CN102181759B - Aluminum alloy suitable for intravascular stent - Google Patents
Aluminum alloy suitable for intravascular stent Download PDFInfo
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- CN102181759B CN102181759B CN201110092761.0A CN201110092761A CN102181759B CN 102181759 B CN102181759 B CN 102181759B CN 201110092761 A CN201110092761 A CN 201110092761A CN 102181759 B CN102181759 B CN 102181759B
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Abstract
The invention relates to an aluminum alloy suitable for an intravascular stent. The aluminum alloy is characterized by consisting of the following components in percentage by mass: 0.8 to 1.2 percent of Al, 0.8 to 1.2 percent of Zn, 0.4 to 0.8 percent of mixed rare-earth RE, 0.4 to 0.7 percent of Mn, and the balance of magnesium and inevitable impurities, wherein the mixed rare-earth consists of the following components in percentage: 60 percent of Ce, 35 percent of La and 5 percent of Pr. The Al and the mixed rare-earth RE in the aluminum alloy play a role in second phase dispersion strengthening; for the aluminum alloy, after deformation processing, the tensile strength is 250 to 300 Mpa, the elongation percentage is 10 to 15 percent; the aluminum alloy is suitable for the intravascular stent to meet the requirements on 6 months of degradation; and the provided stent is in a press-hold or ball-expansion state. The radial supporting force of the provided stent is far more than 40 Kpa of the index standard weight, and after radial press-holding and re-diffusion, the stent has no rupture and returns to the original shape.
Description
Technical field
The present invention relates to a kind of magnesium alloy that is applicable to intravascular stent, relate to or rather a kind of low aluminium wrought magnesium alloys, belong to medical magnesium alloy field.
Background technology
Cardiovascular disorder has become the first killer of modern humans, and adopting intravascular stent interventional therapy is one of effective means of Cardiovarscular.Desirable vascular stent material should physiologically acceptable, biodegradable again, and meanwhile, it is moderate and controlled that degradation speed is wanted.Magnesium has excellent mechanical features (intensity, elasticity, ductility, stable), has again biodegradability, is that a kind of desirable body is implanted into novel material.Receive biomaterial worker's concern from the degradable/corrosive nature of magnesium alloy, it is rapid at orthopaedics and the development of blood vessel section, especially there is the Biotronik of foreign biomolecule medical apparatus corporation, Ltd to get involved and develop as degradable blood vessel bracket, entered clinical experimental stage.The units such as domestic Peking University, Shenyang Inst. of Metals, Chinese Academy of Sciences, University Of Chongqing, Ha Er shore polytechnical university have carried out experimental study in recent years, will carry out experimentation on animals.
AMS (the absorb metal stent) intravascular stent of Biotronik company of Germany has been released two and has been substituted in clinical trial, jointly participate in clinical trial in eight medical centres of seven countries such as Australia, Belgium, Germany, Switzerland, New Zealand, UK and USAs, 71 routine AMS intravascular stents are implanted in success, find that security is good.Without death, without myocardial infarction, without thrombosis; Available MRI/CT means detect; Reconstructing blood vessel rate is similar to bare mental stents; After IVUS detection technique, 4 months supports are degradable.Within postoperative three days, observe blood vessel endothelium.And then still there are some problems as degradable blood vessel bracket in magnesium alloy, such as degraded is too fast, cause loss of strength very fast, theca interna hyperplasia causes official jargon narrow, and intensity is low causes early stage resilience etc., all urgently to be resolved hurrily.Have been reported about Magnesiumalloy surface modifying, improve the research that alloy system improves magnesium alloy strength, improves supporting structure design and improve corrosion resistance, therefore address the above problem and become possibility based on the suitable approach of existing research searching, need biomaterial worker further to study.
