CN102206782A - Degradable Mg-Zn-Y-Ca intravascular stent material and preparation method thereof - Google Patents
Degradable Mg-Zn-Y-Ca intravascular stent material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a degradable Mg-Zn-Y-Ca intravascular stent material and a preparation method thereof, which belong to the fields of design and manufacture of metal materials. The intravascular stent material is characterized by comprising the following chemical components in percentage by weight (wt%): Zn 1.00 to 4.00, Y 0.10 to 1.00, Ca 0.01 to 0.50 and the balance of Mg; the chemical components are subjected to sub-rapid solidification at (200+/-10) K/S and heat treatment of heating at 320 to 420 DEG C and heat preservation for 20 to 30h; and the texture characteristic of the intravascular stent material is that: even and fine spherical quasicrystalline phases Mg3YZn6 are dispersed and distributed on an alpha-Mg matrix. The potential difference between the spherical quasicrystalline phases Mg3YZn6 and magnesium is lower so that the formation of a galvanic cell is restrained and galvanic corrosion is alleviated; the sphericity quasicrystal Mg3YZn6 has good corrosion resistance and can obviously enhance the corrosion resistant performance of magnesium alloy; and at the same time, the quasicrystal also has the characteristics of high hardness, low friction coefficient, low interface energy and the like and can greatly enhance the mechanical performance of the magnesium alloy.
Description
Technical field
A kind of degradable Mg-Zn-Y-Ca of the present invention vascular stent material and preparation method thereof belongs to the design and the preparation field of metallic substance.
Background technology
The metallic blood vessel bracket material mainly is divided into two big classes: non-degradable vascular stent material and degradable blood vessel bracket material.The 316L stainless steel is a non-degradable vascular stent material commonly used clinically at present, and it has the good mechanical performance, also has excellent corrosion resistance nature simultaneously.But because the ferromegnetism that has of stainless steel causes it can not Magnetic resonance imaging, do not have the MRI visuality, influence it and carry out angiography.In addition, stainless steel stent is a permanent stents, can not degrade in vivo, also just have the total problem of permanent stents inevitably, comprise long-term tunica intima functional disorder, blood vessel endothelium process lag, cause embolism reaction, permanent mechanical stretch and damage, chronic inflammatory reaction, support are inserted the position and non-support is inserted the coronary artery vascular tumor risk that the position vasomotion is inharmonious and cause thus.Especially insert support in infants, because the metallics of inserting forever exists, the blood vessel diameter that has suppressed this place increases with the growth at age, easily brings out the narrow once more of tube chamber.These problems become the bottleneck of restriction metal permanent support development.And biodegradable metals is made intravascular stent, supports tube chamber within a certain period of time, keeps vascular patency, degraded and even disappearance gradually later on, effectively acute obturation and the restenosis after the treatment of vascular expansion.Biodegradable scaffold can will finally replace permanent support from complying with the normal physiological self-regeneration of human body process in essence, becomes the cardiovascular obstructive disease interventional therapy main product in future.At present, the degradable metallic substance that can be used for making intravascular stent is mainly magnesium alloy, and magnesium alloy blood vessel rack is considered to present most promising blood vessel and inserts support.Reason is: can degrade fully after (1) is inserted.This characteristic not only can be improved conformability, the naturality of blood vessel to a certain extent, and later on also can carry out once more support in the same lesion of blood vessel and not insert and the overlapping phenomenon that the non-degradable support brings can occur.The treating cardiovascular disease that is particularly useful for the infant; (2) excellent biological compatibility.Magnesium is the necessary for human body nutritive element.(diameter is about 2mm because the intravascular stent size is small, thickness is about 0.1-0.2mm, length is about 15mm), the amount of metal ion that its degradation process discharges is fewer, therefore, the small amount of magnesium ion that discharges in the magnesium alloy blood vessel rack degradation process not only can not bring harm to human body, can be human body Mg supplementation element on the contrary, to guarantee the demand of human body normal physiological function to magnesium; (3) have the MRI visuality, can carry out angiography it.
