-Li systems alloy of loose structure.
In above-mentioned preparation method, methods described is also including the step of being machined the kirsite；
The machining is rolling, forging, quickly at least one of solidification and extruding.
In the present invention, the rolling, which includes progress hot rolling and finish rolling, the hot rolling successively, to be carried out at 200~300 DEG C,
The finish rolling can be carried out at 150~250 DEG C, and the thickness after the kirsite rolling can be 1~2mm；The hot rolling tool
Body can be carried out at 260 DEG C, and the finish rolling can specifically be carried out at 260 DEG C, and the thickness after the kirsite rolling is specific
Can be 1mm；
The forging includes being incubated the kirsite under conditions of 150~200 DEG C and at 200~300 DEG C
Under the conditions of the step of being forged, the time of the insulation is 3~50 hours, and the speed of the forging is not less than
350mm/s；
The quick solidification comprises the following steps：Under inert atmosphere (argon gas) protection, using high vacuum fast quenching system
Prepare rapid coagulation band, then the strip is broken into it is powdered, finally under conditions of 150~350 DEG C, very
Empty 1~24h of hot pressing；The setting of the high vacuum fast quenching system is as follows：2~8g of feeding quantity, induction heating power are
3~7kW, nozzle and roller spacing are 0.80mm, injection pressure is 0.05~0.2MPa, roller speed is 500~3000r/min
And nozzle slot size is 1film × 8mm × 6mm；
The temperature of the extruding can be 150~280 DEG C, concretely 260 DEG C；Ingot casting extruding the preincubation time can be
0.5~24h, concretely 2h, extrusion ratio can be 10~70, concretely 36, extrusion speed is 0.1~10mm/s,
Can be 1mm/s.
Invention further provides the kirsite prepare can be in degraded by body fluid medical implant application.
In above-mentioned application, it is described can degraded by body fluid medical implant be degradable blood vessel bracket, degradable orthopaedics plant
Enter at least one of thing, degradable dental material and degradable suture material.
The present invention has advantages below：
(1) mechanical performance of Zn-Li systems alloy prepared by the present invention is excellent, has the characteristics of intensity is high, and plasticity is good,
It disclosure satisfy that physical efficiency bearing position requirement.It can in vivo absorb, degrade again simultaneously, having " regulatable rotten in vivo
The characteristics of erosion degradation characteristic " and " effective mechanical support is provided ".
(2) can be injured portion after implanting when Zn-Li systems of the present invention alloy is used for degradable medical implant
The permanently effective medical science support protective effect of position offer (such as fixed protection bone tissue supports narrow blood vessel), and can
While chance tissue repair, gradually absorbed, degrade by vivo environment.Material quantity and volume gradually decrease, material
The catabolite of material and the ion discharged can be absorbed by organisms, be metabolized, and help body recovery and gradually discharge body
Outside, after body recovers completely, material is absorbed completely degrades, without secondary taking-up.
(3) it is provided by the invention can degraded by body fluid medical implant it is nontoxic, possess good histocompatbility and blood
Compatibility.
Brief description of the drawings
Fig. 1 is the picture of Zn-Li alloy cast ingots prepared by the embodiment of the present invention 1.
Fig. 2 is the picture of Zn-Li alloy bar materials prepared by the embodiment of the present invention 2.
Fig. 3 is the metallograph of Zn-Li alloy bar materials prepared by the embodiment of the present invention 2, and wherein Fig. 3 (a) is pure zinc
Metallograph, Fig. 3 (b) is Zn：0.1Li metallograph, Fig. 3 (c) are Zn：0.4Li metallograph,
Fig. 3 (d) is Zn：0.8Li metallograph.
Fig. 4 is the X-ray diffraction analysis of Zn-Li alloys prepared by the embodiment of the present invention 2.
Fig. 5 is the photo of the Zn-Li systems alloy tensile sample prepared according to testing standard.
Fig. 6 is the photo that the Zn-Li systems alloy prepared according to testing standard compresses sample.
Fig. 7 is the tensile mechanical properties of Zn-Li alloys.