The bio-medical material of being led by the Yang Ke of Shenyang Institute of Metal Research, Chinese Academy of Sciences and device seminar, select AZ31 magnesium alloy as biodegradable stent material, designed, designed also adopts laser cutting method to process magnesium alloy angiocarpy bracket, the impacts of problem on deformation of timbering performance such as magnesium alloy self plasticity is low are overcome, pass through surface modification treatment, realize the segmentation controlled degradation of magnesium alloy bracket, made it provide enough mechanics supporting roles at the implantation initial stage.In order further to reduce angiogenesis inner film thickness, increase lumen diameter, at magnesium alloy bracket skin, prepared the degradable polymer coating of carrying medicine, make it slowly discharge the rapamycin medicine that suppresses intimal hyperplasia at vascular lesion position, reach synchronous therapeutic effect.The shortcoming of this alloy is to contain more aluminium element, and the biocompatibility of alloy itself is poor.
On forefathers' Research foundation, the present invention is directed to the requirement of intravascular stent, develop a kind of magnesium alloy that is applicable to intravascular stent.Content with respect to AZ31 magnesium alloy aluminium element is lower, and biocompatibility is better, in the case of low aluminium content, has better mechanical property.
Summary of the invention
The object of the present invention is to provide a kind of magnesium alloy that is applicable to intravascular stent, the mass percent of the composition that is applicable to intravascular stent magnesium alloy provided by the invention is: aluminium Al is 0.8-1.2%, zinc Zn is 0.8-1.2%, mixed rare earth is 0.4-0.8%, manganese is Mn 0.4-0.7%, and surplus is magnesium and inevitable impurity (foreign matter content≤0.02%).Intravascular stent of the present invention is characterised in that with magnesium alloy the quality percentage composition containing in mixed rare earth is 60%Ce, 35%La, 5%Pr).
In order to further illustrate the performance that intravascular stent magnesium alloy is better than the existing trade mark that is applicable to provided by the invention, the present invention has successively chosen WE43, AZ31, AZ11 and alloy provided by the invention, carry out melting and extruding, top-priority is the corrosion resisting property of alloy.Fig. 1 demonstrates the erosion rate in various magnesium alloy simulate blood environment.As can be seen from Figure, WE43 Corrosion Behaviors of Magnesium Alloys speed maximum, AZ11 and AZ31 magnesium alloy take second place, the minimum 0.228mm/y left and right that reaches of erosion rate of magnesium alloy provided by the invention.
Meanwhile, then the present invention has further carried out again the immersion test of 30 days to AZ31 and magnesium alloy provided by the invention, investigates its corrosion resisting property (seeing Fig. 2).
The erosion rate of finding AZ31 magnesium alloy after the immersion test of 30 days increases considerably, and the amplitude that magnesium alloy provided by the invention increases is less, and the erosion rate of particularly soaking 30 days is 0.794mm/y.
Integrated survey is got off, and the erosion rate of magnesium alloy provided by the invention is comparatively desirable, and the aluminium content of this alloy is lower, and the biocompatibility of alloy is favourable.
The mechanical property of the various magnesium alloy extrusion states of table 1
Table 1 demonstrates the mechanical property of various magnesium alloy extrusion states, and as can be seen from Table 1, tensile strength and the yield strength of WE43 and magnesium alloy provided by the invention are higher, and AZ11 and AZ31 tensile strength and yield strength are lower.Generally speaking, aspect mechanical property, magnesium alloy provided by the invention can meet intensity 250-300Mpa, the requirement of unit elongation 10-15%.
The intravascular stent magnesium alloy that is applicable to provided by the invention is characterised in that and 1. on the basis of AZ11 magnesium alloy, adds a small amount of mishmetal, generate Al-RE second-phase, play the effect of second-phase dispersion strengthening, the intensity of alloy is greatly improved, the requirement that plasticity also can meet intravascular stent processing and use simultaneously; 2. the composition of Aluminum in Alloy is lower, can reduce the disadvantageous effect of aluminium element to biocompatibility; Utilize the component of low aluminium can put forward again heavy alloyed solidity to corrosion simultaneously; 3. the present invention is under the synergy of aluminium element, zinc element, rare earth element, manganese element, meet the requirement of intravascular stent degraded in six months, mechanical property after deformation processing (tensile strength 250-300Mpa, unit elongation 10-15%) meets the requirement of intravascular stent manufacture and use.(referring to embodiment 1-6)
The various extruded Magnesium Alloys of Fig. 1 are in the erosion rate of artificial 37 DEG C of two days immersion tests of blood plasma.
