CN104328319A - Biomedical degradable Mg-Gd-Nd-Zn-Zr alloy, and preparation method and application thereof - Google Patents
Biomedical degradable Mg-Gd-Nd-Zn-Zr alloy, and preparation method and application thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C23/00—Alloys based on magnesium
- C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
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Abstract
The invention belongs to the technical field of biomedical materials, and particularly relates to a biomedical degradable Mg-Gd-Nd-Zn-Zr alloy, and a preparation method and application thereof. The alloy is composed of the following components in percentage by weight: 2-7% of Gd, 0-2% of Nd, 0.1-1% of Zn, 0.1-0.5% of Zr, and the balance of Mg and inevitable impurity elements. The preparation method comprises the following steps: proportioning, and sequentially smelting Mg, Zn, an Mg-Gd interalloy, an Mg-Gd interalloy and an Mg-Zr interalloy under protective atmosphere conditions; and after finishing smelting, adding a refining solvent, refining, and finally, casting to obtain the biomedical degradable Mg-Gd-Nd-Zn-Zr alloy. The alloy has favorable biocompatibility and mechanical strength, and can be used for preparing vessel stent medical materials.
Description
Technical field
The invention belongs to biology medical material technical field, be specifically related to a kind of biological medical degradable Mg-Gd-Nd-Zn-Zr Alloy And Preparation Method and application.
Background technology
In recent years, the sickness rate of cardiovascular disorder is more and more higher, and stent is one of most effective means of Cardiovarscular.Be applied to the material making intravascular stent at present and mainly comprise medical macromolecular materials and medical metal material.Medical macromolecular materials low strength, and degraded product easily causes the problem such as inflammation and swelling.And metallic substance such as stainless steel, cobalt base alloy and titanium base alloy are bio-inert material, after implantation, forever internal blood vessel will be present in.The Long Term Contact of support and blood vessel causes vascular damaged and intimal hyperplasia.Therefore, take Mg-based hydrogen storage as the study hotspot that the medical metal material of new generation with biodegradable characteristics of main representative becomes biomedical materials field.
Compare with non-degradable metallic substance with the medical polymer now having dropped into Clinical practice, magnesium alloy has following outstanding advantage: the histocompatibility that (1) is good, not easily the problems such as restenosis occurs after stenter to implant; (2) magnesium is one of nutritive element required in human body, in adult body every day magnesium demand more than 350mg, excessive magnesium can be discharged by urine, has no side effect.Therefore, the magnesium ion produced in magnesium alloy bracket degradation process not only to human body without harm, and the normal physiological demand of human body to magnesium can be met; (3) its aboundresources, cheap.But the standard potential (-2.37V) of magnesium and alloy thereof is very low, there is the problem that corrosion speed is too fast.The too fast meeting of degradation speed causes embedded material just heavy corrosion to occur before organizing healing completely, and its stability reduces, and then affects body physiological function.For the problem of corrosion stability of magnesium alloy difference, people develop medical corrosion-resisting type magnesium alloy.Such as application number is 201310275808.6, name is called in the patent document of " Biomedical degradable corrosion-resistant Mg-Zn-Zr alloy and preparation method " and discloses a kind of biomedical corrosion-proof magnesium alloy that can be used for body implanting material.But there is the lower problem of intensity in this alloy.The crystalline structure of magnesium is close-packed hexagonal, and the independent slip-system under room temperature is less, only has basal slip, and therefore at room temperature plasticity is low for magnesium alloy, shapes difficulty.Alloying is the effective way overcome the above problems, and adopts alloying can not only improve the corrosion resisting property of alloy, and can also improve alloy toughness plasticity by crystal grain thinning.But for biological medical magnesium alloy, alloy property is being improved simultaneously by alloying, note also and can not introduce harmful alloying element, as although Al element can improve corrosion stability of magnesium alloy energy, but Al element is not the essential trace element of human body, on the contrary there is neurotoxicity, easily cause presenile dementia.
Summary of the invention
In order to solve the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is to provide a kind of biological medical degradable Mg-Gd-Nd-Zn-Zr alloy.
