CN100372574C - Multi-elements magnesium alloy contg. Mg-Zn-Ca-Fe of bio-absorbable type - Google Patents
Multi-elements magnesium alloy contg. Mg-Zn-Ca-Fe of bio-absorbable type Download PDFInfo
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- CN100372574C CN100372574C CNB2005101117920A CN200510111792A CN100372574C CN 100372574 C CN100372574 C CN 100372574C CN B2005101117920 A CNB2005101117920 A CN B2005101117920A CN 200510111792 A CN200510111792 A CN 200510111792A CN 100372574 C CN100372574 C CN 100372574C
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Abstract
The present invention relates to bio-absorbable Mg-Zn-Ca-Fe multi-element magnesium alloy materials, which belongs to the technical field of biologic medical materials. The present invention comprises the components of the percentage by weight: 1 to 8% of Zn, 0.1 to 2% of CaO, 0.1 to 2% of Fe, and Mg as the rest. The Mg-Zn-Ca-Fe multi-element magnesium alloy materials of the present invention are made of high-purity raw materials by a high-cleanliness smelting technology. The present invention is a multi-element magnesium alloy system prepared from full nutritive elements such as Mg, Zn, Ca and Fe. Zn is used as a significant alloying element in Mg to form MgZn phases, the strength of magnesium is increased, and the corrosion performance of magnesium is improved. Ca has a grain refining function, and thereby, the strength, the degradability, etc. of magnesium are increased. Fe has important influence on changing corrosion-resisting property, etc. The present invention has favorable biocompatibility and favorable mechanical property bases, and can satisfy the requirements of comprehensive mechanical property and biology safety for materials in the technical field of the medical application of endovascular stents, bone pegs, bone lamellas, etc.
Description
Technical field
What the present invention relates to is a kind of complex magnesium alloy of biomedical materials field, specifically, is a kind of organism absorbable Mg-Zn-Ca-Fe complex magnesium alloy material.
Background technology
Biological degradable in vivo absorbing material is one of important directions of biomaterial development, and the biological degradable in vivo absorbing material of research and development mainly is polymeric material and some ceramic material at present, as polylactic acid, polycaprolactone, calcium phosphate etc.But because the common plasticity and toughness lower, ceramic material of the mechanical property of polymeric material are relatively poor, metal material then has better comprehensive mechanical property, and therefore, the biological degradable in vivo absorbing material of Metal Substrate has important medical applications and is worth.Magnesium is one of the abundantest element of reserves on the earth, also is second cation the abundantest in the 4th, cell in the human body, is indispensable important nutrient in the human body, and total amount about more than 20 restrains in human body.Magnesium promotes the formation of bone and cell in life process, catalysis or activation body 300 plurality of enzymes system participate in the energy i (in vivo) metabolism, and are crucial elements in conveying, storage and the utilization of energy.Magnesium plays a crucial role to proteinic synthesizing by the structure of regulating rDNA and RNA in the three big metabolism in vivo.The balance adjustment of magnesium is finished by intestinal absorption and renal excretion in the human body.Magnesium has important function to nerve, muscle and the cardiac function of human body, and magnesium deficiency is one of etiology factor of some severe arrhythmia, ischemic heart desease, hypertension, particularly arteriosclerosis, myocardial infarction, sudden death.Magnesium has good medical science safety basis as bio-medical material, is particularly useful in the treatment of cardiovascular disease.
