CN108165782A - A kind of medical zinc-containing alloy band and preparation method thereof - Google Patents
A kind of medical zinc-containing alloy band and preparation method thereof Download PDFInfo
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- CN108165782A CN108165782A CN201711472254.3A CN201711472254A CN108165782A CN 108165782 A CN108165782 A CN 108165782A CN 201711472254 A CN201711472254 A CN 201711472254A CN 108165782 A CN108165782 A CN 108165782A
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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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- 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
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
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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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- 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
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Abstract
The invention discloses a kind of medical zinc-containing alloy bands and preparation method thereof, and the alloy strip steel rolled stock is by following material composition：Mg 0.2~3wt.%, Li 0.05~1.5wt.%, Ca 0.02~0.3wt.% of 0.02~0.5wt.%, Y, remaining is Zn and a small amount of (content ＜ 0.1wt.%) inevitable impurity.Smelting obtained alloy cast ingot can prepare ultra-thin alloy strip steel rolled stock, while realize alloy structure regulation and control and refinement, achieve the effect that significantly improve its comprehensive mechanical property by a series of plastic deformation processing and the combination of annealing process.The medical zinc-containing alloy band of the present invention has high-strength tenacity (283~451MPa of tensile strength, fracture elongation 19~42%), numerous advantages such as the degradation rate (0.07~0.23mm/year) of good biocompatibility and appropriate regulator, belong to medical zinc-containing alloy implantation instrument field of material preparation, be expected to expand the scope of application of the zinc-containing alloy in more medical indications and medical instrument.
Description
Technical field
The present invention relates to a kind of medical zinc-containing alloy band and its technologies of preparing, belong to medical zinc-containing alloy implantation instrument material
Expect preparing technical field.
Background technology
At present, clinical implantation medical metal material is mainly using inertia non-degradable metal material, for example, (1) austenite
Stainless steel 316 LSS；(2) simple metal (titanium, niobium, zirconium etc.)；(3) titanium-base alloy；(4) cobalt-base alloys；(5) cochrome；(6) nickel
Evanohm；(7) niti-shaped memorial alloy.These bio-inert materials are usually deposited in as permanent fixture in vivo
In tissue, energy stable for extended periods of time, but there is also various drawbacks.For example, (1) permanent metal medical instrument is implanted into people
After body, there is the easy thrombus that formed to cause in-stent restenosis, intimal fibrosis insufficient, and implantation material can not take out, once
Blood vessel blockage occurs again for same position, then is implanted into and will become extremely difficult；(2) implantation such as stainless steel, titanium alloy nail, bone plate
After human body, if being drawn off after organization healing by second operation, pain and the financial burden of patient can be increased, made simultaneously
Into the waste of medical resource；(3) its higher elasticity modulus can cause stress-shielding effect, poor biocompatibility, in physiology
Harmful ion can be spread to surrounding tissue under corrosive environment, toxic side effect is generated to human body, causes inflammation.Therefore exploitation has excellent
The medical material of good mechanical property and biocompatibility becomes the important development direction in the field.
At present, in degradable medical metal material field, ferrous alloy, magnesium base alloy are the more deep materials of Recent study
Material.But obvious shortcoming existing for this kind of degradable metal material limits their extensive uses in the field.Ferrous alloy
Corrosion rate is too slow, and the degradable time is up to the several years, can cause the bad human response similar to bio-inert material.Magnesium-based
For alloy although with good biocompatibility, corrosion resistance is poor, is degraded quickly in human body, generates a large amount of hydrogen, sternly
Ghost image rings the structural strength of implantation material and mechanical support effect.
