CN103526091B - A kind of degradable biological medical magnesium alloy and preparation method thereof - Google Patents
A kind of degradable biological medical magnesium alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of degradable biological medical magnesium alloy, be made up of the material of following weight percent: Zn1.0 ~ 3.0%, Y0.20 ~ 1.50%, Nd0.40 ~ 1.50%, Zr0.30 ~ 0.50%, all the other are Mg and inevitable impurity element.Also disclose the preparation method of this alloy, this magnesium alloy makes ordinary magnesium alloy by melting, in furnace charge the consumption of Zn, Y, Nd be its in the magnesium alloy content 1.2-1.4 doubly, the consumption of Zr be its in the magnesium alloy content 2-2.5 doubly.The present invention passes through the magnesium alloy adding rare earth element y in magnesium-zinc alloy, Nd, Zr make preparation, overcome cytotoxicity and the problem such as erosion rate is too fast, and through extrusion processing, the nanometer MgZn Particle Phase that in its matrix, even dispersion distributes a large amount of, reduce the potential difference with matrix, the corrosion resistance nature of alloy is improved greatly; There is good mechanical property simultaneously.
Description
Technical field
The invention belongs to biomedical materials field, be specifically related to a kind of degradable biological medical magnesium alloy and preparation method thereof.
Background technology
In recent years, with the raising of people's living standard and the change of dietary structure, the cardiovascular and cerebrovascular diseases caused because of hyperlipidemia, hypertension has become one of primary disease threatening human health.As far back as 20th century, Minimally Interventional Therapy vascular disease technology starts to be applied, and being recognized subsequently is one of the most effective means for the treatment of cardiovascular and cerebrovascular diseases; Intravascular stent implantation is arisen at the historic moment, and develops rapidly, is being widely used in cardiovascular disorder interventional therapy.The implantation of small support, makes the clinical disease such as myocardial ischemia and coronary heart disease can be eased at once after surgery, has saved life, and patient can leave hospital after 24 hours in walking, evident in efficacy.Intravascular stent can be classified in the following manner: be divided into from expansion formula and balloon-expandable with support at Ink vessel transfusing expansion mode; Exposed type, coating type and multiple (film) type is divided into rack surface disposition; Support type and therapeutic type is divided into cradling function type; Permanent support and biodegradable stent (the most frequently used sorting technique) is divided into degrading.Non-degradable material wherein for permanent support has: (1) austenitic stainless steel (316LSS); (2) cochrome; (3) Medical tantalum; (4) titanium and titanium alloys; (5) niti-shaped memorial alloy; (6) platinum iridium alloy; Permanent type support, due to its non-biodegradable, easily forms thrombus, causes secondary narrow.Therefore, the novel degradable magnesium alloy materials developed is the requirement needed badly.Magnesium alloy has as the major advantage of degradable blood vessel bracket material: (1) degradability; (2) excellent biocompatibility; (3) low thrombogenicity; (4) cost of alloy is low; (5) excellent in mechanical performance; (6) there is MRI visuality, radiography can be carried out to blood vessel.
Mainly contain in the research of magnesium alloy as medical material at present: first Heublein etc. study using magnesium alloy AE21 as absorbable metal support.20 AE21 supports are successfully inserted 11 pig intra-arterial, and animal does not have thrombosis at duration of test (10,35,56 days), and arteries expansion is good, and 11 pigs are in stent area without visible Inflammatory response, and biocompatibility is good; When inserting 35 ~ 56 days, scaffold degradation and lose anchorage force, but blood vessel occurs that forward reconstructs, and makes the vessel lumen of the 56th day be greater than the 35th day.66 WE43 magnesium alloy brackets and 33 stainless steel stents are inserted 33 miniature pig coronary artery internal reference researchs by DiMario etc., research shows that magnesium alloy bracket has good vasodilation ability, and inserting of magnesium alloy bracket inhibits smooth muscle cell proliferation and accelerate endothelialization speed.Metal institute of the Chinese Academy of Sciences and Chinese Medical Sciences University have carried out the basic research work of degradable magnesium alloy vascular support.Select AZ31 magnesium alloy to be timbering material, prepared the degradable magnesium alloy support carrying medication coat, and complete animal and insert experimental study.AZ31 magnesium alloy bracket loses supporting role in 2 months in rabbit aorta, and this shows that the research emphasis of blood vessels present support magnesium alloy is still control degradation speed, extends effective supporting time.First Peeters etc. apply degradable magnesium alloy vascular stent in the treatment and seriously damage ischemia diseases at one's knees, confirm that magnesium alloy blood vessel rack is applied to clinical very high potential.Erbel etc. report first, the whole world about degradable magnesium alloy stent applications is in perspective, the multicenter of human coronary artery, nonrandom clinical trial, result shows, rack mechanical support performance is good, is not in the mood for the events such as stalk, subacute or advanced thrombus in follow-up period.The research such as Waksman confirms the security of such support, points out simultaneously, and degradable metal support needs research further to make it slowly degrade, and provides enough radial support power, thus prevents from elastical retraction and improve long term vascular taking up rate.
