CN102181759A - Aluminum alloy suitable for intravascular stent - Google Patents
Aluminum alloy suitable for intravascular stent Download PDFInfo
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- CN102181759A CN102181759A CN 201110092761 CN201110092761A CN102181759A CN 102181759 A CN102181759 A CN 102181759A CN 201110092761 CN201110092761 CN 201110092761 CN 201110092761 A CN201110092761 A CN 201110092761A CN 102181759 A CN102181759 A CN 102181759A
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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 a kind of low aluminium wrought magnesium alloys or rather, belong to the medical magnesium alloy field.
Background technology
Cardiovascular disorder has become modern humans's first killer, and adopting the intravascular stent interventional therapy is one of effective means of treatment cardiovascular disorder.The ideal vascular stent material should physiologically acceptable, biodegradable again, and simultaneously, it is moderate and controlled that degradation speed is wanted.Magnesium has excellent mechanical features (intensity, elasticity, ductility, stable), has biodegradability again, is that a kind of ideal 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 has been the Biotronik of foreign biomolecule medical apparatus corporation, Ltd to get involved and exploitation as degradable blood vessel bracket, entered clinical experimental stage.Units such as domestic Peking University, Shenyang Inst. of Metals, Chinese Academy of Sciences, University Of Chongqing, youngster shore, Kazakhstan polytechnical university have carried out experimental study in recent years, will carry out experimentation on animals.
AMS (the absorb metal stent) intravascular stent of Germany Biotronik company has been released two and has been substituted in clinical trial, participated in clinical trial jointly in eight medical centres of seven countries such as Australia, Belgium, Germany, Switzerland, New Zealand, Britain and the U.S., 71 routine AMS intravascular stents are implanted in success, find that security is good.Do not have death, do not have myocardium infarct, no thrombosis; Available MRI/CT means detect; The reconstructing blood vessel rate is similar to naked through metal; 4 months supports are degraded fully behind the IVUS detection technique.Postoperative was observed blood vessel endotheliumization in three days.And then still there are some problems in magnesium alloy as degradable blood vessel bracket, and is too fast such as degraded, causes loss of strength very fast, and the theca interna hyperplasia causes official jargon narrow, and intensity is low to cause early stage resilience etc., all needs to be resolved hurrily.The research that existing report improves magnesium alloy strength, improves the supporting structure design and improve corrosion resistance about Magnesiumalloy surface modifying, improvement alloy system, therefore addressing the above problem based on existing research searching suitable way becomes possibility, needs the biomaterial worker further to study.
Bio-medical material and device seminar by the Yang Ke of Shenyang metal institute of Chinese Academy of Sciences leader, select the AZ31 magnesium alloy as the biodegradable stent material, design voluntarily and adopt laser cutting method to process magnesium alloy angiocarpy bracket, problems such as magnesium alloy self plasticity is low have been overcome to the deformation of timbering Effect on Performance, pass through surface modification treatment, realized 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 the angiogenesis inner film thickness, increase lumen diameter,, prepared the degradable polymer coating of carrying medicine at the magnesium alloy bracket skin, make it slowly discharge the rapamycin medicine that suppresses intimal hyperplasia at the vascular lesion position, reach the synchronous therapeutic effect.The shortcoming of this alloy is to contain more aluminium element, and the biocompatibility of alloy itself is relatively poor.
On the former study basis, the present invention is directed to the requirement of intravascular stent, developed 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, has better mechanical property under the situation of low aluminium content.
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 intravascular stent that is applicable to provided by the invention with the mass percent of the composition of magnesium alloy is: aluminium Al is 0.8-1.2%, zinc Zn is 0.8-1.2%, mishmetal RE is 0.4-0.8%, manganese is Mn 0.4-0.7%, and surplus is magnesium and unavoidable impurities (foreign matter content≤0.02%).Intravascular stent of the present invention is characterised in that with magnesium alloy the quality percentage composition that contains among the mishmetal RE is 60%Ce, 35%La, 5%Pr).
Be better than the performance of the existing trade mark with magnesium alloy in order to further specify the intravascular stent 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 corrosion resistance of alloy.Fig. 1 demonstrates the erosion rate in the various magnesium alloy simulate blood environment.As can be seen from Figure, WE43 magnesium alloy erosion rate maximum, AZ11 and AZ31 magnesium alloy take second place, and the erosion rate of magnesium alloy provided by the invention is minimum to be reached about 0.228mm/y.