Recently as further investigation of the researcher to zinc and its alloy, it is found that zinc and its kirsite are very potential
As a kind of novel degradable medical metal material.Zinc is nearly all in participant's body as one of human body necessity trace element
Physiological metabolism process.Other than catalysis and structure effect are played in various metals enzyme, transcription factor and albumen, zinc is also with god
Form through mediator or quenched sample functions.Facilitation is played to the metabolic turnover of cell, the immunity of human body can be enhanced；
The growth and development of human body are maintain, zinc-deficiency may result in the disorder of all physiological functions of human body.Zn content in adult body
For 1.4~2.3g, the allowance,dietary of the daily zinc of health adult is 15~40mg, and the zinc of the daily intake of about 300mg of adult is
There may be toxic reactions.Therefore, kirsite has good biocompatibility.Meanwhile the standard electrode potential of pure zinc for-
0.763V, between pure magnesium (- 2.37V) and pure iron (- 0.44V), the corrosion rate of zinc-containing alloy is between magnesium base alloy and iron
Between based alloy, therefore its degradation rate has some superiority in the requirement of the clinical plant of matching.
But the comprehensive mechanical property of the pure zinc of as cast condition is too poor, corrosion rate is also relatively slow, it is difficult to meet the need of clinical plant
It asks.Therefore, there is an urgent need for exploitation one kind to have an excellent comprehensive mechanical property, the controllable novel degradable zinc-containing alloy of corrosion rate and its
Preparation method.
Invention content
Technical problem：The present invention provides one kind and solves the problems, such as that the pure zinc comprehensive mechanical property of as cast condition is poor, realizes implantation material
Expect that degradation rate is controllable, improve the biocompatibility of material, realize scantling microminiaturization medical zinc-containing alloy band and
Preparation method.
Technical solution：The medical zinc-containing alloy band of the present invention, is prepared in accordance with the following steps：
(1) metallic zinc is heated to 420~450 DEG C, after metallic zinc is completely melt, melt temperature is risen to for heat preservation
In CO at 620~660 DEG C2And SF6Mixed atmosphere protection is lower to add in lithium metal, calcium metal, magnesium metal and metallic yttrium, stirs evenly,
After metal all fusing, standing forms alloy melt, is cooled to 520~560 DEG C, and casting after standing obtains alloy cast ingot；
(2) alloy cast ingot keeps the temperature to 12 at 310~350 DEG C~for 24 hours, alloy cast ingot is then air-cooled to room temperature, is obtained
Alloy cast ingot blank；
(3) alloy cast ingot blank at 150~250 DEG C is kept the temperature and hot extrusion is carried out after 15~30min, extrusion ratio for (9~
36): 1, obtain alloy crin；
(4) the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains φ=0.1~0.3mm's
Alloy wire；
(5) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, be processed into width for 4~
15mm, the medical zinc-containing alloy band that thickness is 10~60 μm.
Further, in the medical zinc-containing alloy band of the present invention, the mass fraction of raw material is in the step (1)：Mg
0.2~3 part, 0.02~0.5 part of 0.05~1.5 part of Li, Ca, 0.02~0.1 part of Y, Zn94.7~99.71 part.
Further, it in the medical zinc-containing alloy band of the present invention, in the step (1), further includes and is injected to alloy melt
Carbon trichloride is refined, and the injection rate of the carbon trichloride accounts for the 0.2~0.5% of alloy melt gross mass, is then cooled to
520~560 DEG C, stand casting acquisition alloy cast ingot after 10~30min.
Further, in the medical zinc-containing alloy band of the present invention, during the cold drawing of the step (4), silk material per pass
Secondary deflection be 9~20%, once annealed when cumulative deformation reaches 180~200%, annealing temperature be 200~
300 DEG C, the time is 10~20min.
Further, it is also thin to rolling alloy in the step (5) in the medical zinc-containing alloy band of the present invention
Band carries out whole passage annealing, and temperature is 200~300 DEG C, and the time is 10~20min, is then air-cooled to room temperature.
The medical zinc-containing alloy band of the present invention, hundred number≤0.1 of quality of impurity, impurity may be Fe, Mn, Cu, Si
Deng.
The medical zinc-containing alloy band of the present invention, tensile strength can reach 283~451MPa, and fracture elongation can reach
19~42%.