At present, the existing employed magnesium alloy of clinical experiment mostly is commercial magnesium alloy (WE43, AE21, AZ31 etc.), compares with the stainless material support, and the deficiency that commercial magnesium alloy angiocarpy bracket exists mainly is that intensity is low, and fragility is big, and plastic deformation ability is poor.Secondly, the corrosion resisting property of commercial magnesium alloy is relatively poor, is easy to take place spot corrosion, is especially containing Cl
-The human body internal corrosion speed that exists is bigger.In case insert inside of human body, before tissue does not fully heal, insert thing and will lose its mechanical integrity.In addition, if contain a certain amount of Al in the commercial magnesium alloy, in case support is inserted in the body, the Al element can cause organ damage, causes symptoms such as osteomalacia, anaemia and nervous disorders.
Summary of the invention
The problem that the purpose of a kind of degradable Mg-Zn-Y-Ca of the present invention vascular stent material and preparation method thereof is to solve above-mentioned existence is avoided and is overcome its deficiency, by add the quasicrystal particle that contains some amount in the magnesium alloy that rare earth element y makes preparation in magnesium-zinc alloy; Adding activating element Ca makes accurate crystalline phase all become sphere; Handling the acquisition average grain size through the inferior rapid solidification of (200 ± 10) K/S is the Mg-Zn-Y-Ca alloy of 15 μ m and accurate crystalline phase Mg occurs
3YZn
6Prepare the magnesium alloy that has some amount, equally distributed, tiny, spherical quasi crystal particle enhanced, satisfies desirable intravascular stent performance requriements again through Overheating Treatment.
A kind of degradable Mg-Zn-Y-Ca of the present invention vascular stent material, it is characterized in that chemical ingredients by mass percentage Wt% count: Zn 1.00-4.00, Y 0.10-1.00, Ca 0.01-0.50, all the other are Mg, through the thermal treatment of the inferior rapid solidification of (200 ± 10) K/S and 320-420 ℃ of heating, insulation 20-30h, its tissue signature is: the even accurate crystalline phase Mg3YZn6 disperse of fine spherical grains is distributed on α-Mg matrix.
The method for preparing above-mentioned a kind of degradable Mg-Zn-Y-Ca vascular stent material is characterized in that concrete processing step is:
The setting of I device:
In vacuum induction body of heater 1, place quartz crucible 2, mother alloy ingot bar 3, induction heating circle 4, melt outlet 5, wear ring 6, casting in bronze type 7 and vacuumize switch 8, it is characterized in that it being that mother alloy ingot bar 3 surface finish are clean, put into quartz crucible customized 2, put it in the vacuum induction body of heater 1, by induction heating circle 4 induction meltings mother alloy ingot bar 3 is heated to fusing, connection vacuumizes switch 8 and vacuumizes up to it is exported sucking-off 5 from melt, and the alloy melt that has melted injects water-cooled copper casting mold 7 apace and can solidify at once under the effect of pull of vacuum, take off casting in bronze type 7 and take out alloy sample, obtain thin bar-shaped inferior rapid solidification attitude alloy sample;
The technology that II is concrete:
The first step. the molten of mother alloy ingot bar joined
I. Qian Qi preparation
This tests needed raw material: 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy;
Be oxidation and the burning that prevents magnesium alloy, be connected with shielding gas always in whole fusion process, the shielding gas that adopts 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;
II. specific operation process
A, with 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy Wt% are by mass percentage counted: Zn 1.00-4.00, and Y 0.10-1.00, Ca 0.01-0.50, all the other are the ratio requirement of Mg, weigh up raw material for standby;