Another object of the present invention is to the preparation method that above-mentioned biological medical degradable Mg-Gd-Nd-Zn-Zr alloy is provided.
Another object of the present invention is to provide the application of above-mentioned biological medical degradable Mg-Gd-Nd-Zn-Zr alloy in intravascular stent medical material.
The object of the invention is achieved through the following technical solutions:
A kind of biological medical degradable Mg-Gd-Nd-Zn-Zr alloy, described alloy is made up of the component of following weight percent: Gd2 ~ 7%, Nd0 ~ 2%, Zn0.1 ~ 1%, Zr0.1 ~ 0.5%, and surplus is Mg and inevitable impurity element.
The weight percent of each component of described alloy is preferably: Gd2.63 ~ 6.35%, Nd0 ~ 1.6%, Zn0.48 ~ 0.86%, Zr0.12 ~ 0.39%, all the other are Mg.
The preparation method of above-mentioned biological medical degradable Mg-Gd-Nd-Zn-Zr alloy, comprises the following steps:
(1) with high-purity magnesium ingot, high-purity zinc ingot metal, Mg-Gd master alloy, Mg-Nd master alloy, Mg-Zr master alloy for raw material, get the raw materials ready according to the weight percent of each component in the weight percentage of Gd, Nd and Zr in three kinds of master alloys and the Mg-Gd-Nd-Zn-Zr alloy that need prepare;
(2) at nitrogen and difluorochloromethane (CHClF
2) mixed atmosphere protection under, high-purity magnesium ingot is heated to melt completely, high-purity zinc ingot metal is added when melt temperature is 700 ~ 720 DEG C, be warming up to 750 DEG C and add Mg-Gd, Mg-Nd, Mg-Zr master alloy successively, in adition process, current a kind of master alloy adds lower one after melting completely again, and constantly stirs to make it to mix and obtain alloy melt;
(3) the refining solvent refined 3 ~ 5min of raw material gross weight 0.5% ~ 0.8% will be added in the alloy melt of step (2), and stop stirring, leave standstill 15 ~ 20min;
(4) alloy melt temperature is down to 700 ~ 720 DEG C, removing surface scum, pouring into preheating temperature is form alloy cast ingot in the mould of 240 ~ 260 DEG C, by carrying argon gas to bath surface in casting process, remain that melt directly contacts with air, after cooling, obtain biological medical degradable Mg-Gd-Nd-Zn-Zr alloy.
High-purity magnesium ingot described in step (1) and high-purity zinc ingot metal refer to magnesium ingot and zinc ingot metal that mass percentage is greater than 99.99%; Described Mg-Gd master alloy refers to that the mass percentage of Gd is the Mg-Gd master alloy of 25%; Described Mg-Nd master alloy refers to that the mass percentage of Nd is the Mg-Nd master alloy of 30%; Described Mg-Zr master alloy refers to that the percentage composition of Zr is the Mg-Zr master alloy of 30%.
Nitrogen described in step (2) refers to the nitrogen of volume basis Han Liang≤99.999%.
Refining solvent described in step (3) refers to RJ-5 refining solvent.