Magnesium confirms the feasibility of magnesium for bio-medical material as the application of surgery medical material early clinic, but magnesium matrix exists cytotoxicity, corrodes the problems such as too fast, need study improvement further.
Summary of the invention
The object of the present invention is to provide and a kind ofly overcome cytotoxicity and the degradable medical magnesium alloy of the problem such as erosion rate is too fast, provide the preparation method of this magnesium alloy simultaneously.
For achieving the above object, the present invention adopts following technical scheme:
A kind of degradable medical magnesium alloy, be made up of the material of following weight percent: Zn1.0 ~ 3.0%, Y0.20 ~ 1.50%, Nd0.40 ~ 1.50%, Zr0.30 ~ 0.50%, all the other are Mg and inevitable impurity element.
The preparation method of described degradable medical magnesium alloy, found for furnace charge with high-purity magnesium ingot, high-purity zinc ingot metal, Mg-Y master alloy, Mg-Nd master alloy, Mg-Zr master alloy, in furnace charge, the consumption of Zn, Y, Nd is 1.2-1.4 times of its content in degradable biological medical magnesium alloy, the consumption of Zr is 2-2.5 times of its content in degradable biological medical magnesium alloy, purity >=99.9% of high-purity magnesium ingot and high-purity zinc ingot metal.
Preferably, Mg-Y master alloy is Mg-28.5wt%Y master alloy, and Mg-Nd master alloy is Mg-30wt%Nd master alloy, and Mg-Zr master alloy is Mg-30wt%Zr master alloy.
The preparation method of above-mentioned degradable medical magnesium alloy, comprises the following steps:
(1) crucible after process is put into stove to heat, after furnace temperature rises to 300-500 DEG C, in stove, pass into carbonic acid gas and sulfur hexafluoride gas mixture; Wherein, the volume ratio of carbonic acid gas and sulfur hexafluoride is 99: 1;
(2) add high-purity magnesium ingot after logical gas mixture 8-12min, be warming up to 650-770 DEG C, after magnesium ingot melts completely, add Mg-Zr master alloy, be warming up to 780-830 DEG C after heating 15-20min, be then incubated 40-90min; Mg-Nd master alloy and Mg-Y master alloy is added after insulation terminates, add zinc ingot metal after reducing temperature to 650-770 DEG C, 10-15min, at the uniform velocity, counterclockwise stir after heating 10-15min, churning time is 3-8min, then through skimming, casting, namely the demoulding obtain intermediates;
(3) carry out homogenizing annealing to intermediates, annealing temperature is 340-400 DEG C, and annealing time is 20-28h; Carry out after annealing extruding to obtain target product, extrusion ratio is 20-36, and extruding rate is 1-3m/min, and in extrusion process, the temperature of container, pad, mould is respectively 250-280 DEG C, 280-320 DEG C, 330-360 DEG C.