The medical zinc-containing alloy band of the present invention, the corrosion rate in simulated body fluid are 0.07~0.23mm/year.
The medical zinc-containing alloy band of the present invention, cytotoxicity are 0~1 grade, possess good biocompatibility.
The preparation method of the medical zinc-containing alloy band of the present invention, includes the following steps：
(1) metallic zinc is heated to 420~450 DEG C, after metallic zinc is completely melt, melt temperature is risen to for heat preservation
In CO at 620~660 DEG C2And SF6Mixed atmosphere protection is lower to add in lithium metal, calcium metal, magnesium metal and metallic yttrium, stirs evenly,
After metal all fusing, standing forms alloy melt, is cooled to 520~560 DEG C, and casting after standing obtains alloy cast ingot；
(2) alloy cast ingot keeps the temperature to 12 at 310~350 DEG C~for 24 hours, alloy cast ingot is then air-cooled to room temperature, is obtained
Alloy cast ingot blank；
(3) alloy cast ingot blank at 150~250 DEG C is kept the temperature and hot extrusion is carried out after 15~30min, extrusion ratio for (9~
36): 1, obtain alloy crin；
(4) the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains φ=0.1~0.3mm's
Alloy wire；
(5) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, be processed into width for 4~
15mm, the medical zinc-containing alloy band that thickness is 10~60 μm.
Further, in the method for the present invention, the mass fraction of raw material is in the step (1)：0.2~3 part of Mg, Li
0.05~1.5 part, 0.02~0.1 part of 0.02~0.5 part of Ca, Y, Zn94.7~99.71 part.
Further, it in the method for the present invention, in the step (1), is also refined to alloy melt injection carbon trichloride,
The injection rate of the carbon trichloride accounts for the 0.2~0.5% of alloy melt gross mass, is then cooled to 520~560 DEG C, stands 10
Casting obtains alloy cast ingot after~30min.
Further, in the method for the present invention, during the cold drawing of the step (4), every time deflection of silk material is 9
~20%, it is once annealed when cumulative deformation reaches 180~200%, annealing temperature is 200~300 DEG C, the time 10
~20min.
Further, in the method for the present invention, in the step (5), also the alloy thin band that rolling obtains after the completion is carried out
Whole passage annealing, temperature are 200~300 DEG C, and the time is 10~20min, is then air-cooled to room temperature.
In step 1 of the present invention, high-strength tenacity is had both to obtain, degradation rate matching is controllable, the good doctor of biocompatibility
With zinc-containing alloy band, the content (＜ 0.1wt.%) of the impurity such as Fe, Mn, Cu, Si need to be strictly controlled.After step (5) rolling
To strip width be 4~15mm, thickness is 10~60 μm.
The above-mentioned medical zinc-containing alloy band of the present invention can include bone within plant, jaw in degradable medical instrument is prepared
Medical embedded instrument and the various medical instruments such as face surgery and neurocranial surgery implantation instrument, various operation sticking patch, such as active plant
Enter shell, surgical instrument of formula electromedical equipment etc..
Medical zinc-containing alloy band and preparation method thereof of the present invention is having high-strength tenacity and good biocompatibility
Simultaneously, moreover it is possible to adjust its corrosion degradation rate in vivo.
Advantageous effect：Compared with prior art, the present invention it has the following advantages：
1. compared with traditional inert metal material, a kind of medical zinc-containing alloy band of the invention can be used as medical treatment implantation
Body natural degradation in vivo can be completed to degrade and pass through metabolism safety from internal within a certain period of time after reaching medical effect
It excretes, the financial burden for alleviating patient also allows patient to avoid the pain that second operation taking-up implantation material is brought.
2. the alloying elements such as magnesium elements, calcium constituent, elemental lithium in a kind of medical zinc-containing alloy band of the present invention, can have
Crystal grain thinning is imitated, the intensity and plasticity for making alloy are significantly improved, while can keep the consistency of alloy corrosion.The pure zinc of as cast condition
Tensile strength only have 20MPa, by the addition and adjusting of alloying element, the mechanical property of material can be increased substantially.