Simultaneously, then the present invention has further carried out 30 days immersion test again to AZ31 and magnesium alloy provided by the invention, investigates its corrosion resisting property (see figure 2).
The erosion rate of finding the AZ31 magnesium alloy behind 30 days immersion test 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 is favourable to the biocompatibility of alloy.
The mechanical property of the various magnesium alloy extruding of table 1 attitude
Table 1 demonstrates the mechanical property of various magnesium alloy extruding attitudes, can find out that 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 is lower.Generally speaking, aspect mechanical property, magnesium alloy provided by the invention can satisfy intensity 250-300Mpa, the requirement of unit elongation 10-15%.
The intravascular stent that is applicable to provided by the invention is characterised in that the 1. a spot of mishmetal of adding on the basis of AZ11 magnesium alloy with magnesium alloy, generate Al-RE second phase, play the effect that second-phase dispersion is strengthened, the intensity of alloy is greatly improved, and plasticity also can satisfy the requirement of 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 that hangs down aluminium can improve the solidity to corrosion of alloy again simultaneously; 3. the present invention is under the synergy of aluminium element, zinc element, rare earth element, manganese element, satisfy the requirement of intravascular stent degraded in six months, mechanical property after the deformation processing (tensile strength 250-300Mpa, unit elongation 10-15%) satisfies the requirement of intravascular stent manufacturing and use.(seeing embodiment 1-6 for details)
The various extruding attitude of Fig. 1 magnesium alloy is in the erosion rate of artificial 37 ℃ of two days immersion tests of blood plasma.
The various extruding attitude of Fig. 2 magnesium alloy is in the erosion rate of artificial 37 ℃ of 30 days immersion tests of blood plasma.
Fig. 3 presses the state of holding and ball for magnesium alloy bracket of the present invention and expands state, a) holds the 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 washes away the pattern of testing support afterwards for magnesium alloy bracket of the present invention through quickening 10 times of artificial blood plasma.
Embodiment
The present invention is further illustrated below in conjunction with embodiment and accompanying drawing, and with further elaboration substantive distinguishing features of the present invention and obvious improvement, but the present invention only is confined to embodiment by no means.
Embodiment 1: a kind of intravascular stent magnesium alloy, and the percentage composition of alloying constituent quality is: aluminium Al is 0.8%, and zinc Zn is 1.0%, and mishmetal RE is 0.5%, manganese Mn 0.4%, surplus is Mg and unavoidable impurities, foreign matter content≤0.02%.Shape processing back mechanical property: intensity 280Mpa, unit elongation 18% from erosion rate 0.018mm/y, satisfies biocompatibility requirement under the rete protection.
Embodiment 2: a kind of intravascular stent magnesium alloy, and alloying constituent aluminium Al is 0.9%, and zinc Zn is 1.0%, and mishmetal RE is 0.6%, and manganese Mn is 0.4%, surplus is Mg and unavoidable impurities, foreign matter content≤0.02%.Shape processing back mechanical property: intensity 285Mpa, unit elongation 17% from erosion rate 0.02mm/y, satisfies biocompatibility requirement under the rete protection.
Embodiment 3: a kind of intravascular stent magnesium alloy, and alloying constituent aluminium Al is 0.9%, and zinc Zn is 1.0%, and mishmetal RE is 0.5%, and manganese Mn is 0.4%, surplus is Mg and unavoidable impurities, foreign matter content≤0.02%.Shape processing back mechanical property: intensity 283Mpa, unit elongation 18% from erosion rate 0.019mm/y, satisfies biocompatibility requirement under the rete protection.
Embodiment 4: a kind of intravascular stent magnesium alloy, and alloying constituent aluminium Al is 1.2%, and zinc Zn is 1.2%, and mishmetal RE is 0.8%, and manganese Mn is 0.4%, surplus is Mg and unavoidable impurities, foreign matter content≤0.02%.Shape processing back mechanical property: intensity 300Mpa, unit elongation 15% from erosion rate 0.015mm/y, satisfies biocompatibility requirement under the rete protection.
Embodiment 5: a kind of intravascular stent magnesium alloy, and alloying constituent aluminium Al is 0.8%, and zinc Zn is 0.8%, and mishmetal RE is 0.4%, and manganese Mn is 0.4%, surplus is Mg and unavoidable impurities, foreign matter content≤0.02%.Shape processing back mechanical property: intensity 265Mpa, unit elongation 20% from erosion rate 0.022mm/y, satisfies biocompatibility requirement under the rete protection.