Under preparation technology's state of the same race, compared with existing degradable magnesium alloy bio-medical material, harmless metallic element and polynary milligram ammonia theory is all selected to synthesize in degradable magnesium alloy of the present invention, not only increase substantially the biocompatibility of alloy, decrease the segregation of element in alloy simultaneously, there is better erosion resistance, Nd is as alloy surface active element, in crystallization and freezing process, on the solid-liquid interface of second-phase and liquid phase, the growth of second-phase is stopped, Zr element is in process of setting simultaneously, promote forming core, increase nucleation rate, second-phase is made to obtain obvious refinement.Employing hot extrusion is processed, the average grain size of magnesium alloy can be made to control at 1 ~ 2 μm, tiny crystal grain can ensure that the plasticity of alloy and the strength of materials are improved simultaneously, nano level MgZn Particle Phase Dispersed precipitate is in matrix, reduce the potential difference with matrix, inhibit the formation of galvanic cell, alleviate galvanic corrosion, that the erosion rate of material in simulated body fluid obviously reduces, and uniform corrosion.
The present invention passes through the magnesium alloy adding rare earth element y in magnesium-zinc alloy, Nd, Zr make preparation, and make its as cast condition obtain equiax crystal, the further refinement of crystal grain, make its tensile strength of mechanical property reach 215MPa, yield strength reaches 93MPa, and unit elongation reaches 37%.Obtain the Mg-Zn-Y-Nd-Zr alloy of average crystal grain 1-2 μm through hot extrusion and occur a large amount of nanometers, evenly, the Second Phase Particle of Dispersed precipitate, meeting the performance requriements of biological medical magnesium alloy.
Accompanying drawing explanation
Fig. 1 is the micro-organization chart of embodiment 2 gained magnesium alloy;
Fig. 2 is SEM and the EDS analysis chart of embodiment 2 gained magnesium alloy;
Fig. 3 is the macro morphology figure of embodiment 2 gained magnesium alloy stretching fracture;
Fig. 4 is the microscopic appearance figure of embodiment 2 gained magnesium alloy stretching fracture;
Fig. 5 is the galvanic corrosion test result figure of embodiment 2 gained magnesium alloy.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited in this.
embodiment 1
The preparation of the first step as cast condition Mg-1.0wt%Zn-0.2wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy (target product)
I early-stage preparations
Raw material needed for this experiment is:
High-purity magnesium ingot (purity >=99.9%): 1326g
High-purity zinc ingot metal (purity >=99.9%): 17.7g, wherein the content of zinc is its in gained magnesium alloy (target product) 1.25 times;
Mg-28.5wt%Y master alloy: 12.5g, wherein the content of Y is its in gained magnesium alloy (target product) 1.4 times;
Mg-30wt%Nd master alloy: 29.6g, wherein the content of Nd is its in gained magnesium alloy (target product) 1.3 times;
Mg-30wt%Zr master alloy: 47.2g, wherein the content of Zr is its in gained magnesium alloy (target product) 2.5 times;
For preventing oxidation and the burning of magnesium alloy, in whole fusion process, be connected with shielding gas, the shielding gas adopted in this test is the mixed gas of carbonic acid gas and sulfur hexafluoride, and wherein the throughput ratio of carbonic acid gas and sulfur hexafluoride is 99:1 always.
II specific operation process
A, by crucible, Slag Tool, stirring rod and mold heated to 100 DEG C, then take out, brush the coating that one deck is evenly very thin, then put into oven for drying, simultaneously pre-heating drying furnace charge;
B, the crucible handled well is put into resistance furnace, design temperature is 300 DEG C, when furnace temperature reaches, passes into the mixed gas of carbonic acid gas and sulfur hexafluoride;
C, pass into hybrid protection gas and add high-purity magnesium ingot after 8 minutes, be warming up to 650 DEG C simultaneously;
D, after high-purity magnesium ingot melts completely, in crucible, add Mg-30wt%Zr master alloy;
E, after 15 minutes, temperature is risen to 780 DEG C, start timing insulation, soaking time is 40min;
After f, insulation terminate, add Mg-30wt%Nd, Mg-28.5wt%Y master alloy, be cooled to 650 DEG C simultaneously;
High-purity zinc ingot metal is added after g, 10min;
Stir after h, 10min, stirring velocity is even, and direction is counterclockwise, and churning time is 3 minutes, skims, and leaves standstill 15 minutes;
I, take out crucible, cast, namely obtainedly after the demoulding commonly solidify state Mg-1.0wt%Zn-0.2wt%Y-0.5wt%Nd-0.4wt%Zr alloy (intermediates).