3. kirsite lacks plastic deformation ability force difference because of the close-packed hexagonal structure of itself, slip system.One kind of the present invention is medical
Zinc-containing alloy is had the processing hardening phenomenon that plastic deformation generates by being plastically deformed the combination with intermediate annealing process
Effect softening, realizes large plastometric set and the ultra-thin zinc-containing alloy band of small size prepares feasibility, so as to be implanted into for it in medical treatment
Application provide more possibilities.
4. the present invention a kind of medical zinc-containing alloy band, can according to needed for its different medical implant performance will
It asks, adjusts the additive amount of alloying element, to obtain corresponding mechanical property and corrosion resisting property.Magnesium elements, calcium member are reduced as appropriate
The content of element etc., you can obtain moderate strength high-ductility corrosion resistant material, suitable for be drawn into silk material bar, stent tubing or
It is rolled into band and plank；The appropriate content for increasing magnesium elements, calcium constituent etc., you can the material of the medium plasticity of high intensity is obtained,
It is implanted into suitable for bone.
5. the present invention medical zinc-containing alloy band, compared with magnesium base alloy, ferrous alloy, have in simulated body fluid compared with
It is 0.07~0.23mm/year for suitable corrosion rate, it can holding structure supportive and mechanics be complete during one's term of military service at it
Property, and discharge is metabolized after organization healing, meet requirement of the implantation material to corrosion rate.
6. only pipe is now for the safety of medical treatment implantation kirsite still in the exploratory stage, but one kind of the present invention is medical
Zinc-containing alloy band has good biocompatibility, and cytotoxicity is 0~1 grade, meets medical embedded material standard.With zinc member
Element is similar, and the magnesium elements in alloy of the present invention are also one of human essential elements；Magnesium has good biocompatibility and biology
Safety.Magnesium is indispensable mineral element during human metabolism, and general adult need to take in 300-350mg daily
Magnesium；Magnesium metal implantation in animal body is it was found that, magnesium ion can enhance the activity of osteoblast, promotion implantation material week
The growth of new bone is enclosed, while dirty to the important device such as the heart, liver,spleen,kidney will not be damaged.Similar with zinc, magnesium elements, calcium, lithium are equal
For the element that human body contains in itself, calcium is healthy and beneficial to human skeleton, and lithium can effectively improve and stablize the mood of people.Meanwhile
Micro yttrium is harmless.
Specific embodiment
With reference to embodiment, the present invention is further illustrated.
In following embodiment, purity >=99.99% of metallic zinc, purity >=99.99% of magnesium metal, the purity of lithium metal
>=99.99%, purity >=99.99% of calcium metal, purity >=99.99% of metallic yttrium has both good comprehensive mechanics to obtain
The material of performance, biological corrosion performance and bio-compatible performance should strictly control the content of impurity F e, Mn, Cu, Si.