B, crucible is put in the resistance furnace, in resistance furnace, feed simultaneously carbonic acid gas and sulfur hexafluoride mixed gas, when crucible is heated to 400-500 ℃ by the time, load weighted magnesium ingot and zinc ingot metal before in crucible, adding;
C, the temperature of resistance furnace is increased to about 700-800 ℃, after furnace charge melts fully, in crucible, adds the rare earth yttrium that weighs up in advance again, stir, and spoonful drag at the bottom of crucible bottom prevents that the rare earth yttrium from sinking to crucible with stirring;
Behind d, the about 20-30min, add the Mg-30%Ca master alloy fritter that weighs up in advance, and stir;
E, by the time the furnace charge in the crucible all after the fusing, stirs, skims, and leaves standstill in the casting mold that pours into prior preheating behind the 15-25min and is frozen into the mother alloy ingot bar;
Second step. the preparation of inferior rapidly solidified alloy sample and thermal treatment
What the preparation of inferior rapidly solidified alloy sample was adopted is the method for water cooled copper mould vacuum suction, the bottom part aperture diameter of silica tube is about Φ 1mm, the intracavity diameter of copper mold is Φ 3mm, at first mother alloy ingot bar 3 is broken into the square fritter of 7-10mm, put into quartz crucible customized 2 after surface finish is clean, put it in the vacuum induction body of heater 1, by induction heating circle 4 induction heating to 700-800 ℃ of melting, mother alloy ingot bar 3 is heated to fusing, connection vacuumizes switch 8 and vacuumizes up to it is exported sucking-off 5 from melt, the alloy melt that has melted injects water-cooled copper casting mold 7 apace and can solidify at once under the effect of pull of vacuum, take off casting in bronze type 7 and take out alloy sample, obtain thin bar-shaped inferior rapid solidification attitude alloy sample, the quick alloy sample in Asia is carried out the thermal treatment of homogenizing, treatment temp is 320-420 ℃, and soaking time is 20-30h.
The advantage and the purposes of a kind of degradable Mg-Zn-Y-Ca of the present invention vascular stent material and preparation method thereof are: material of the present invention all selects for use harmless metallic element to synthesize, adopt the inferior method for rapid cooling of water cooled copper mould vacuum suction, control its speed of cooling in (200 ± 10) K/S scope, can guarantee accurate crystalline phase Mg
3YZn
6Formation, the average grain size of magnesium alloy is controlled at below the 15 μ m, small grains can guarantee that the strength of materials and plasticity are improved simultaneously.Ca is a surface active element, and Ca mainly accumulates in accurate crystalline phase Mg in the crystallization and freezing process
3YZn
6On the solid-liquid interface of liquid phase, accurate brilliant growth on the main direction of growth is stopped, accelerating the speed of growth on the secondary growth direction, make accurate crystalline phase Mg
3YZn
6Spheroidization.The accurate crystalline phase Mg of spheric
3YZn
6Be the main dispersion-strengthened phase of Mg-Zn-Y-Ca alloy, the spheric quasicrystal particle can make its dispersion-strengthened effect reach maximization, and the mechanical property of spherical quasi crystal mutual-assistance magnesium alloy evenly tiny, that disperse distributes is significantly improved.Spherical quasi crystal phase Mg
3YZn
6Lower with the potential difference of magnesium, suppressed galvanic cell formation, alleviated galvanic corrosion, making the forms of corrosion of material in dynamic simulation body fluid is uniform corrosion, has obviously improved the corrosion resistance nature of magnesium alloy.
Because the erosion rate 0.23-0.30mm/a of material of the present invention in 37 ℃ of dynamic simulation body fluid, yield strength under 37 ℃ is greater than 200MPa, unit elongation is greater than 15%, its corrosion resistance nature and mechanical property all can satisfy the performance requriements of desirable intravascular stent simultaneously, can be used for making degradable blood vessel and insert support.