The preparation of second step extruded alloy sample
The common state Mg-1.0wt%Zn-0.2wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy (intermediates) that solidifies prepared in the first step is carried out homogenizing annealing, and annealing temperature is 340 DEG C, annealing time 20 hours.Be processed into the cylinder that diameter is 60mm, and by clean for alloy surface polishing, conventional extrusion technique as well known to those skilled in the art is adopted to carry out extruding obtained As-extruded Mg-1.0wt%Zn-0.2wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy, the optimum configurations of extrusion process process is: extrusion ratio is 20, extruding rate is 1m/min, in extrusion process, the temperature of container, pad, mould is respectively 250 DEG C, 280 DEG C, 330 DEG C.
embodiment 2
The preparation of the first step as cast condition Mg-2.0wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy (target product)
I early-stage preparations
Raw material needed for this experiment is:
High-purity magnesium ingot (purity >=99.9%): 1360g
High-purity zinc ingot metal (purity >=99.9%): 37.3g, wherein the content of zinc is its in gained magnesium alloy (target product) 1.25 times;
Mg-28.5wt%Y master alloy: 32.6g, wherein the content of Y is its in gained magnesium alloy (target product) 1.25 times;
Mg-30wt%Nd master alloy: 31g, wherein the content of Nd is its in gained magnesium alloy (target product) 1.25 times;
Mg-30wt%Zr master alloy: 49.6g, wherein the content of Zr is its in gained magnesium alloy (target product) 2.5 times;
For preventing oxidation and the burning of magnesium alloy, in whole fusion process, be connected with shielding gas, the shielding gas adopted in this test is the mixed gas of carbonic acid gas and sulfur hexafluoride, and wherein the throughput ratio of carbonic acid gas and sulfur hexafluoride is 99:1 always.
II specific operation process
A, by crucible, Slag Tool, stirring rod and mold heated to 120 DEG C, then take out, brush the coating that one deck is evenly very thin, then put into oven for drying, simultaneously pre-heating drying furnace charge;
B, the crucible handled well is put into resistance furnace, design temperature is 500 DEG C, when furnace temperature reaches, passes into the mixed gas of carbonic acid gas and sulfur hexafluoride;
C, pass into hybrid protection gas and add high-purity magnesium ingot after 12 minutes, be warming up to 770 DEG C simultaneously;
D, after high-purity magnesium ingot melts completely, in crucible, add Mg-30wt%Zr master alloy;
E, after 20 minutes, temperature is risen to 830 DEG C, start timing insulation, soaking time is 90min;
After f, insulation terminate, add Mg-30wt%Nd, Mg-28.5wt%Y master alloy, be cooled to 770 DEG C simultaneously;
G, after 15 minutes, add high-purity magnesium ingot;
H, stir after 15 minutes, stirring velocity is even, and direction is counterclockwise, and churning time is 8 minutes, skims, and leaves standstill 10 minutes;
I, take out crucible, cast, namely obtainedly after the demoulding commonly solidify state Mg-2.0wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr alloy (intermediates).
The preparation of second step extruded alloy sample
The common state Mg-2.0wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy (intermediates) that solidifies prepared in the first step is carried out homogenizing annealing, and annealing temperature is 400 DEG C, annealing time 24 hours.Be processed into the cylinder that diameter is 60mm, and by clean for alloy surface polishing, conventional extrusion technique as well known to those skilled in the art is adopted to carry out extruding obtained As-extruded Mg-2.0wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy (target product), the optimum configurations of extrusion process process is: extrusion ratio is 36, extruding rate is 1m/min, in extrusion process, the temperature of container, pad, mould is respectively 250 DEG C, 300 DEG C, 350 DEG C.