Following embodiment surveys simulated body fluid during corrosion rate, component and its a concentration of：8g/1NaCl, 0.4g/1KCl,
0.14g/1CaCl2, 0.35g/1NaHCO3, 1g/l C6H12O6, 0.1g/l MgCl2·6H2O, 0.06g/1MgSO4·7H2O,
0.06g/1KH2PO4, 0.06g/1Na2HPO4·12H2O。
Embodiment 1：
The medical zinc-containing alloy band of the present invention, raw materials used mass fraction are as follows：Mg is 0.2 part, and Li is 0.05 part,
Ca be 0.02 part, Y be 0.02 part, Zn be 99.71 parts remaining be Zn.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 420 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 620 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, be cooled to 520 DEG C；
(3) into alloy melt, in mass ratio, the carbon trichloride for accounting for alloy melt total weight 0.2% is added in, stirred and quiet
10min is put, casting obtains alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature into 12h at 310 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 15min at 150 DEG C, extrusion ratio 36: 1 obtains
Alloy crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.1mm
Golden filament；Wherein, every time deflection is 20%, is once annealed when cumulative deformation reaches 200%, annealing temperature
It is 200 DEG C, time 10min；
Step 5, it rolls：
(1) alloy threadlet for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 15mm, thick
Spend the ultra-thin alloy strip steel rolled stock for 10 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 200 DEG C, time 10min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 2：
The medical zinc-containing alloy band of the present invention, raw materials used mass fraction are as follows：Mg is 0.3 part, and Li is 0.1 part,
Ca is 0.1 part, and Y is 0.05 part, and Zn is 99.45 parts.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 420 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 620 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, after being cooled to 520 DEG C, casting obtains
Obtain alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature for 24 hours at 310 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 20min at 150 DEG C, extrusion ratio 24: 1 obtains
Alloy crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.1mm
Golden filament；Wherein, every time deflection is 20%, is once annealed when cumulative deformation reaches 200%, annealing temperature
It is 250 DEG C, time 10min；
Step 5, it rolls：
(1) alloy threadlet for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 15mm, thick
Spend the ultra-thin alloy strip steel rolled stock for 20 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 250 DEG C, time 10min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 3：
The medical zinc-containing alloy band of the present invention, raw materials used mass fraction are as follows：Mg is 3 parts, and Li is 1.5 parts, Ca
It it is 0.5 part, Y is 0.3 part, and Zn is 94.7 parts.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 450 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 660 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, be cooled to 560 DEG C；
(3) into alloy melt, in mass ratio, the carbon trichloride for accounting for alloy melt total weight 0.5% is added in, stirred,
30min is stood at 560 DEG C, casting obtains alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature for 24 hours at 350 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 30min at 250 DEG C, extrusion ratio 9: 1 is closed
Golden crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.3mm
Golden filament；Wherein, every time deflection is 9%, is once annealed when cumulative deformation reaches 180%, annealing temperature
It is 300 DEG C, time 20min；
Step 5, it rolls：
(1) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 4mm, thick
Spend the ultra-thin alloy strip steel rolled stock for 60 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 300 DEG C, time 20min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 4：
The medical zinc-containing alloy band of the present invention, raw materials used mass fraction are as follows：Mg is 1.5 parts, and Li is 0.8 part,
Ca is 0.3 part, and Y is 0.12 part, and Zn is 97.28 parts.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 430 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 640 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, be cooled to 530 DEG C；
(3) into alloy melt, in mass ratio, the carbon trichloride for accounting for alloy melt total weight 0.4% is added in, stirred,
20min is stood at 530 DEG C, casting obtains alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature into 18h at 330 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 20min at 225 DEG C, extrusion ratio 16: 1 obtains
Alloy crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.2mm
Golden filament；Wherein, every time deflection is 16%, is once annealed when cumulative deformation reaches 176%, annealing temperature
It is 250 DEG C, time 20min；
Step 5, it rolls：
(1) alloy threadlet for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 9mm, thick
Spend the ultra-thin alloy thin band for 30 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 250 DEG C, time 20min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 5：
The medical zinc-containing alloy band of the present invention, raw materials used mass fraction are as follows：Mg is 0.8 part, and Li is 0.3 part,
Ca is 0.12 part, and Y is 0.08 part, and Zn is 98.7 parts.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 430 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 630 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, be cooled to 535 DEG C；