Embodiment 6: the foregoing description degradation speed satisfies the requirement of intravascular stent degraded in six months, and mechanical property satisfies the requirement of intravascular stent manufacturing and use after the deformation processing, satisfies biocompatibility requirement under the rete protection.
Fig. 3 presses state (a) and the ball expansion state (b) held for magnesium alloy bracket provided by the invention.In test process, fracture does not appear in support.The radial support power of magnesium alloy bracket of the present invention (the promptly radially anti-ability of subsiding) is considerably beyond the heavy 40Kpa of index.Support fracture do not occur after further expansion is held in overvoltage, reply former state.
Magnesium alloy bracket of the present invention as can be seen from Figure 4 washes away through 10 times of artificial blood plasma of an acceleration in month after the experiment, the 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.The Profile value refers to the support size that its diameter is reached when being held on the sacculus by pressure.
Table 2 support radial support power and Profile value
Claims (8)
1. one kind is applicable to the intravascular stent magnesium alloy, it is characterized in that described magnesium alloy mass percent consists of: Al 0.8-1.2%, Zn are that 0.8-1.2%, mishmetal RE are that 0.4-0.8, Mn are 0.4-0.7%, and surplus is magnesium and unavoidable impurities; Forming percentage composition in the mishmetal is 60%Ce, 35%Ce and 5%Pr.
2. by the described magnesium alloy of claim 1, it is characterized in that unavoidable impurities quality percentage composition is≤0.02%.
3. by the described magnesium alloy of claim 1, it is characterized in that:
A) percentage composition of described magnesium alloy quality is that Al is 0.8%, and Zn is 1.0%; Mishmetal RE is 0.5%, and Mn is 0.4%, and surplus is Mg and unavoidable impurities;
B) percentage composition of described magnesium alloy quality is: Al is 0.9%, and Zn is 1.0%, and rare earth RE mass percent is 0.6%, and Mn 0.4%;
C) percentage composition of described magnesium alloy quality is: Al is 0.9%, and Zn is 1.0%, and rare earth RE mass percent is 0.5%, and Mn 0.4%;
D) percentage composition of described magnesium alloy quality is: Al is 1.2%, and Zn is 1.2%, and rare earth RE mass percent is 0.8%, and Mn 0.4%;
E) percentage composition of described magnesium alloy quality is: Al is 0.8%, and Zn is 0.8%, and rare earth RE mass percent is 0.4%, and Mn 0.4%.
4. by claim 1 or 2 described magnesium alloy, it is characterized in that Al and mixed rare-earth elements RE play the second-phase dispersion strengthening effect in the described magnesium alloy.
5. application rights requires 1 or 3 described magnesium alloy, it is characterized in that being applicable to intravascular stent, satisfies six requirements of degraded mutually.
6. by the described application of claim 5, it is characterized in that the support that provides expands state for pressing the state of holding or ball.
7. by claim 5 or 6 described application, it is characterized in that the support radial support power that is provided far surpasses the 40Kpa of index indicated weight, support fracture do not occur after diffusion is again held in overvoltage, reply former state.
8. by claim 5 or 6 described application, the support that it is characterized in that being provided keeps continuously through quickening 10 times of artificial blood plasma spurt, and the artificial blood plasma that can stand 10 months washes away.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108543118A (en) * | 2018-05-21 | 2018-09-18 | 申英末 | The magnesium alloy fixing screws of internal controlled degradation |
| CN108714252A (en) * | 2018-05-21 | 2018-10-30 | 申英末 | The preparation method of the magnesium alloy fixing screws of internal controlled degradation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062427A (en) * | 2006-04-29 | 2007-10-31 | 中国科学院金属研究所 | Medical corrosion-resisting type magnesium alloy |
| CN101085377A (en) * | 2007-06-11 | 2007-12-12 | 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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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101062427A (en) * | 2006-04-29 | 2007-10-31 | 中国科学院金属研究所 | Medical corrosion-resisting type magnesium alloy |
| CN101085377A (en) * | 2007-06-11 | 2007-12-12 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 《材料导报》 20071231 高家诚等 医用Mg-RE合金血管内支架的研究进展 132-135 1-8 第21卷, 第5A期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108543118A (en) * | 2018-05-21 | 2018-09-18 | 申英末 | The magnesium alloy fixing screws of internal controlled degradation |
| CN108714252A (en) * | 2018-05-21 | 2018-10-30 | 申英末 | The preparation method of the magnesium alloy fixing screws of internal controlled degradation |
| 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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| CN102181759B (en) | 2014-06-25 |
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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. |