embodiment 3
The preparation of the first step as cast condition Mg-3.0wt%Zn-1.5wt%Y-1.5wt%Nd-0.4wt%Zr magnesium alloy (target product)
I early-stage preparations
Raw material needed for this experiment is:
High-purity magnesium ingot (purity >=99.9%): 1280g
High-purity zinc ingot metal (purity >=99.9%): 58.4g, wherein the content of zinc is its in gained magnesium alloy (target product) 1.25 times;
Mg-28.5wt%Y master alloy: 102.5g, wherein the content of Y is its in gained magnesium alloy (target product) 1.25 times;
Mg-30wt%Nd master alloy: 97.3g, wherein the content of Nd is its in gained magnesium alloy (target product) 1.25 times;
Mg-30wt%Zr master alloy: 51.8g, wherein the content of Zr is its in gained magnesium alloy (target product) 2.5 times;
For preventing oxidation and the burning of magnesium alloy, in whole fusion process, be connected with shielding gas, the shielding gas adopted in this test is the mixed gas of carbonic acid gas and sulfur hexafluoride, and wherein the throughput ratio of carbonic acid gas and sulfur hexafluoride is 99:1 always.
II specific operation process
A, by crucible, Slag Tool, stirring rod and mold heated to 140 DEG C, then take out, brush the coating that one deck is evenly very thin, then put into oven for drying, simultaneously pre-heating drying furnace charge;
B, the crucible handled well is put into resistance furnace, design temperature is 450 DEG C, when furnace temperature reaches, passes into the mixed gas of carbonic acid gas and sulfur hexafluoride;
C, pass into hybrid protection gas and add high-purity magnesium ingot after 10 minutes, be warming up to 720 DEG C simultaneously;
D, after furnace charge melts completely, in crucible, add Mg-30wt%Zr master alloy;
E, after 17 minutes, temperature is risen to 800 DEG C, start timing insulation, soaking time is 60min;
After f, insulation terminate, add Mg-30wt%Nd, Mg-28.5wt%Y master alloy, be cooled to 720 DEG C simultaneously;
G, after 13 minutes, add high-purity zinc ingot metal;
H, stir after 12 minutes, stirring velocity is even, and direction is counterclockwise, and churning time is 5 minutes, skims, and leaves standstill 15 minutes;
I, take out crucible, cast, namely obtainedly after the demoulding commonly solidify state Mg-3.0wt%Zn-0.5wt%Y-1.5wt%Nd-0.4wt%Zr alloy (intermediates).
The preparation of second step extruded alloy sample
The common state Mg-3.0wt%Zn-1.5wt%Y-1.5wt%Nd-0.4wt%Zr magnesium alloy (intermediates) that solidifies prepared in the first step is carried out homogenizing annealing, and annealing temperature is 370 DEG C, annealing time 28 hours.Be processed into the cylinder that diameter is 60mm, and by clean for alloy surface polishing, conventional extrusion technique as well known to those skilled in the art is adopted to carry out extruding obtained As-extruded Mg-3.0wt%Zn-1.5wt%Y-1.5wt%Nd-0.4wt%Zr magnesium alloy (target product), the optimum configurations of extrusion process process is: extrusion ratio is 36, extruding rate is 1m/min, in extrusion process, the temperature of container, pad, mould is respectively 280 DEG C, 320 DEG C, 360 DEG C.
embodiment 4
The preparation of the first step as cast condition Mg-2.0wt%Zn-1.0wt%Y-0.4wt%Nd-0.3wt%Zr magnesium alloy (target product)
I early-stage preparations
Raw material needed for this experiment is:
High-purity magnesium ingot (purity >=99.9%): 908.5g
High-purity zinc ingot metal (purity >=99.9%): 24g, wherein the content of zinc is its in gained magnesium alloy (target product) 1.2 times;
Mg-28.5wt%Y master alloy: 42.1g, wherein the content of Y is its in gained magnesium alloy (target product) 1.2 times;
Mg-30wt%Nd master alloy: 16g, wherein the content of Nd is its in gained magnesium alloy (target product) 1.2 times;
Mg-30wt%Zr master alloy: 20g, wherein the content of Zr is its in gained magnesium alloy 2 times;
For preventing oxidation and the burning of magnesium alloy, in whole fusion process, be connected with shielding gas, the shielding gas adopted in this test is the mixed gas of carbonic acid gas and sulfur hexafluoride, and wherein the throughput ratio of carbonic acid gas and sulfur hexafluoride is 99:1 always.