(3) into alloy melt, in mass ratio, the carbon trichloride for accounting for alloy melt total weight 0.3% is added in, stirred,
15min is stood at 535 DEG C, casting obtains alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature into 12h at 320 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 30min at 200 DEG C, extrusion ratio 25: 1 obtains
Alloy crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.1mm
Golden filament；Wherein, every time deflection is 12%, is once annealed when cumulative deformation reaches 192%, annealing temperature
It is 225 DEG C, time 14min；
Step 5, it rolls：
(1) alloy threadlet for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 6mm, thick
Spend the ultra-thin alloy thin band for 20 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 225 DEG C, time 14min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 6：
The medical zinc-containing alloy thin-band material of the present invention, raw materials used mass fraction are as follows：Mg is 2.4 parts, Li 1
Part, Ca is 0.35 part, and Y is 0.2 part, and Zn is 96.05 parts.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 445 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 650 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, casting after being cooled to 550 DEG C obtains
Alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature into 18h at 340 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 30min at 225 DEG C, extrusion ratio 9: 1 is closed
Golden crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.3mm
Golden filament；Wherein, every time deflection is 10%, is once annealed when cumulative deformation reaches 180%, annealing temperature
It is 275 DEG C, time 15min；
Step 5, it rolls：
(1) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 5mm, thick
Spend the ultra-thin alloy strip steel rolled stock for 50 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 250 DEG C, time 20min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 7：
The medical zinc-containing alloy thin-band material of the present invention, raw materials used mass fraction are as follows：Mg is 0.5 part, Li 0.2
Part, Ca is 0.12 part, and Y is 0.05 part, and Zn is 99.13 parts.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 425 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 630 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, be cooled to 530 DEG C；
(3) into alloy melt, in mass ratio, the carbon trichloride for accounting for alloy melt total weight 0.35% is added in, stirred,
20min is stood at 530 DEG C, casting obtains alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature for 24 hours at 320 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 15min at 250 DEG C, extrusion ratio 20: 1 obtains
Alloy crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.1mm
Golden filament；Wherein, every time deflection is 11%, is once annealed when cumulative deformation reaches 198%, annealing temperature
It is 250 DEG C, time 15min；
Step 5, it rolls：
(1) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 12mm, thick
Spend the ultra-thin alloy strip steel rolled stock for 15 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 275 DEG C, time 15min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 8：
The medical zinc-containing alloy thin-band material of the present invention, raw materials used mass fraction are as follows：Mg is 0.4 part, and Li is
0.05 part, Ca is 0.02 part, and Y is 0.02 part, and Zn is 99.51 parts.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 450 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 650 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, casting after being cooled to 560 DEG C obtains
Alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature for 24 hours at 340 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 30min at 220 DEG C, extrusion ratio 24: 1 obtains
Alloy crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.1mm
Golden filament；Wherein, every time deflection is 20%, is once annealed when cumulative deformation reaches 180%, annealing temperature
It is 250 DEG C, time 15min；
Step 5, it rolls：
(1) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 4mm, thick
Spend the ultra-thin alloy strip steel rolled stock for 30 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 275 DEG C, time 15min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 9：
The medical zinc-containing alloy thin-band material of the present invention, raw materials used mass fraction are as follows：Mg is 1.5 parts, Li 0.2
Part, Ca is 0.5 part, and Y is 0.1 part, and Zn is 97.7 parts.
The preparation process of the zinc-containing alloy band is as follows：
Step 1,
(1) raw material are weighed according to above-mentioned alloy proportion；
(2) after inner wall is coated with the iron crucible preheating of protective layer, metallic zinc is put into, 430 DEG C is warming up to and treats that pure zinc is completely molten
After change, when zinc melt is warming up to 660 DEG C, in CO2And SF6Mixed atmosphere protection is lower to add in magnesium metal, calcium metal, lithium metal, gold
Belong to yttrium, stir evenly, after metal all fusing, stand and form alloy melt for a period of time, casting after being cooled to 550 DEG C obtains
Alloy cast ingot.
Step 2, Homogenization Treatments：
(1) alloy cast ingot is kept the temperature for 24 hours at 320 DEG C；
(2) alloy cast ingot after heat preservation is air-cooled to room temperature, obtains alloy cast ingot blank.
