CN102652840A - Medical biology degradable magnesium alloy composite material - Google Patents
Medical biology degradable magnesium alloy composite material Download PDFInfo
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- CN102652840A CN102652840A CN2011100492765A CN201110049276A CN102652840A CN 102652840 A CN102652840 A CN 102652840A CN 2011100492765 A CN2011100492765 A CN 2011100492765A CN 201110049276 A CN201110049276 A CN 201110049276A CN 102652840 A CN102652840 A CN 102652840A
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Abstract
The invention relates to a novel degradable medical magnesium alloy composite material. The medical magnesium alloy composite material provided by the invention has the characteristics of high strength, good temperature memory and controllable degradation velocity and can be used in the field of orthopedic implantation. The composite material is characterized in that the composite material contains Mg-Al-Zn magnesium alloys, wherein the content of Al is 0.5-3.5wt% and the content of Zn is 0.5-1.8wt%; besides, the magnesium alloy material can contain a few impurities including Fe, Mn, Cu and Ni, wherein the total of the impurities is not greater than 0.3wt%; and a medical biology degradable material exists on the surface layer of the composite material and can be a pure carbon dioxide copolymer, pure polyhydroxyalkanoate or a blend of the carbon dioxide copolymer and polyhydroxyalkanoate, which has to be medically purified before use.
Description
Technical field:
The present invention relates to a kind of medical bio degradable magnesium alloy composite, its inside is the medical magnesium alloy material, and surface layer is the medical bio degradation material.Combine through coating or Shooting Technique.
Technical background:
Magnesium alloy has the specific strength height; Density is hanged down characteristics such as reaching good biocompatibility; As biomaterial for medical purpose very big potentiality are arranged, the relatively poor corrosion resistance of magnesium alloy has limited it in other extensive applications, but for can in human body, having created new purposes by the bio-medical material of safe disposal.Behind magnesium alloy medical device implant into body, this implantation equipment can be degraded until disappearance along with the healing of wounded tissue gradually.Corrosion rate is too fast but existing magnesium alloy is degraded in human body, needs further control.How to control magnesium alloy at the intravital degradation speed of people, become the research focus.
In human body pendular ring border, magnesium is that people's in-vivo content is only second to cation in the cell of potassium, in human body in the numerous metal ion; The content of magnesium elements comes the 4th, mainly is distributed in the cell, participates in a series of cell metabolism procedures; Comprise the formation of osteocyte, the accelerated bone healing.Magnesium is to muscle in the human body, nerve, and heart has important role.Magnesium can reduce resistance of blood flow in the blood vessel, reduces hematoblastic gathering, improves heart metabolism and the mortality rate that reduces acute myocardial infarction.Therefore play an important role for angiocardiopathy preventing and sudden death.Therefore the Mg supplementation element has caused enough attention in clinical medicine, in preventing and curing diseases and keeping healthy, has important function, and the magnesium intake of nutritionist suggestion is 300-350mg/ day.It is thus clear that magnesium has good medical science safety basis as bio-medical material.And magnesium resource is contained abundant, and reserves are 2.37% in the earth's crust.Low (the 1.74g/cm of the density of magnesium
3) and people's bone density (1.5g/cm
3) approaching; The Young's modulus of magnesium is 45GPa, more near people's flexible bone modulus 20GPa: therefore can effectively alleviate the effect that the human body internal stress is blocked.The above-mentioned characteristic of magnesium and magnesium alloy provides wide space for it as biomaterial for medical purpose.Therefore, magnesium and magnesium alloy are as biomaterial, and the trace of the magnesium ion in the implant discharges not only to human body inanimate object toxicity, and be still useful.
Although magnesium and magnesium alloy have above-mentioned advantage; But it is used as biomaterial and receives restriction significantly; Main cause is that the chemical property of magnesium is extremely active; Oxide-film in that the corrosive medium invading the exterior is looked unfamiliar is loose porous, can not good protective effect be arranged to matrix, also is accompanied by a large amount of hydrogen in the corrosion process and generates.Especially in containing the corrosive medium of chloride ion, the integrity of mgo surface film can be destroyed, and causes the corrosion aggravation.
The achievement in research of implanting the field about the medical degradable material at orthopaedics at present has a lot; A large amount of documents and materials and patent have also been produced; But they all have the problem of a general character; Use magnesium alloy materials can't solve the too fast problem of degradation speed separately, and use the medical bio macromolecular material can't solve the problem of undercapacity separately.So develop a kind of existing very high specific strength, good biocompatibility, and the medical bio magnesium alloy materials of may command degraded again becomes a new field.
Summary of the invention:
The present invention provides a kind of novel degradable medical magnesium alloy composite.
Medical magnesium alloy composite provided by the invention has intensity height, temperature memory property is good, degradation speed is controlled characteristics.