II specific operation process
A, by crucible, Slag Tool, stirring rod and mold heated to 130 DEG C, then take out, brush the coating that one deck is evenly very thin, then put into oven for drying, simultaneously pre-heating drying furnace charge;
B, the crucible handled well is put into resistance furnace, design temperature is 400 DEG C, when furnace temperature reaches, passes into the mixed gas of carbonic acid gas and sulfur hexafluoride;
C, pass into hybrid protection gas and add high-purity magnesium ingot after 11 minutes, be warming up to 700 DEG C simultaneously;
D, after furnace charge melts completely, in crucible, add Mg-30wt%Zr master alloy;
E, after 18 minutes, temperature is risen to 790 DEG C, start timing insulation, soaking time is 70min;
After f, insulation terminate, add Mg-30wt%Nd, Mg-28.5wt%Y master alloy, be cooled to 700 DEG C simultaneously;
G, after 14 minutes, add high-purity zinc ingot metal;
H, stir after 13 minutes, stirring velocity is even, and direction is counterclockwise, and churning time is 6 minutes, skims, and leaves standstill 17 minutes;
I, take out crucible, cast, namely obtainedly after the demoulding commonly solidify state Mg-2.0wt%Zn-1.0wt%Y-0.4wt%Nd-0.3wt%Zr alloy (intermediates).
The preparation of second step extruded alloy sample
The common state Mg-2.0wt%Zn-1.0wt%Y-0.4wt%Nd-0.3wt%Zr magnesium alloy (intermediates) that solidifies prepared in the first step is carried out homogenizing annealing, and annealing temperature is 390 DEG C, annealing time 26 hours.Be processed into the cylinder that diameter is 60mm, and by clean for alloy surface polishing, conventional extrusion technique as well known to those skilled in the art is adopted to carry out extruding obtained As-extruded Mg-2.0wt%Zn-1.0wt%Y-0.4wt%Nd-0.3wt%Zr magnesium alloy (target product), the optimum configurations of extrusion process process is: extrusion ratio is 28, extruding rate is 3m/min, in extrusion process, the temperature of container, pad, mould is respectively 260 DEG C, 290 DEG C, 340 DEG C.
embodiment 5
The preparation of the first step as cast condition Mg-3.0wt%Zn-1.2wt%Y-1.0wt%Nd-0.5wt%Zr magnesium alloy (target product)
I early-stage preparations
Raw material needed for this experiment is:
High-purity magnesium ingot (purity >=99.9%): 842.2g
High-purity zinc ingot metal (purity >=99.9%): 42g, wherein the content of zinc is its in gained magnesium alloy (target product) 1.4 times;
Mg-28.5wt%Y master alloy: 59g, wherein the content of Y is its in gained magnesium alloy (target product) 1.4 times;
Mg-30wt%Nd master alloy: 46.7g, wherein the content of Nd is its in gained magnesium alloy (target product) 1.4 times;
Mg-30wt%Zr master alloy: 38.3g, wherein the content of Zr is its in gained magnesium alloy (target product) 2.3 times;
For preventing oxidation and the burning of magnesium alloy, in whole fusion process, be connected with shielding gas, the shielding gas adopted in this test is the mixed gas of carbonic acid gas and sulfur hexafluoride, and wherein the throughput ratio of carbonic acid gas and sulfur hexafluoride is 99:1 always.
II specific operation process
A, by crucible, Slag Tool, stirring rod and mold heated to 125 DEG C, then take out, brush the coating that one deck is evenly very thin, then put into oven for drying, simultaneously pre-heating drying furnace charge;
B, the crucible handled well is put into resistance furnace, design temperature is 380 DEG C, when furnace temperature reaches, passes into the mixed gas of carbonic acid gas and sulfur hexafluoride;
C, pass into hybrid protection gas and add high-purity magnesium ingot after 11 minutes, be warming up to 680 DEG C simultaneously;
D, after furnace charge melts completely, in crucible, add Mg-30wt%Zr master alloy;
E, after 18 minutes, temperature is risen to 810 DEG C, start timing insulation, soaking time is 55min;
After f, insulation terminate, add Mg-30wt%Nd, Mg-28.5wt%Y master alloy, be cooled to 680 DEG C simultaneously;
G, after 12 minutes, add high-purity zinc ingot metal;
H, stir after 14 minutes, stirring velocity is even, and direction is counterclockwise, and churning time is 8 minutes, skims, and leaves standstill 15 minutes;
I, take out crucible, cast, namely obtainedly after the demoulding commonly solidify state Mg-3.0wt%Zn-1.2wt%Y-1.0wt%Nd-0.5wt%Zr alloy (intermediates).