Fig. 8 is the Compressive Mechanical Properties of Zn-Li alloys.
Fig. 9 is the stress strain curve of Zn-Li alloys.
Figure 10 is the compression curve of Zn-Li alloys.
Figure 11 is electrochemical corrosion curve of the Zn-Li alloys in simulated body fluid.
Figure 12 be Zn-Li alloys in 50% leaching liquor to the cell after cytosis different time with respect to proliferation rate.
Figure 13 be Zn-Li alloys in 10% leaching liquor to the cell after cytosis different time with respect to proliferation rate.
Figure 14 is the hemolysis rate of Zn-Li alloys.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
Percentage composition used, is weight/mass percentage composition unless otherwise instructed in following embodiments.
Embodiment 1, prepare as cast condition Zn-Li systems alloy
Made with pure Zn (99.99wt.%), pure Li (99.95wt.%) (being purchased from Huludao Zinc Industry Co., Ltd.)
For raw material, by different mass ratioes, (Zn and Li mass ratio are respectively 99：1、99.2：0.8、99.4:0.6、99.5：
0.5、99.65:0.35、99.7:0.3、99.75:0.25、99.8:0.2、99.85:0.15、99.9:0.1) mix, in CO2+SF6
Under atmosphere protection, 800 DEG C of meltings, after raw material fully melts, after being incubated 10min, recirculated water quickly cools down, and is made
Zn-Li systems alloy pig (Zn-Li systems kirsite i.e. of the present invention, as shown in Figure 1), wherein, Zn-0.1Li represent Zn with
Li mass ratio is 99.9：0.1, Zn-0.4Li expression Zn and Li mass ratio is 99.6：0.4, Zn-0.8Li represents
Zn and Li mass ratio is 99.6：0.8.
Embodiment 2, prepare As-extruded Zn-Li systems alloy
The Zn-Li systems alloy pig of as cast condition is prepared in the step being first according in the embodiment of the present invention 1, using extruding
Mode prepares Zn-Li systems alloy bar material (Zn-Li systems kirsite i.e. of the present invention, as shown in Figure 2), using radial compression,
Ingot casting is incubated 2h, 260 DEG C of holding temperature, and extrusion temperature is 260 DEG C, extrusion ratio 36, extrusion speed 1mm/s systems
It is standby go out a diameter of 10mm Zn-Li systems alloy bar material.
Embodiment 3, the kirsite microscopic examination of Zn-Li systems
By the Zn-Li systems alloy bar material in the embodiment of the present invention 2, φ 10x1mm samples are prepared by wire cutting, according to
It is secondary through 400#, 800#, 1200# and 2000#SiC sand paper series sanding and polishing.In acetone, absolute ethyl alcohol and deionization
After being cleaned by ultrasonic 15min respectively in water, dried at 25 DEG C.Sample is subjected to X-ray diffraction analysis and with 4% nitric acid
Cleaned after 5~30s of alcohol etch sample with deionized water, after drying, in metallography microscope sem observation.
Fig. 3 is the metallograph of Zn-Li systems kirsite, from figure 3, it can be seen that after extruding, crystal grain is thin
Small, the second phase is evenly distributed on matrix, and Fig. 4 is X ray diffracting spectrum, as seen from Figure 4, adds Li
Afterwards, pure zinc crystal structure changes, and with the increase of Li contents, many new diffraction maximums occurs, illustrates to add Li
Significant impact is generated to the structure of pure zinc.
Embodiment 4, the kirsite Mechanics Performance Testing of Zn-Li systems
Will according to 1-2 of the embodiment of the present invention method prepare Zn-Li systems kirsite, respectively according to
ASTM-E8/E8M-09 extension tests standard and ASTM-E9 compression standards prepare stretching sample and compression sample (such as
Fig. 5, shown in 6), Che Guang.After being cleaned by ultrasonic 15min respectively in acetone, absolute ethyl alcohol and deionized water, use
Universal material mechanics machine carries out Compression and Expansion experiment, draw speed and compression speed to be respectively at room temperature
0.05mm/mmmin and 0.005m/mmin.