The various extruded Magnesium Alloys of Fig. 2 are in the erosion rate of artificial 37 DEG C of 30 days immersion tests of blood plasma.
Fig. 3 is that magnesium alloy bracket of the present invention presses the state of holding and ball to expand state, a) holds state magnesium alloy bracket for pressure provided by the invention; B) be the enzyme alloy bracket that ball provided by the invention expands state.
Fig. 4 is that magnesium alloy bracket of the present invention is through accelerating the pattern of 10 times of artificial blood plasma scouring experiments support afterwards.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is further illustrated, and further to set forth substantive distinguishing features of the present invention and significant progressive, but the present invention is only confined to by no means embodiment.
Embodiment 1: a kind of intravascular stent magnesium alloy, the percentage composition of alloying constituent quality is: aluminium Al is 0.8%, and zinc Zn is 1.0%, and mixed rare earth is 0.5%, manganese Mn 0.4%, surplus is Mg and inevitable impurity, foreign matter content≤0.02%.Mechanical property: intensity 280Mpa after shape processing, unit elongation 18% from erosion rate 0.018mm/y, meets biocompatibility requirement under rete protection.
Embodiment 2: a kind of intravascular stent magnesium alloy, alloying constituent aluminium Al is 0.9%, and zinc Zn is 1.0%, and mixed rare earth is 0.6%, and manganese Mn is 0.4%, surplus is Mg and inevitable impurity, foreign matter content≤0.02%.Mechanical property: intensity 285Mpa after shape processing, unit elongation 17% from erosion rate 0.02mm/y, meets biocompatibility requirement under rete protection.
Embodiment 3: a kind of intravascular stent magnesium alloy, alloying constituent aluminium Al is 0.9%, and zinc Zn is 1.0%, and mixed rare earth is 0.5%, and manganese Mn is 0.4%, surplus is Mg and inevitable impurity, foreign matter content≤0.02%.Mechanical property: intensity 283Mpa after shape processing, unit elongation 18% from erosion rate 0.019mm/y, meets biocompatibility requirement under rete protection.
Embodiment 4: a kind of intravascular stent magnesium alloy, alloying constituent aluminium Al is 1.2%, and zinc Zn is 1.2%, and mixed rare earth is 0.8%, and manganese Mn is 0.4%, surplus is Mg and inevitable impurity, foreign matter content≤0.02%.Mechanical property: intensity 300Mpa after shape processing, unit elongation 15% from erosion rate 0.015mm/y, meets biocompatibility requirement under rete protection.
Embodiment 5: a kind of intravascular stent magnesium alloy, alloying constituent aluminium Al is 0.8%, and zinc Zn is 0.8%, and mixed rare earth is 0.4%, and manganese Mn is 0.4%, surplus is Mg and inevitable impurity, foreign matter content≤0.02%.Mechanical property: intensity 265Mpa after shape processing, unit elongation 20% from erosion rate 0.022mm/y, meets biocompatibility requirement under rete protection.
Embodiment 6: above-described embodiment degradation speed meets the requirement of intravascular stent degraded in six months, and after deformation processing, mechanical property meets the requirement of intravascular stent manufacture and use meets biocompatibility requirement under rete protection.
Fig. 3 is that magnesium alloy bracket provided by the invention is pressed state (a) and the ball expansion state (b) held.In test process, there is not fracture in support.The radial support power (i.e. the radially anti-ability of subsiding) of magnesium alloy bracket of the present invention is considerably beyond the heavy 40Kpa of index.After further expansion is held in overvoltage, there is not fracture in support, replys former state.
After magnesium alloy bracket of the present invention accelerated 10 times of artificial blood plasma scouring experiments through one month as can be seen from Figure 4, basic maintenance continuously.10 months supports of this experimental simulation are in the process of washing away of artificial blood plasma.Illustrate that the artificial blood plasma that support that magnesium alloy of the present invention is made can stand 10 months washes away.
Of the present invention magnesium alloy bracket radial support power and the Profile value of table 2 for recording.Its diameter is reached while being held on sacculus by pressure size that Profile value refers to support.