Had the following advantages and beneficial effect by preparation method of the present invention and the product tool that obtains:
(1) Mg-Gd-Nd-Zn-Zr alloy of the present invention all selects harmless metallic element to be prepared from, and is conducive to improving alloy biocompatibility, and its degraded product does not have toxic action to human body;
(2) Mg-Gd-Nd-Zn-Zr alloy of the present invention adopts polynary milligram ammonia design concept, give full play to the advantage of each metallic element self, Gd, Nd and Zn add the effect all having solution strengthening and ageing strengthening, improve the intensity of magnesium alloy, Zr element can promote forming core in process of setting simultaneously, increase nucleation rate, second-phase obtains refinement;
(3) Mg-Gd-Nd-Zn-Zr alloy of the present invention has good corrosion resisting property, and the raw material that melting adopts is high purity magnesium and high purity master alloy, can reduce the content of impurity element by high degree, thus improve the corrosion resisting property of magnesium alloy; Nd element add the electropotential that can increase substantially magnesium alloy substrate, reduce galvanic corrosion tendency, significantly strengthen corrosion stability of magnesium alloy energy;
(4) preparation method of Mg-Gd-Nd-Zn-Zr alloy of the present invention is by adopting rational master alloy addition sequence, reaches being uniformly distributed of second-phase, reduces the scaling loss in fusion process; This preparation method is low for equipment requirements simultaneously, and preparation technology is simple, and production cost is low, easily realizes large-scale industrial production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
The preparation of the Mg-2.63%Gd-1.6%Nd-0.48%Zn-0.39%Zr alloy of the present embodiment, concrete preparation process is:
(1) with the mass percentage of high-purity magnesium ingot, high-purity zinc ingot metal, Gd be the Mg-Gd master alloy of 25%, the mass percentage of Nd is the Mg-Nd master alloy of 30%, the mass percentage of Zr is that the Mg-Zr master alloy of 30% is for raw material, according to weight percentage Gd2.63%, Nd1.6%, Zn0.48%, the Zr0.39% by weight percentage of Gd, Nd and Zr in three kinds of master alloys, all the other are got the raw materials ready for Mg;
(2) at nitrogen and difluorochloromethane (CHClF
2) mixed atmosphere protection under, magnesium ingot is heated to melt completely, zinc ingot metal is added when melt temperature is 700 ~ 720 DEG C, Mg-Gd, Mg-Nd, Mg-Zr master alloy is added successively when being warming up to 750 DEG C, just can add lower one after only having current a kind of master alloy to melt completely in adition process, and constantly stir to make it to mix and obtain alloy melt;
(3) the RJ-5 solvent refined 5min of raw material gross weight 0.5% will be added in the alloy melt of step (2), stop stirring, leave standstill 15min;
(4) alloy melt temperature is down to 700 ~ 720 DEG C, removing surface scum, pouring into preheating temperature is form alloy cast ingot in the mould of 240 ~ 260 DEG C, by carrying argon gas to bath surface in casting process, remain that melt directly contacts with air, alloy cast ingot cooling obtains Mg-2.63%Gd-1.6%Nd-0.48%Zn-0.39%Zr alloy.
Room temperature tensile Mechanics Performance Testing is carried out on microcomputer control universal testing machine (SANSCMT5105, China), and strain rate is 2.0 × 10
-3s
-1, the room-temperature yield strength of this alloy is 86MPa, and tensile strength is 160MPa, and elongation is 11%.This magnesium alloy erosion rate in Hank ' s simulated body fluid is 0.29mm/year, and degradable absorbs in vivo.
Embodiment 2
The preparation of the Mg-4.25%Gd-1.42%Nd-0.59%Zn-0.37%Zr alloy of the present embodiment, concrete preparation process is:
(1) with the mass percentage of high-purity magnesium ingot, high-purity zinc ingot metal, Gd be the Mg-Gd master alloy of 25%, the mass percentage of Nd is the Mg-Nd master alloy of 30%, the mass percentage of Zr is that the Mg-Zr master alloy of 30% is for raw material, according to weight percentage Gd4.25%, Nd1.42%, Zn0.59%, the Zr0.37% by weight percentage of Gd, Nd and Zr in three kinds of master alloys, all the other are got the raw materials ready for Mg;
(2) at nitrogen and difluorochloromethane (CHClF
2) mixed atmosphere protection under, magnesium ingot is heated to melt completely, zinc ingot metal is added when melt temperature is 700 ~ 720 DEG C, Mg-Gd, Mg-Nd, Mg-Zr master alloy is added successively when being warming up to 750 DEG C, just can add lower one after only having current a kind of master alloy to melt completely in adition process, and constantly stir to make it to mix and obtain alloy melt;
(3) the RJ-5 solvent refined 3min of raw material gross weight 0.8% will be added in the alloy melt of step (2), stop stirring, leave standstill 20min;
(4) alloy melt temperature is down to 700 ~ 720 DEG C, removing surface scum, pouring into preheating temperature is form alloy cast ingot in the mould of 240 ~ 260 DEG C, by carrying argon gas to bath surface in casting process, remain that melt directly contacts with air, alloy cast ingot cooling obtains Mg-4.25%Gd-1.42%Nd-0.59%Zn-0.37%Zr alloy.