Description of drawings
Accompanying drawing 1 is a device for carrying out said synoptic diagram of the present invention
Number in the figure is: 1. vacuum induction body of heater 2. quartz crucibles 3. mother alloy ingot bars 4. induction heating circles 5. melts export 6. wear rings, 7. casting in bronze types 8. and vacuumize switch
Embodiment
Embodiment 1:
The first step. the molten of mother alloy ingot bar joined
I. Qian Qi preparation
This tests needed raw material: 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy;
Be oxidation and the burning that prevents magnesium alloy, be connected with shielding gas always in whole fusion process, the shielding gas that adopts 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;
II. specific operation process
A, with 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy Wt% are by mass percentage counted: Zn 1.00, and Y 0.10, and Ca 0.01, and all the other are the ratio requirement of Mg, weigh up raw material for standby;
B, crucible is put in the resistance furnace, in resistance furnace, feed simultaneously carbonic acid gas and sulfur hexafluoride mixed gas, when crucible is heated to 450 ℃ by the time, load weighted pure magnesium and pure zinc before in crucible, adding;
C, the temperature of resistance furnace is increased to about 760 ℃, after furnace charge melts fully, in crucible, adds the pure yttrium that weighs up in advance again, make it even, and spoonful drag at the bottom of crucible bottom prevents that metallic yttrium from sinking to crucible with stirring through stirring;
Behind d, the about 25min, add Mg-30%Ca master alloy fritter, and stir;
E, by the time the furnace charge in the crucible all after the fusing, stirs, skims, and leaves standstill in the casting mold that pours into prior preheating behind the 15min and is frozen into the mother alloy ingot bar;
Second step. the preparation of inferior rapidly solidified alloy sample and thermal treatment
What the preparation of inferior rapidly solidified alloy sample was adopted is the method for water cooled copper mould vacuum suction, the bottom part aperture diameter of silica tube is about Φ 1mm, the intracavity diameter of copper mold is Φ 3mm, at first mother alloy ingot bar 3 is broken into the square fritter of 8mm, put into quartz crucible customized 2 after surface finish is clean, put it in the vacuum induction body of heater 1, by ℃ melting of induction heating circle 4 induction heating to 750, mother alloy ingot bar 3 is heated to fusing, connection vacuumizes switch 8 and vacuumizes up to it is exported sucking-off 5 from melt, the alloy melt that has melted injects water-cooled copper casting mold 7 apace and can solidify at once under the effect of pull of vacuum, take off casting in bronze type 7 and take out alloy sample, obtain thin bar-shaped inferior rapid solidification attitude alloy sample, the quick alloy sample in Asia is carried out the thermal treatment of homogenizing, treatment temp is 370 ℃, and soaking time is 24h.The magnesium alloy yield strength 210MPa that obtains under this technology, unit elongation 25%, the erosion rate in dynamic simulation body fluid is 0.23mm/a, satisfies the performance requriements of desirable intravascular stent.
Embodiment 2:
The magnesium alloy composition proportion changes as follows: with 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy Wt% are by mass percentage counted: Zn 2.00, and Y 0.40, Ca0.15, and all the other are Mg, other is with embodiment 1.
The magnesium alloy Yield strength 225 MPa that obtains under this technology, unit elongation 22%, the erosion rate in dynamic simulation body fluid is 0.25mm/a, satisfies the performance requriements of desirable intravascular stent.
Embodiment 3:
The magnesium alloy composition proportion changes as follows: with 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy Wt% are by mass percentage counted: Zn 3.00, and Y 0.70, Ca0.35, and all the other are Mg, other is with embodiment 1.
The magnesium alloy yield strength 240MPa that obtains under this technology, unit elongation 20%, the erosion rate in dynamic simulation body fluid is 0.28mm/a, satisfies the performance requriements of desirable intravascular stent.
Embodiment 4:
The magnesium alloy composition proportion changes as follows: with 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy Wt% are by mass percentage counted: Zn 4.00, Y1.00, and Ca0.50, all the other are Mg, other is with embodiment 1.