The room temperature tensile and compression performance such as Fig. 7 of each sample of Zn-Li systems kirsite, shown in 8, are compared, Zn-0.1Li with pure zinc
Excellent combination property, yield strength 341MPa, tensile strength 431MPa, elongation percentage 28%, compressive strength 788MPa,
Being improved with lithium content, the intensity of alloy further improves, but plasticity declines, when lithium content reaches 0.8wt.%, material
Show fragility feature.After extruding, the mechanical property of material is significantly improved.
Fig. 9, the stretching under the 10 Zn-Li systems kirsite squeezed states prepared for the present invention and compression curve, by the figure
Understand, with the increase of alloy lithium content, the intensity of material significantly increases but elongation percentage and compression plasticity all substantially reduce,
When lithium content reaches 0.8wt.%, material shows Brittleness, can not measure tensile strength.
Embodiment 5, the test of Zn-Li alloy corrosions performance
By the Zn-Li alloys through extruding in the embodiment of the present invention 2, φ 10x1mm Zn-Li alloys are prepared by wire cutting
Coupons, successively through 400#, 800#, 1200# and 2000#SiC sand paper series sanding and polishing.In acetone, anhydrous second
After being cleaned by ultrasonic 15min respectively in alcohol and deionized water, dried at 25 DEG C.Electro-chemical test, electrochemistry are carried out afterwards
Test is to carry out the above-mentioned sample handled well in Hank ' s simulated body fluids by Autolab electrochemical workstations
Electro-chemical test.(Hank ' s simulated body fluid NaCl 8.0g, CaCl2 0.14g,KCl 0.4g,NaHCO30.35g, Portugal
Grape sugar 1.0g, MgCl2·6H2O 0.1g,Na2HPO4·2H2O 0.06g,KH2PO4 0.06g,MgSO4·7H2O
0.06g is dissolved in 1L deionized waters)
Figure 11 is anodic polarization curves of pure zinc and the Zn-Li alloy in Hank ' s simulated body fluids, can from Figure 11
To find out, after Li is added, the corrosion potential of material is negative to be moved, and corrosion rate is substantially accelerated, pure by being calculated
Zinc, Zn-0.1Li, Zn-0.8Li degradation speed are 0.027mm/year, 0.038mm/year, 0.629 respectively
mm/year。
The cell compatibility experiment of embodiment 6, Zn-Li alloys
The Zn-Li alloys prepared by the method for the embodiment of the present invention 2, φ 10x1mm coupons are prepared by wire cutting,
Through 400#, 800#, 1200# and 2000#SiC sand paper series sanding and polishing.In acetone, absolute ethyl alcohol and deionized water
After the middle 15min of ultrasonic cleaning respectively, dried at 25 DEG C.Contact angle test, sample are carried out to sample by deionized water
Through ultraviolet-ray sterilizing, it is placed in sterile orifice plate, is accumulated by specimen surface and contain 10% serum and 1% dual anti-(mould
Element plus streptomysin mixed solution) DMEM cell culture mediums by the ratio between volume be 1.25cm2/ mL ratio adds
DMEM cell culture mediums, be placed in 37 DEG C, 95% relative humidity, 5%CO224h in incubator, obtain Zn-Li conjunctions
Golden leaching liquor stoste, it is 50% that leaching liquor stoste is diluted into concentration respectively, 10% dilution leaching liquor, sealing, 4 DEG C
Refrigerator saves backup.
Leaching liquor is diluted to observe with cell inoculated and cultured and result：After HUVEC cell recoveries, passage, it is suspended in
In DMEM cell culture mediums, it is inoculated on 96 well culture plates, after cultivating 24 hours, negative control group adds DMEM
Cell culture medium, positive controls add the cell culture medium containing 10%DMSO, and experimental group adds obtained above
Zn-Li alloys dilute leaching liquor, and it is 2~5 × 10 to make final cell concentration4/mL.It is placed in 37 DEG C, 5%CO2Incubator
Middle culture, culture plate is taken out respectively after 1,2,4 day, the form of living cells is observed under inverted phase contrast microscope and is led to
Cross the test that CCK8 kits carry out cell survival rate.