Table 2 support radial support power and Profile value
Claims (6)
1. be applicable to an intravascular stent magnesium alloy, it is characterized in that:
1. described magnesium alloy is under the synergy of aluminium element, zinc element, rare earth element, manganese element, meets the requirement of intravascular stent degraded in six months;
2. described magnesium alloy mass percent is any in following a)～e) 5 component;
A) described magnesium alloy quality percentage composition is that Al is that 0.8%, Zn is 1.0%; Mixed rare earth is that 0.5%, Mn is 0.4%, and surplus is Mg and inevitable impurity;
B) described magnesium alloy quality percentage composition is: Al is that 0.9%, Zn is 1.0%, and mixed rare earth mass percent is 0.6%, Mn0.4%, and surplus is Mg and inevitable impurity;
C) described magnesium alloy quality percentage composition is: Al is that 0.9%, Zn is 1.0%, and mixed rare earth mass percent is 0.5%, Mn0.4%, and surplus is Mg and inevitable impurity;
D) described magnesium alloy quality percentage composition is: Al is that 1.2%, Zn is 1.2%, and mixed rare earth mass percent is 0.8%, Mn0.4%, and surplus is Mg and inevitable impurity;
Or e) described magnesium alloy quality percentage composition is: Al is that 0.8%, Zn is 0.8%, and rare earth RE mass percent is 0.4%, Mn0.4%, and surplus is Mg and inevitable impurity;
The percentage composition of described mishmetal is 60%Ce, 35%La and 5%Pr; Described inevitable impurity quality percentage composition is≤0.02%.
2. by magnesium alloy claimed in claim 1, in the magnesium alloy described in it is characterized in that, Al and mixed rare-earth elements RE play second-phase dispersion strengthening effect.
3. by magnesium alloy application claimed in claim 1, the intravascular stent that it is characterized in that being applicable to intravascular stent provides is to press the state of holding or ball to expand state.
4. by application claimed in claim 3, it is characterized in that provided magnesium alloy bracket radial support power far exceedes the 40kPa of index indicated weight, after diffusion is again held in overvoltage, there is not fracture in support, replys former state.
5. by application claimed in claim 3, it is characterized in that provided magnesium alloy bracket washes away through accelerating 10 times of artificial blood plasma, keep continuously, the artificial blood plasma that can stand 10 months washes away.
6. by application claimed in claim 5, it is characterized in that provided magnesium alloy bracket radial support power is 168.7kPa, Profile value is 1.3623mm, the diameter that described Profile value representation support is reached while being held on sacculus by pressure.
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| CN107675054A (en) * | 2017-09-30 | 2018-02-09 | 江苏瑞腾涂装科技有限公司 | A kind of cardiac stent alloy material |
| CN108543118B (en) * | 2018-05-21 | 2022-04-26 | 申英末 | Magnesium alloy fixing screw capable of being degraded controllably in vivo |
| CN108714252B (en) * | 2018-05-21 | 2022-04-26 | 申英末 | Preparation method of magnesium alloy fixing screw capable of being degraded controllably in vivo |
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| CN101062427A (en) * | 2006-04-29 | 2007-10-31 | 中国科学院金属研究所 | Medical corrosion-resisting type magnesium alloy |
| CN101085377B (en) * | 2007-06-11 | 2011-05-04 | 沈阳工业大学 | Process for forming magnesium alloy ultra-fine thin-wall tube used for degradable blood vessel bracket |
| CN101953709A (en) * | 2010-09-29 | 2011-01-26 | 上海交通大学医学院附属第三人民医院 | Absorbable rib intramedullary nail |
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Effective date of registration: 20180827 Address after: 226600 No. 8, C District, Chengbei industrial concentration area, Haian County, Nantong, Jiangsu. Patentee after: JIANGSU ZHONGKE YAMEI NEW MATERIAL CO., LTD. Address before: 200050 No. 865, Changning Road, Shanghai, Changning District Patentee before: Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences |
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Address after: 226600 No. 8, C District, Chengbei industrial concentration area, Haian County, Nantong, Jiangsu. Patentee after: Jiangsu Zhongke Yamei New Materials Co.,Ltd. Address before: 226600 No. 8, C District, Chengbei industrial concentration area, Haian County, Nantong, Jiangsu. Patentee before: JIANGSU ZHONGKE YAMEI NEW MATERIAL Co.,Ltd. |