Step 3, hot extrusion is carried out after alloy cast ingot blank being kept the temperature 30min at 250 DEG C, extrusion ratio 16: 1 obtains
Alloy crin；
Step 4, the multi-pass cold drawing by the progress of obtained alloy crin at room temperature, finally obtains the conjunction of φ=0.2mm
Golden filament；Wherein, every time deflection is 16%, is once annealed when cumulative deformation reaches 192%, annealing temperature
It is 250 DEG C, time 10min；
Step 5, it rolls：
(1) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 6mm, thick
Spend the ultra-thin alloy strip steel rolled stock for 20 μm；
(2) rolling alloy thin band being subjected to whole passage annealing, temperature is 275 DEG C, time 10min, after
Room temperature is air-cooled to, high tough medical zinc-containing alloy is obtained and is implanted into ultra-thin strip.
Embodiment 10：
With zinc-containing alloy band medical made from Examples 1 to 9, vitro cytotoxicity test is carried out.
The present embodiment according to GB/T16886.5-2003 to medical zinc-containing alloy carrying material carry out cell in vitro (L-929 into
Fibrocyte) toxotest, cytotoxicity is shown as 0~1 grade, and catabolite is on cell activity without significantly influencing and inhibiting
Effect, shows excellent cell compatibility.
With zinc-containing alloy band made from Examples 1 to 9, in-vitro simulated body fluid immersion test is carried out, measures each ingredient zinc
Based alloy thin-band material corrosion rate such as table 1：
Table 1
External degradation rate of the present embodiment according to ASTM-G31-72 standard method of test research kirsite bands, finds
In 37 DEG C of simulated body fluid environment, the degradation rate of kirsite band is moderate, maintains 0.4mm/y hereinafter, and can pass through
The corrosion degradation rate of the additive amount regulation and control alloy of alloying element.
With zinc-containing alloy band medical made from Examples 1 to 9, it is as shown in table 2 to carry out Tensile Test Results.
Table 2
The present embodiment stretches medical kirsite band Examples 1 to 9 according to GB/T228.1-2010 testing standards
Mechanics Performance Testing, the results are shown in Table 2.Research shows that the tensile strength of medical kirsite band is up to 451MPa, fracture
Elongation percentage reaches as high as 42%.
Claims (10)
1. a kind of medical zinc-containing alloy band, which is characterized in that the band is prepared in accordance with the following steps：
(1) metallic zinc is heated to 420~450 DEG C, heat preservation, after metallic zinc is completely melt, melt temperature is risen to 620~
In CO at 660 DEG C2And SF6Mixed atmosphere protection is lower to add in lithium metal, calcium metal, magnesium metal and metallic yttrium, stirs evenly, treats gold
After belonging to all fusings, standing forms alloy melt, is cooled to 520~560 DEG C, and casting after standing obtains alloy cast ingot；
(2) alloy cast ingot keeps the temperature to 12 at 310~350 DEG C~for 24 hours, alloy cast ingot is then air-cooled to room temperature, obtains alloy
Ingot casting blank；
(3) hot extrusion is carried out after alloy cast ingot blank to be kept the temperature to 15~30min at 150~250 DEG C, extrusion ratio is (9~36):
1, obtain alloy crin；
(4) the multi-pass cold drawing by the progress of obtained alloy crin at room temperature finally obtains the alloy of φ=0.1~0.3mm
Silk material；
(5) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 4~15mm, thickness
Spend the medical zinc-containing alloy band for 10~60 μm.
2. medical zinc-containing alloy band according to claim 1, which is characterized in that the quality of raw material in the step (1)
Number is：0.05~1.5 part of 0.2~3 part of Mg, Li, 0.02~0.1 part of 0.02~0.5 part of Ca, Y, Zn94.7~99.71
Part.
3. medical zinc-containing alloy band according to claim 1, which is characterized in that in the step (1), further include to conjunction
Golden melt injection carbon trichloride is refined, and the injection rate of the carbon trichloride accounts for the 0.2~0.5% of alloy melt gross mass,
Then 520~560 DEG C are cooled to, stands casting acquisition alloy cast ingot after 10~30min.