Room temperature tensile Mechanics Performance Testing is carried out on microcomputer control universal testing machine (SANSCMT5105, China), and strain rate is 2.0 × 10
-3s
-1, the room-temperature yield strength of this alloy is 95MPa, and tensile strength is 190MPa, and elongation is 13%.This magnesium alloy erosion rate in Hank ' s simulated body fluid is 0.14mm/year, and degradable absorbs in vivo.
Embodiment 3
The preparation of the Mg-6.35%Gd-0.86%Zn-0.12%Zr alloy of the present embodiment, concrete preparation process is:
(1) with the mass percentage of high-purity magnesium ingot, high-purity zinc ingot metal, Gd be the Mg-Gd master alloy of 25%, the mass percentage of Zr is that the Mg-Zr master alloy of 30% is for raw material, according to weight percentage Gd6.35%, Zn0.86%, the Zr0.12% by weight percentage of Gd and Zr in two kinds of master alloys, all the other are got the raw materials ready for Mg;
(2) at nitrogen and difluorochloromethane (CHClF
2) mixed atmosphere protection under, magnesium ingot is heated to melt completely, zinc ingot metal is added when melt temperature is 700 ~ 720 DEG C, Mg-Gd, Mg-Zr master alloy is added successively when being warming up to 750 DEG C, just can add lower one after only having current a kind of master alloy to melt completely in adition process, and constantly stir to make it to mix and obtain alloy melt;
(3) the RJ-5 solvent refined 5min of raw material gross weight 0.8% will be added in the alloy melt of step (2), stop stirring, leave standstill 20min;
(4) alloy melt temperature is down to 700 ~ 720 DEG C, removing surface scum, pouring into preheating temperature is form alloy cast ingot in the mould of 240 ~ 260 DEG C, by carrying argon gas to bath surface in casting process, remain that melt directly contacts with air, after alloy cast ingot cooling, obtain Mg-6.35%Gd-0.86%Zn-0.12%Zr alloy.
Room temperature tensile Mechanics Performance Testing is carried out on microcomputer control universal testing machine (SANSCMT5105, China), and strain rate is 2.0 × 10
-3s
-1, the room-temperature yield strength of this alloy is 92MPa, and tensile strength is 210MPa, and elongation is 15%.This magnesium alloy erosion rate in Hank ' s simulated body fluid is 0.24mm/year, and degradable absorbs in vivo.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a biological medical degradable Mg-Gd-Nd-Zn-Zr alloy, it is characterized in that: described alloy is made up of the component of following weight percent: Gd2 ~ 7%, Nd0 ~ 2%, Zn0.1 ~ 1%, Zr0.1 ~ 0.5%, surplus is Mg and inevitable impurity element.
2. a kind of biological medical degradable Mg-Gd-Nd-Zn-Zr alloy according to claim 1, it is characterized in that: the weight percent of each component of described alloy is: Gd2.63 ~ 6.35%, Nd0 ~ 1.6%, Zn0.48 ~ 0.86%, Zr0.12 ~ 0.39%, all the other are Mg.