The magnesium alloy yield strength 255MPa that obtains under this technology, unit elongation 18%, the erosion rate in dynamic simulation body fluid is 0.30mm/a, satisfies the performance requriements of desirable intravascular stent.
Embodiment 5:
B, crucible is put in the resistance furnace, in resistance furnace, feed simultaneously carbonic acid gas and sulfur hexafluoride mixed gas, when crucible is heated to 400 ℃ by the time, load weighted pure magnesium and pure zinc before in crucible, adding;
C, the temperature of resistance furnace is increased to about 700 ℃, after furnace charge melts fully, in crucible, adds the pure yttrium that weighs up in advance again, make it even, and spoonful drag at the bottom of crucible bottom prevents that metallic yttrium from sinking to crucible with stirring through stirring;
Behind d, the about 20min, add Mg-30%Ca master alloy fritter, and stir;
E, by the time the furnace charge in the crucible all after the fusing, stirs, skims, and leaves standstill in the casting mold that pours into prior preheating behind the 20min and is frozen into the mother alloy ingot bar;
Second step. the preparation of inferior rapidly solidified alloy sample and thermal treatment
What the preparation of inferior rapidly solidified alloy sample was adopted is the method for water cooled copper mould vacuum suction, the bottom part aperture diameter of silica tube is about Φ 1mm, the intracavity diameter of copper mold is Φ 3mm, at first mother alloy ingot bar 3 is broken into the square fritter of 7mm, put into quartz crucible customized 2 after surface finish is clean, put it in the vacuum induction body of heater 1, by ℃ melting of induction heating circle 4 induction heating to 700, mother alloy ingot bar 3 is heated to fusing, connection vacuumizes switch 8 and vacuumizes up to it is exported sucking-off 5 from melt, the alloy melt that has melted injects water-cooled copper casting mold 7 apace and can solidify at once under the effect of pull of vacuum, take off casting in bronze type 7 and take out alloy sample, obtain thin bar-shaped inferior rapid solidification attitude alloy sample, the quick alloy sample in Asia is carried out the thermal treatment of homogenizing, treatment temp is 320 ℃, and soaking time is 20h, and other is with embodiment 2.
Embodiment 6:
B, crucible is put in the resistance furnace, in resistance furnace, feed simultaneously carbonic acid gas and sulfur hexafluoride mixed gas, when crucible is heated to 500 ℃ by the time, load weighted pure magnesium and pure zinc before in crucible, adding;
C, the temperature of resistance furnace is increased to about 800 ℃, after furnace charge melts fully, in crucible, adds the pure yttrium that weighs up in advance again, make it even, and spoonful drag at the bottom of crucible bottom prevents that metallic yttrium from sinking to crucible with stirring through stirring;
Behind d, the about 30min, add Mg-30%Ca master alloy fritter, and stir;
E, by the time the furnace charge in the crucible all after the fusing, stirs, skims, and leaves standstill in the casting mold that pours into prior preheating behind the 25min and is frozen into the mother alloy ingot bar;
Second step. the preparation of inferior rapidly solidified alloy sample and thermal treatment
What the preparation of inferior rapidly solidified alloy sample was adopted is the method for water cooled copper mould vacuum suction, the bottom part aperture diameter of silica tube is about Φ 1mm, the intracavity diameter of copper mold is Φ 3mm, at first mother alloy ingot bar 3 is broken into the square fritter of 10mm, put into quartz crucible customized 2 after surface finish is clean, put it in the vacuum induction body of heater 1, by ℃ melting of induction heating circle 4 induction heating to 800, mother alloy ingot bar 3 is heated to fusing, connection vacuumizes switch 8 and vacuumizes up to it is exported sucking-off 5 from melt, the alloy melt that has melted injects water-cooled copper casting mold 7 apace and can solidify at once under the effect of pull of vacuum, take off casting in bronze type 7 and take out alloy sample, obtain thin bar-shaped inferior rapid solidification attitude alloy sample, the quick alloy sample in Asia is carried out the thermal treatment of homogenizing, treatment temp is 420 ℃, and soaking time is 30h, and other is with embodiment 2.