The preparation of second step extruded alloy sample
The common state Mg-3.0wt%Zn-1.2wt%Y-1.0wt%Nd-0.5wt%Zr magnesium alloy (intermediates) that solidifies prepared in the first step is carried out homogenizing annealing, and annealing temperature is 350 DEG C, annealing time 24 hours.Be processed into the cylinder that diameter is 60mm, and by clean for alloy surface polishing, conventional extrusion technique as well known to those skilled in the art is adopted to carry out extruding obtained As-extruded Mg-3.0wt%Zn-1.2wt%Y-1.0wt%Nd-0.5wt%Zr magnesium alloy (target product), the optimum configurations of extrusion process process is: extrusion ratio is 25, extruding rate is 2m/min, in extrusion process, the temperature of container, pad, mould is respectively 260 DEG C, 280 DEG C, 355 DEG C.
The room temperature tensile intensity of Mg-3.0wt%Zn-1.5wt%Y-1.5wt%Nd-0.4wt%Zr two kinds of magnesium alloy that after testing prepared by the Mg-1.0wt%Zn-0.2wt%Y-0.5wt%Nd-0.4wt%Zr for preparing of embodiment 1 and embodiment 3 is respectively 315 ± 3MPa and 325 ± 5MPa yield strength is respectively 255 ± 3MPa and 246 ± 3MPa, unit elongation reaches 25% and 24% respectively, all reach the requirement as Biological magnesium alloy
Test analysis is carried out to the Microstructure and properties of embodiment 2 gained magnesium alloy Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr As-extruded: the tensile strength under Mg-2.0wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr Alloy At Room Temperature (25 DEG C) reaches 345 ± 5MPa, yield strength reaches 275 ± 3MPa, and unit elongation is greater than 28%.
The microstructure of embodiment 2 gained As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy as shown in Figure 1, the as can be seen from the figure homogeneous microstructure of this alloy, crystal grain is tiny, and average grain size reaches 1-2 μm;
SEM and EDS of embodiment 2 gained As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy analyzes picture as shown in Figure 2, and as can be seen from the figure, be dispersed with nano particle phase in this alloy, it is mainly MgZn phase;
The stretching fracture both macro and micro pattern of embodiment 2 gained As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy is respectively Fig. 3 and Fig. 4, as can be seen from the figure, containing a large amount of dimple in this Alloy Fracture, belong to ductile rupture, the tensile strength of this alloy that tension test records reaches 345MPa, yield strength reaches 275MPa, and unit elongation is 28%, and this performance can meet biological medical magnesium alloy requirement;
As shown in Figure 5, from figure, matching can obtain the galvanic corrosion test result of embodiment 2 gained As-extruded Mg-2wt%Zn-0.5wt%Y-0.5wt%Nd-0.4wt%Zr magnesium alloy, and the corrosion potential of this alloy is-1.705V, and corrosion electric current density is 1.08 × 10
-5a/cm
2, its corrosive nature meets biological medical magnesium alloy requirement.