4. a kind of medical zinc-containing alloy band according to claim 1,2 or 3, which is characterized in that the step (4) it is cold
In drawing process, every time deflection of silk material is 9~20%, is once moved back when cumulative deformation reaches 180~200%
Fire, annealing temperature are 200~300 DEG C, and the time is 10~20min.
5. a kind of medical zinc-containing alloy band according to claim 1,2 or 3, which is characterized in that in the step (5),
Whole passage annealing is also carried out to rolling alloy thin band, temperature is 200~300 DEG C, and the time is 10~20min, so
After be air-cooled to room temperature.
6. a kind of preparation method of medical zinc-containing alloy band, which is characterized in that this method includes the following steps：
(1) metallic zinc is heated to 420~450 DEG C, heat preservation, after metallic zinc is completely melt, melt temperature is risen to 620~
In CO at 660 DEG C2And SF6Mixed atmosphere protection is lower to add in lithium metal, calcium metal, magnesium metal and metallic yttrium, stirs evenly, treats gold
After belonging to all fusings, standing forms alloy melt, is cooled to 520~560 DEG C, and casting after standing obtains alloy cast ingot；
(2) alloy cast ingot keeps the temperature to 12 at 310~350 DEG C~for 24 hours, alloy cast ingot is then air-cooled to room temperature, obtains alloy
Ingot casting blank；
(3) hot extrusion is carried out after alloy cast ingot blank to be kept the temperature to 15~30min at 150~250 DEG C, extrusion ratio is (9~36):
1, obtain alloy crin；
(4) the multi-pass cold drawing by the progress of obtained alloy crin at room temperature finally obtains the alloy of φ=0.1~0.3mm
Silk material；
(5) alloy wire for obtaining multi-pass cold drawing rolls on finishing mill, is processed into width as 4~15mm, thickness
Spend the medical zinc-containing alloy band for 10~60 μm.
A kind of 7. preparation method of medical zinc-containing alloy band according to claim 6, which is characterized in that the step
(1) mass fraction of raw material is in：0.05~1.5 part of 0.2~3 part of Mg, Li, 0.02~0.5 part of Ca, Y 0.02~0.1
Part, Zn94.7~99.71 part.
A kind of 8. preparation method of medical zinc-containing alloy band according to claim 6, which is characterized in that the step
(1) it in, is also refined to alloy melt injection carbon trichloride, the injection rate of the carbon trichloride accounts for alloy melt gross mass
0.2~0.5%, 520~560 DEG C are then cooled to, stands casting acquisition alloy cast ingot after 10~30min.
9. the preparation method of a kind of medical zinc-containing alloy band according to claim 6,7 or 8, which is characterized in that described
During the cold drawing of step (4), every time deflection of silk material is 9~20%, when cumulative deformation reaches 180~200%
Shi Jinhang once anneals, and annealing temperature is 200~300 DEG C, and the time is 10~20min.
10. the preparation method of a kind of medical zinc-containing alloy band according to claim 6,7 or 8, which is characterized in that described
In step (5), whole passage annealing is also carried out to the alloy thin band that rolling obtains after the completion, temperature is 200~300 DEG C, when
Between for 10~20min, be then air-cooled to room temperature.
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| CN111331128A (en) * | 2020-04-16 | 2020-06-26 | 长沙镁捷新材料科技有限公司 | Method for preparing zinc alloy degradable material by sintering metal powder |
| CN112430764A (en) * | 2019-08-26 | 2021-03-02 | 上海交通大学 | Biodegradable high-strength and high-toughness medical Zn-Cu-Mn-Zr alloy in organism |
| CN113186427A (en) * | 2021-04-27 | 2021-07-30 | 河海大学 | High-toughness degradable zinc alloy with high work hardening rate and preparation method and application thereof |
| CN113528870A (en) * | 2021-07-15 | 2021-10-22 | 东南大学 | Degradable Zn-Li-X alloy wire and preparation method thereof |
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