Figure 12,13 are relative survival rate of the HUVEC cells in 50%, 10%Zn-Li alloy leaching liquors respectively,
From Figure 12,13 it can be seen that in 50% leaching liquor group, pure zinc and Zn-0.1Li alloy has overt toxicity to cell
Function cells survival rate is less than 70%.When Li contents are 0.8, material is to cytotoxic.And 10% leaching liquor group,
Cell survival rate exceedes negative control group, has excellent cell compatibility.In vivo in environment, because body fluid follows
Ring, catabolite can be diluted by body fluid caused by material degradation, so assessing cytocompatibility using dilution leaching liquor
Property is more reasonable.Found by cell experiment, Zn-Li alloys have good biocompatibility.
Embodiment 7, the test of Zn-Li alloys blood compatibility
By Zn-Li alloy of the embodiment of the present invention 2 through rolling, φ 10x1mm Zn-Li alloys are prepared by wire cutting and tried
Print, through 400#, 800#, 1200# and 2000#SiC sand paper series sanding and polishing.In acetone, absolute ethyl alcohol and go
After being cleaned by ultrasonic 15min respectively in ionized water, dried at 25 DEG C.New blood with healthy volunteer is gathered, is placed in
The anticoagulant tube that 3.8wt.% sodium citrates are included as anti-coagulants preserves.4 are pressed with 0.9% physiological saline：5 ratio is dilute
Release and dilute blood sample is made.Sample is immersed in 10mL physiological saline, 37 ± 0.5 DEG C of insulation 30min, adds 0.2mL
Dilute blood sample, 37 ± 0.5 DEG C of insulation 60min.Using 10mL physiological saline as negative control group, 10mL
Deionized water is as positive controls.Centrifuged 5 minutes through 3000rpm, take supernatant Unic-7200 UV, visible lights
Spectrophotometer 545nm measures absorbance OD values, sets three groups of Duplicate Samples to carry out statistical analysis.
Hemolysis rate is calculated with below equation：
Hemolysis rate=(experimental group OD values-feminine gender group OD values)/(positive group OD values-feminine gender group OD values) × 100%.
Experimental result such as Figure 14, the hemolysis rate of Zn-Li alloys of the present invention are below 1%, and far smaller than Clinical practice will
The secure threshold 5% asked, Zn-Li systems of the present invention kirsite show good blood compatibility.
Claims (10)
- A kind of 1. Zn-Li systems kirsite, it is characterised in that：The kirsite includes Zn and Li；By weight percentage, Li weight/mass percentage composition is 0~30% in the kirsite, but does not include 0.
- 2. kirsite according to claim 1, it is characterised in that：Also include trace element in the kirsite, The trace element is at least one of magnesium, calcium, strontium, silicon, phosphorus, manganese, silver, copper, tin, iron and rare earth element；In the kirsite, the micro- weight/mass percentage composition is 0~3%, but does not include 0.
- 3. kirsite according to claim 1 or 2, it is characterised in that：The surface of the kirsite is also coated with Coating；The thickness of the coating is 0.01~5mm；The coating is degradable macromolecule coating, ceramic coating, chemical conversion film layer, differential arc oxidation film layer and medicine At least one of coating；Specifically, the degradable macromolecule coating prepare material for it is following 1) and 2) in extremely Few one kind：1) PCL, PLA, polyglycolic acid, PLLA, polybutylcyanoacrylate, condensing model, At least one of poly phosphazene, poly- para-dioxane ketone, poly- butyric ester and poly- hydroxyl valerate；2) gather Lactic acid, PCL, polyglycolic acid, PLLA, polybutylcyanoacrylate and poly- para-dioxane ketone In at least two composition copolymers；The molecular weight for preparing material of the degradable macromolecule coating is 5000~100000；The ceramic coating prepares material as hydroxyapatite, tricalcium phosphate, the calcium of phosphoric acid oxygen four, calcium monohydrogen phosphate, nothing At least one of water calcium monohydrogen phosphate, calcium octahate phosphate, fluor-apatite, magnesium hydroxide and strontium phosphide；The chemical conversion film layer is fluorinated film and/or phosphate film layer；The material for preparing of the fluorinated film is hydrogen fluorine At least one of acid, sodium fluoride, potassium fluoride and ammonium fluoride；The material for preparing of the phosphate film layer is biphosphate Salt；The differential arc oxidation film layer prepares material to add at least one in sodium hydroxide and/or potassium hydroxide electrolyte Following compositions：Phosphate, silicate, meta-aluminate, fluoride, zirconates and permanganate；The medication coat can be anticoagulation medicine, rapamycin and its derivative coating, taxol coating, actinomyces Plain D, endothelial growth factor, everolimus coating, sirolimus coating, mitomycin coating and antimicrobial coating At least one of；Specifically, the anticoagulation medicine is heparin, hirudin and a receptor antagonists of II b/ of GP III.