Claims (3)
1. the preparation method of a degradable biological medical magnesium alloy, it is characterized in that, described degradable biological medical magnesium alloy is made up of the material of following weight percent: Zn1.0 ~ 3.0%, Y0.20 ~ 1.50%, Nd0.40 ~ 1.50%, Zr0.30 ~ 0.50%, and all the other are Mg and inevitable impurity element; Found for furnace charge with high-purity magnesium ingot, high-purity zinc ingot metal, Mg-Y master alloy, Mg-Nd master alloy, Mg-Zr master alloy, in furnace charge, the consumption of Zn, Y, Nd is 1.2-1.4 times of its content in degradable biological medical magnesium alloy, the consumption of Zr is 2-2.5 times of its content in degradable biological medical magnesium alloy, purity >=99.9% of high-purity magnesium ingot and high-purity zinc ingot metal, Mg-Y master alloy is Mg-28.5wt%Y master alloy, Mg-Nd master alloy is Mg-30wt%Nd master alloy, and Mg-Zr master alloy is Mg-30wt%Zr master alloy; Carry out homogenizing annealing to intermediates, annealing temperature is 340-400 DEG C, and annealing time is 20-28h; Carry out after annealing extruding to obtain target product, extrusion ratio is 20-36, and extruding rate is 1-3m/min, and in extrusion process, the temperature of container, pad, mould is respectively 250-280 DEG C, 280-320 DEG C, 330-360 DEG C.
2. the preparation method of a kind of degradable biological medical magnesium alloy as claimed in claim 1, is characterized in that, comprise the following steps:
(1) crucible after process is put into stove to heat, after furnace temperature rises to 300-500 DEG C, in stove, pass into carbonic acid gas and sulfur hexafluoride gas mixture; Wherein, the volume ratio of carbonic acid gas and sulfur hexafluoride is 99: 1;
(2) add high-purity magnesium ingot after logical gas mixture 8-12min, be warming up to 650-770 DEG C, after magnesium ingot melts completely, add Mg-Zr master alloy, be warming up to 780-830 DEG C after heating 15-20min, be then incubated 40-90min; Mg-Nd master alloy and Mg-Y master alloy is added after insulation terminates, add zinc ingot metal after reducing temperature to 650-770 DEG C, 10-15min, at the uniform velocity, counterclockwise stir after reheating 10-15min, churning time is 3-8min, then through skimming, casting, namely the demoulding obtain intermediates.
3. the preparation method of a kind of degradable biological medical magnesium alloy as claimed in claim 2, it is characterized in that, described heating stove is resistance furnace.
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| CN104451316B (en) * | 2014-12-30 | 2017-01-04 | 山东宏泰科技有限公司 | High-ductility forging and stamping magnesium alloy materials and preparation method thereof |
| CN104894446A (en) * | 2015-03-15 | 2015-09-09 | 湖南工程学院 | Heatproof rare earth magnesium alloy used for casting of metal mold and preparation method thereof |
| CN105695787A (en) * | 2016-03-31 | 2016-06-22 | 青岛百瑞吉生物工程有限公司 | Preparation method of medical implantation magnesium alloy material |
| CN106361476B (en) * | 2016-09-13 | 2018-05-15 | 郑州大学 | A kind of Weaving type degradable magnesium alloy airway stent and preparation method thereof |
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| CN108715963A (en) * | 2018-05-21 | 2018-10-30 | 山东银光钰源轻金属精密成型有限公司 | One kind is containing Y, Nd magnesium-rare earth and preparation method thereof |
| CN111228577A (en) * | 2020-01-15 | 2020-06-05 | 太原科技大学 | Medical magnesium alloy capable of being degraded in short term and preparation method thereof |
| CN112472868B (en) * | 2020-11-18 | 2024-02-23 | 郑州大学 | Degradable Mg-Nd-Zn-Sc biomedical magnesium alloy and preparation method thereof |
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| CN113322403A (en) * | 2021-06-03 | 2021-08-31 | 郑州大学 | Novel degradable high-toughness magnesium alloy bone nail material and preparation method thereof |
| CN113388767A (en) * | 2021-08-02 | 2021-09-14 | 西安四方超轻材料有限公司 | High-performance magnesium alloy material and preparation method thereof |
| CN114561579A (en) * | 2022-03-03 | 2022-05-31 | 上海康德莱医疗器械股份有限公司 | Biodegradable magnesium alloy without rare earth elements and preparation method and application thereof |
| CN114990370B (en) * | 2022-05-11 | 2022-11-11 | 山东商业职业技术学院 | Preparation method of magnesium alloy composite material with high biocompatibility |
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