Described novel degradable composite material of magnesium alloy can be used for orthopaedics and implant the field.Composite inner is the Mg-Al-Zn series magnesium alloy; Wherein Al content is 0.5-3.5% (percentage by weight); Zn content is 0.5%-1.8% (percentage by weight), in addition, can contain small amount of impurities in this magnesium alloy materials; Comprise Fe, Mn, Cu, Ni etc., total impurities is not more than 0.3% (percentage by weight); Composite surface layer is the medical bio degradation material, and this material can be simple carbon dioxide copolymer, PHA, and perhaps the blend of the two must carry out medical purification before using.
Described magnesium alloy materials can (by patent " semi-solid-state injection molding method of magnesium alloy and device " (patent No.: the equipment of mentioning ZL200610016645.X) is accomplished), gaining in strength solves the even problem of magnesium alloy materials density unevenness through the semi-solid-state injection molding method preparation.The thickness of the medical bio degradation material of surface layer is 0.001mm～1mm.The surface applied compound capable of using or the injection molded technology of two kinds of materials are accomplished.
Advantage of the present invention and beneficial effect are:
(1) utilize the magnesium alloy semi solid state injection molding equipment can prepare goods in the difform body, and the thickness of surface biological degradable material capable of using is controlled goods degradation time in vivo;
(2) utilize the good Memorability of medical carbon dioxide copolymer material to temperature, temperature is adjusted to human body temperature and is equated, keeps the equipment surface soft durometer of implant into body similar with tissue, reduces tissue injury, is beneficial to the healing of wounded tissue.
(3) the blend ratio of carbon dioxide copolymer and PHA in the composite skin capable of using is controlled goods degradation time in vivo;
(4) because internal layer adopts magnesium alloy materials, can solve simple with the problem of macromolecular material as vivo degradation strength of materials difference;
(5) adopt semi-solid-state injection molding method to prepare the magnesium alloy materials of internal layer; Compare with other Mg alloy formed method; The product of this manufacturing process preparation has that low, the near clean shape property of the porosity, intensity are higher, the characteristics of excellent corrosion, can prolong the degradable time of magnesium alloy relatively;
Specific embodiment:
At first prepare a long 30mm, wide 4mm, thickness are the magnesium alloy batten of 1mm; Each makes a call to the hole of a diameter 2mm two ends, is prepared into the shape of blade plate, and the biodegradable carbon dioxide copolymer after will purifying then dissolves with DMC dimethyl carbonate; Be mixed with solution, use spray gun that it is sprayed on the blade plate surface, it is dry to put into baking oven; Testing coating thickness is about 0.02mm, and the thigh bone place that prepared sample is implanted animal is observed, and basic in 6 months time do not have to change; Main degradation process began in 12 months, the completion of degrading basically of the individual month magnesium alloy materials of about 2-3, still surplus a spot of carbon dioxide copolymer material.
Claims (6)
1. a medical bio degradable magnesium alloy composite is characterized in that surface layer is a medical biodegradable material, and inside is the medical magnesium alloy material.
2. according to the described composite of claim 1, it is characterized in that the medical bio degradation material comprises one or both blend of carbon dioxide copolymer and PHA.
3. according to the described composite of claim 1; It is characterized in that inner magnesium alloy materials is the Mg-Al-Zn series magnesium alloy, wherein: Al content is 0.5-3.5% (percentage by weight), and Zn content is 0.5%-1.8% (percentage by weight); In addition; Can contain small amount of impurities in this magnesium alloy materials, comprise Fe, Mn, Cu, Ni etc., total impurities is not more than 0.3% (percentage by weight).
4. according to the described composite of claim 1, it is characterized in that the preparation of medical magnesium alloy material is accomplished by the equipment of " semi-solid-state injection molding method of magnesium alloy and device, the patent No.: ZL 200610016645.X ".
5. according to the described composite of claim 1, the thickness that it is characterized in that surface layer medical bio degradation material is between the 0.001mm-1mm.
6. according to the described composite of claim 1, it is characterized in that surface layer medical degradable material combines with inner through dual mode, applies or Shooting Technique.