- 4. the preparation method of the kirsite any one of claim 1-3, comprises the following steps：(1) by described in Zn and Li mixing, obtains mixture；(2) by the mixture according to following a) or b) step is handled, and is then cooled down, that is, obtains the zinc Alloy；A) in CO2And SF6Under atmosphere protection, the mixture is subjected to melting or sintering；B) under vacuum atmosphere protection, hydrogen is dissolved in the mixture and carries out the melting.
- 5. preparation method according to claim 4, it is characterised in that：In methods described, step (1) is also wrapped Include the step of adding the trace element mixing.
- 6. the preparation method according to claim 4 or 5, it is characterised in that：In methods described, step (2) Described in cool down after also include coating the degradable macromolecule coating, the ceramic coating, the chemical conversion film layer, The step of differential arc oxidation film layer or the medication coat.
- 7. according to the preparation method any one of claim 4-6, it is characterised in that：The temperature of the melting is 600~850 DEG C；The sintering uses element powders mixed-sintering method, prealloy powder sintering process or self-propagating high-temperature synthesis.
- 8. according to the preparation method any one of claim 4-8, it is characterised in that：Methods described also includes will The step of kirsite is machined；The machining is rolling, forging, quickly at least one of solidification and extruding.
- 9. kirsite any one of claim 1-3 prepare can be in degraded by body fluid medical implant application.
- 10. application according to claim 9, it is characterised in that：It is described can degraded by body fluid medical implant for can In degraded intravascular stent, degradable orthopaedics implant, degradable dental material and degradable suture material at least It is a kind of.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748313A (en) * | 2008-12-19 | 2010-06-23 | 北京有色金属与稀土应用研究所 | Zinc-lithium alloy material and preparation method thereof |
| CN104212998A (en) * | 2014-08-21 | 2014-12-17 | 北京大学 | Zn-Mg zinc alloy and preparation method and application thereof |
| CN104651665A (en) * | 2015-03-13 | 2015-05-27 | 周功耀 | Corrosion-resistant and high-strength and toughness Zn-Fe-Li-based zinc alloy capable of being degraded in human body and application of corrosion-resistant and high-strength and toughness Zn-Fe-Li-based zinc alloy |
| CN105925847A (en) * | 2016-05-12 | 2016-09-07 | 管仁国 | Novel biodegradable zinc-based metal material and ureteral expandable stent obtained through material |
-
2016
- 2016-06-02 CN CN201610387456.7A patent/CN107460371B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101748313A (en) * | 2008-12-19 | 2010-06-23 | 北京有色金属与稀土应用研究所 | Zinc-lithium alloy material and preparation method thereof |
| CN104212998A (en) * | 2014-08-21 | 2014-12-17 | 北京大学 | Zn-Mg zinc alloy and preparation method and application thereof |
| CN104651665A (en) * | 2015-03-13 | 2015-05-27 | 周功耀 | Corrosion-resistant and high-strength and toughness Zn-Fe-Li-based zinc alloy capable of being degraded in human body and application of corrosion-resistant and high-strength and toughness Zn-Fe-Li-based zinc alloy |
| CN105925847A (en) * | 2016-05-12 | 2016-09-07 | 管仁国 | Novel biodegradable zinc-based metal material and ureteral expandable stent obtained through material |
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