3. the preparation method of the biological medical degradable Mg-Gd-Nd-Zn-Zr alloy described in claim 1 or 2, is characterized in that comprising the following steps:
(1) with high-purity magnesium ingot, high-purity zinc ingot metal, Mg-Gd master alloy, Mg-Nd master alloy, Mg-Zr master alloy for raw material, get the raw materials ready according to the weight percent of each component in the weight percentage of Gd, Nd and Zr in three kinds of master alloys and the Mg-Gd-Nd-Zn-Zr alloy that need prepare;
(2) under nitrogen and the protection of difluorochloromethane mixed atmosphere, high-purity magnesium ingot is heated to melt completely, high-purity zinc ingot metal is added when melt temperature is 700 ~ 720 DEG C, be warming up to 750 DEG C and add Mg-Gd, Mg-Nd, Mg-Zr master alloy successively, in adition process, current a kind of master alloy adds lower one after melting completely again, and constantly stirs to make it to mix and obtain alloy melt;
(3) the refining solvent refined 3 ~ 5min of raw material gross weight 0.5% ~ 0.8% will be added in the alloy melt of step (2), and stop stirring, leave standstill 15 ~ 20min;
(4) alloy melt temperature is down to 700 ~ 720 DEG C, removing surface scum, pouring into preheating temperature is form alloy cast ingot in the mould of 240 ~ 260 DEG C, by carrying argon gas to bath surface in casting process, remain that melt directly contacts with air, after cooling, obtain biological medical degradable Mg-Gd-Nd-Zn-Zr alloy.
4. the preparation method of biological medical degradable Mg-Gd-Nd-Zn-Zr alloy according to claim 3, is characterized in that: the high-purity magnesium ingot described in step (1) and high-purity zinc ingot metal refer to magnesium ingot and zinc ingot metal that mass percentage is greater than 99.99%; Described Mg-Gd master alloy refers to that the mass percentage of Gd is the Mg-Gd master alloy of 25%; Described Mg-Nd master alloy refers to that the mass percentage of Nd is the Mg-Nd master alloy of 30%; Described Mg-Zr master alloy refers to that the percentage composition of Zr is the Mg-Zr master alloy of 30%.
5. the preparation method of biological medical degradable Mg-Gd-Nd-Zn-Zr alloy according to claim 3, is characterized in that: the nitrogen described in step (2) refers to the nitrogen of volume basis Han Liang≤99.999%.
6. the preparation method of biological medical degradable Mg-Gd-Nd-Zn-Zr alloy according to claim 3, is characterized in that: the refining solvent described in step (3) refers to RJ-5 refining solvent.
7. the application of biological medical degradable Mg-Gd-Nd-Zn-Zr alloy in intravascular stent medical material described in claim 1 or 2.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803282A (en) * | 2016-03-22 | 2016-07-27 | 中国兵器科学研究院宁波分院 | Single-phase multi-element rare earth magnesium alloy biodegradable material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080262589A1 (en) * | 2005-01-28 | 2008-10-23 | Terumo Kabushiki Kaisha | Intravascular Implant |
| CN101575683A (en) * | 2009-06-01 | 2009-11-11 | 中国兵器工业第五二研究所 | High strength corrosion resistant rare earth cast magnesium alloy and preparation method thereof |
| EP2213314A1 (en) * | 2009-01-30 | 2010-08-04 | Biotronik VI Patent AG | Implant with a base body of a biocorrodible magnesium alloy |
| CN102828094A (en) * | 2012-09-17 | 2012-12-19 | 中国科学院长春应用化学研究所 | Deforming magnesium alloy and preparation method thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080262589A1 (en) * | 2005-01-28 | 2008-10-23 | Terumo Kabushiki Kaisha | Intravascular Implant |
| EP2213314A1 (en) * | 2009-01-30 | 2010-08-04 | Biotronik VI Patent AG | Implant with a base body of a biocorrodible magnesium alloy |
| CN101575683A (en) * | 2009-06-01 | 2009-11-11 | 中国兵器工业第五二研究所 | High strength corrosion resistant rare earth cast magnesium alloy and preparation method thereof |
| CN102828094A (en) * | 2012-09-17 | 2012-12-19 | 中国科学院长春应用化学研究所 | Deforming magnesium alloy and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803282A (en) * | 2016-03-22 | 2016-07-27 | 中国兵器科学研究院宁波分院 | Single-phase multi-element rare earth magnesium alloy biodegradable material and preparation method thereof |
| CN105803282B (en) * | 2016-03-22 | 2017-12-08 | 中国兵器科学研究院宁波分院 | A kind of single-phase Multielement rare-earth magnesium alloy biodegradation material and preparation method thereof |
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Application publication date: 20150204 |