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| CN2011100492765A CN102652840A (en) | 2011-03-02 | 2011-03-02 | Medical biology degradable magnesium alloy composite material |
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| CN2011100492765A CN102652840A (en) | 2011-03-02 | 2011-03-02 | Medical biology degradable magnesium alloy composite material |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103263697A (en) * | 2013-06-08 | 2013-08-28 | 吉林金源北方科技发展有限公司 | All-biological controllable and degradable bone nail and using method thereof |
| CN103272285A (en) * | 2013-05-24 | 2013-09-04 | 华南理工大学 | All-degradable biological material and preparation method thereof |
| CN103993187A (en) * | 2014-05-21 | 2014-08-20 | 太原理工大学 | Preparation method of medical degradable magnesium-bismuth alloy plate |
| CN104069542A (en) * | 2013-03-26 | 2014-10-01 | 深圳先进技术研究院 | Patella tissue engineering scaffold, and manufacturing material 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 |
| CN105381508A (en) * | 2015-12-28 | 2016-03-09 | 青岛博泰美联化工技术有限公司 | Endovascular stent and preparation method |
| CN105435302A (en) * | 2015-12-28 | 2016-03-30 | 青岛博泰美联化工技术有限公司 | Bone filling material and preparation method thereof |
| CN105603277A (en) * | 2015-12-28 | 2016-05-25 | 青岛博泰美联化工技术有限公司 | Easily-degraded medical magnesium-alloy material and preparation method thereof |
| CN105624496A (en) * | 2015-12-28 | 2016-06-01 | 青岛博泰美联化工技术有限公司 | Bone nail and preparation method |
| CN105624495A (en) * | 2015-12-28 | 2016-06-01 | 青岛博泰美联化工技术有限公司 | Medical suture material and preparation method |
| CN105828742A (en) * | 2013-11-21 | 2016-08-03 | 托莱多大学 | Macroporous granules of alkaline earth phosphates using cement technology and gas evolving porogen |
| TWI568459B (en) * | 2016-11-10 | 2017-02-01 | 呂傳盛 | Method of manufacturing magnesium alloy implant material with selective-stage biodegradation |
| CN107227422A (en) * | 2016-03-25 | 2017-10-03 | 武汉理工大学 | A kind of high intensity saline soluble magnesium alloy materials and preparation method thereof |
| CN111961937A (en) * | 2020-09-11 | 2020-11-20 | 河海大学 | Magnesium-based alloy wire with controllable degradation and preparation method thereof |
| CN114807708A (en) * | 2022-05-26 | 2022-07-29 | 长沙理工大学 | Medical composite magnesium alloy and preparation method thereof |
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| CN104069542A (en) * | 2013-03-26 | 2014-10-01 | 深圳先进技术研究院 | Patella tissue engineering scaffold, and manufacturing material and preparation method thereof |
| CN104069542B (en) * | 2013-03-26 | 2017-12-29 | 深圳先进技术研究院 | Kneecap tissue engineering bracket and its manufacture material and preparation method |
| CN103272285A (en) * | 2013-05-24 | 2013-09-04 | 华南理工大学 | All-degradable biological material and preparation method thereof |
| CN103272285B (en) * | 2013-05-24 | 2014-12-03 | 华南理工大学 | All-degradable biological material and preparation method thereof |
| CN103263697A (en) * | 2013-06-08 | 2013-08-28 | 吉林金源北方科技发展有限公司 | All-biological controllable and degradable bone nail and using 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 |
| CN105828742A (en) * | 2013-11-21 | 2016-08-03 | 托莱多大学 | Macroporous granules of alkaline earth phosphates using cement technology and gas evolving porogen |
| CN103993187A (en) * | 2014-05-21 | 2014-08-20 | 太原理工大学 | Preparation method of medical degradable magnesium-bismuth alloy plate |
| CN105603277A (en) * | 2015-12-28 | 2016-05-25 | 青岛博泰美联化工技术有限公司 | Easily-degraded medical magnesium-alloy material and preparation method thereof |
| CN105624496A (en) * | 2015-12-28 | 2016-06-01 | 青岛博泰美联化工技术有限公司 | Bone nail and preparation method |
| CN105624495A (en) * | 2015-12-28 | 2016-06-01 | 青岛博泰美联化工技术有限公司 | Medical suture material and preparation method |
| CN105435302A (en) * | 2015-12-28 | 2016-03-30 | 青岛博泰美联化工技术有限公司 | Bone filling material and preparation method thereof |
| CN105381508A (en) * | 2015-12-28 | 2016-03-09 | 青岛博泰美联化工技术有限公司 | Endovascular stent and preparation method |
| CN107227422A (en) * | 2016-03-25 | 2017-10-03 | 武汉理工大学 | A kind of high intensity saline soluble magnesium alloy materials and preparation method thereof |
| TWI568459B (en) * | 2016-11-10 | 2017-02-01 | 呂傳盛 | Method of manufacturing magnesium alloy implant material with selective-stage biodegradation |
| CN111961937A (en) * | 2020-09-11 | 2020-11-20 | 河海大学 | Magnesium-based alloy wire with controllable degradation and preparation method thereof |
| CN114807708A (en) * | 2022-05-26 | 2022-07-29 | 长沙理工大学 | Medical composite magnesium alloy and preparation method thereof |
| CN114807708B (en) * | 2022-05-26 | 2022-10-28 | 长沙理工大学 | Medical composite magnesium alloy and preparation method thereof |
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Application publication date: 20120905 |