Claims (2)
1. degradable Mg-Zn-Y-Ca vascular stent material and preparation method thereof, it is characterized in that chemical ingredients by mass percentage Wt% count: Zn 1.00-4.00, Y 0.10-1.00, Ca 0.01-0.50, all the other are Mg, through the thermal treatment of the inferior rapid solidification of (200 ± 10) K/S and 320-420 ℃ of heating, insulation 20-30h, its tissue signature is: the even accurate crystalline phase Mg of fine spherical grains
3YZn
6Disperse is distributed on α-Mg matrix.
2. the method for preparing the described a kind of degradable Mg-Zn-Y-Ca vascular stent material of claim 1 is characterized in that concrete processing step is:
The setting of I device:
In vacuum induction body of heater (1), place quartz crucible (2), mother alloy ingot bar (3), induction heating circle (4), melt outlet (5), wear ring (6), casting in bronze type (7) and vacuumize switch (8), mother alloy ingot bar (3) surface finish is clean, put into quartz crucible customized (2), put it into again in the vacuum induction body of heater (1), by induction heating circle (4) induction melting mother alloy ingot bar (3) is heated to fusing, connection vacuumizes switch (8) and vacuumizes up to it is exported sucking-off (5) from melt, the alloy melt that has melted injects water-cooled copper casting mold (7) apace and can solidify at once under the effect of pull of vacuum, take off casting in bronze type (7) and take out alloy sample, obtain thin bar-shaped inferior rapid solidification attitude alloy sample;
The technology that II is concrete:
I. Qian Qi preparation
This tests needed raw material: 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy;
Be oxidation and the burning that prevents magnesium alloy, be connected with shielding gas always in whole fusion process, the shielding gas that adopts 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;
II. specific operation process
A, with 1
#Magnesium ingot, 1
#Zinc ingot metal, 99.9% pure yttrium and Mg-30%Ca master alloy Wt% are by mass percentage counted: Zn 1.00-4.00, and Y 0.10-1.00, Ca 0.01-0.50, all the other are the ratio requirement of Mg, weigh up raw material for standby;
B, crucible is put in the resistance furnace, in resistance furnace, feed simultaneously carbonic acid gas and sulfur hexafluoride mixed gas, when crucible is heated to 400-500 ℃ by the time, load weighted magnesium ingot and zinc ingot metal before in crucible, adding;
C, the temperature of resistance furnace is increased to 700-800 ℃, after furnace charge melts fully, in crucible, adds the rare earth yttrium that weighs up in advance again, stir, and spoonful drag at the bottom of crucible bottom prevents that the rare earth yttrium from sinking to crucible with stirring;
Behind d, the about 20-30min, add the Mg-30%Ca master alloy fritter that weighs up in advance, and stir;
E, by the time the furnace charge in the crucible all after the fusing, stirs, skims, and leaves standstill in the casting mold that pours into prior preheating behind the 15-25min and is frozen into the mother alloy ingot bar;
Second step. the preparation of inferior rapidly solidified alloy sample and thermal treatment
What the preparation of inferior rapidly solidified alloy sample was adopted is the method for water cooled copper mould vacuum suction, the bottom part aperture diameter of silica tube is about Φ 1mm, the intracavity diameter of copper mold is Φ 3mm, at first mother alloy ingot bar (3) is broken into the square fritter of 7-10mm, put into quartz crucible customized (2) after surface finish is clean, put it in the vacuum induction body of heater (1), by induction heating circle (4) induction heating to 700-800 ℃ of melting, (3 are heated to fusing with the mother alloy ingot bar, connection vacuumizes switch (8) and vacuumizes up to it is exported sucking-off (5) from melt, the alloy melt that has melted injects water-cooled copper casting mold (7) apace and can solidify at once under the effect of pull of vacuum, take off casting in bronze type (7) and take out alloy sample, obtain thin bar-shaped inferior rapid solidification attitude alloy sample, the quick alloy sample in Asia is carried out the thermal treatment of homogenizing, treatment temp is 320-420 ℃, and soaking time is 20-30h.
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| CN103451577A (en) * | 2013-08-12 | 2013-12-18 | 中国科学院宁波材料技术与工程研究所 | Quasicrystal particle strengthening magnesium-based amorphous alloy endogeny composite material and preparation method thereof |
| CN103468988A (en) * | 2013-09-14 | 2013-12-25 | 天津六合镁制品有限公司 | Preparation method of magnesium alloy |
| CN104152747A (en) * | 2014-08-26 | 2014-11-19 | 济南大学 | Mg-Zn-Y magnesium alloy and preparation method thereof |
| CN104593650A (en) * | 2013-11-01 | 2015-05-06 | 上海交通大学医学院附属第九人民医院 | Biodegradable and absorbable magnesium-zinc-copper alloy with antibiotic function, and application thereof |
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| CN103451577A (en) * | 2013-08-12 | 2013-12-18 | 中国科学院宁波材料技术与工程研究所 | Quasicrystal particle strengthening magnesium-based amorphous alloy endogeny composite material and preparation method thereof |
| CN103451577B (en) * | 2013-08-12 | 2015-09-30 | 中国科学院宁波材料技术与工程研究所 | Magnesium base amorphous alloy situ composite material of quasicrystal particle strengthening and preparation method thereof |
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| CN103468988B (en) * | 2013-09-14 | 2015-05-13 | 天津六合镁制品有限公司 | Preparation method of magnesium alloy |
| CN104593650A (en) * | 2013-11-01 | 2015-05-06 | 上海交通大学医学院附属第九人民医院 | Biodegradable and absorbable magnesium-zinc-copper alloy with antibiotic function, and application thereof |
| CN104152747A (en) * | 2014-08-26 | 2014-11-19 | 济南大学 | Mg-Zn-Y magnesium alloy and preparation method thereof |
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| CN107190192B (en) * | 2017-07-10 | 2018-10-02 | 太原理工大学 | A kind of absorbable biological medicinal high-strength anticorrosion magnesium alloy material and preparation method thereof |
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| CN109082569B (en) * | 2018-09-13 | 2020-04-21 | 太原理工大学 | Preparation method of nano silicon dioxide/ferroferric oxide magnetic contrast particle enhanced biological magnesium-based composite material |
| CN109504884A (en) * | 2019-01-10 | 2019-03-22 | 吉林大学 | Polynary a small amount of high-strength plasticity magnesium alloy and its heavy reduction short flow process |
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| CN109777975A (en) * | 2019-01-18 | 2019-05-21 | 中南大学 | A method of utilizing the high tough magnesium alloy pipe of resistance to biological corrosion of baking preparation |
| CN109777975B (en) * | 2019-01-18 | 2020-09-01 | 中南大学 | Method for preparing high-strength-toughness biological corrosion-resistant magnesium alloy pipe by baking |
| CN109628812A (en) * | 2019-01-29 | 2019-04-16 | 吉林大学 | A kind of low-alloy high-performance superplasticity magnesium alloy and preparation method thereof |
| CN111270088A (en) * | 2020-02-10 | 2020-06-12 | 中国恩菲工程技术有限公司 | System and method for continuously smelting magnesium by induction heating liquid stirring |
| CN111270088B (en) * | 2020-02-10 | 2023-10-13 | 中国恩菲工程技术有限公司 | System and method for continuously smelting magnesium by liquid stirring through induction heating |
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Application publication date: 20111005 |