Find through literature search prior art, people such as B.Heublein in " Heart " (heart) magazine 2003 89 volume 651-656 page or leaf, reported " Biocorrosion of Magnesium Alloys:A NewPrinciple in Cardiovascular Implant Technology? " (corrosion biology of magnesium alloy: a kind of new principle of cardiovascular implanted prosthetics?), they are by animal (pig) experimentation AE21 magnesium alloy (Mg-2%Al-1%Re, its middle rare earth Re comprises Ce, Pr, the Nd element) is used as the feasibility of the support of cardiovascular interventional therapy, the biocompatibility that found that magnesium alloy is good, do not produce problems such as thromboembolism behind the implantable intravascular, have good application potential.Contain Al element and rare earth element in the magnesium alloy of studying in the document, though the biocompatibility of magnesium basis is good, but the Al element does not belong to the essential trace element of human body, be considered to have neurotoxicity, it is the factor that causes presenile dementia, and also there is dispute in the biocompatibility of rare earth element, it is generally acknowledged that rare earth element accumulation in vivo will show as toxic action.And existing Mg-Zn and Mg-Zn-Ca-Fe complex magnesium alloy material thereof all are to be applied in the general industry, do not find the complex magnesium alloy material of Mg-Zn base is applied to the report of bio-medical material so far as yet.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of organism absorbable Mg-Zn-Ca-Fe complex magnesium alloy material is provided, make it, overcome technology prejudice as bio-medical material.The present invention utilizes the chemical reaction of magnesium in aqueous medium to change magnesium ion into, and magnesium ion comes adjustment by the metabolism of intravital absorption and kidney, thereby magnesium alloy materials is degraded and absorbed in vivo gradually.Material of the present invention has excellent biological compatibility and mechanical property, has important use at medical domains such as the support of vascular interventional treatment and absorbable nail, hone lamellas and is worth.
The present invention is achieved by the following technical solutions, and each component of the present invention and percentage by weight are: Zn
1-8%, Ca0.1-2%, Fe0.1-2%, surplus is Mg.
For obtain best comprehensive mechanical property and biology corrosive nature, weight percentage ranges further is Zn5.5 ± 0.5%, Ca0.4 ± 0.1%, Fe0.2 ± 0.1%, surplus is Mg.In this scope, Tensile strength of the present invention reaches 300MPa, and plasticity is maintained at about 8%, and the excellent combination of this intensity and plasticity can guarantee the requirement to the strength of materials of the Deformation Properties of Al of material and medical applications.Simultaneously, its corrosive nature biology in biological fluid or blood environment is good, by its absorbed speed of scalable such as composition, ion concentration and pH value in control body fluid or the blood environment, thus when satisfying treatment to the requirement of mechanical property retention time of medical apparatus and instruments.
Mg-Zn-Ca-Fe complex magnesium alloy material of the present invention must adopt the melting technique of highly purified raw material and high-cleanness, high to make.The degree of purity of raw material Mg is more than or equal to 99.99%, and the degree of purity of Zn is more than or equal to 99.999%, and the degree of purity of Ca is more than or equal to 99.75%, and the degree of purity of Fe is more than or equal to 99.9%.High clean melting need be adopted the noble gas argon shield, adopts special-purpose graphite or titanium crucible for smelting, and smelting temperature is poured into a mould ingot casting then at about 750 ℃ in a kind of iron mould of special use.Ingot casting is made required section bar again after heat treatment and deformation processing, make the various medical apparatus and instruments that implant from section bar and use.
The complex magnesium alloy system that the present invention is made up of full nutritive element Mg, Zn, Ca, Fe.Zn can form the MgZn phase as alloying element important among the Mg, not only improves the intensity of magnesium, also improves the corrosive nature of magnesium.Ca has the effect of crystal grain thinning, thus the intensity of raising magnesium and plasticity etc.Fe has material impact to changing decay resistance etc.Simultaneously, Zn is the element that cell growth is grown material impact, and Ca is the main component of bone, and Fe has material impact to blood function etc.Mg, Zn, Ca, Fe are the necessary nutrients of human body, therefore, the alloy system of being made up of them has excellent biological compatibility and mechanical property basis, can satisfy the requirement of medical application fields such as endovascular stent, nail, hone lamella to material comprehensive mechanical property and biological safe preferably.
The specific embodiment
Embodiment 1
Polynary Mg-Zn-Ca-Fe alloy material, wherein wt percentage ratio Zn is 1%, and Ca is 0.1%, and Fe is 0.1%.The degree of purity of raw material Mg is more than or equal to 99.99%, and the degree of purity of Zn is more than or equal to 99.999%, and the degree of purity of Ca is more than or equal to 99.75%, and the degree of purity of Fe is more than or equal to 99.9%.After high-cleanness, high melting under argon shield and casting, after Overheating Treatment and deformation processing, make bar or tubing again.This material has excellent biological compatibility and mechanical property, and its tensile strength is 210MPa, and plasticity is 12%, can be in biological fluid or blood environment degraded and absorbed.
Embodiment 2
Polynary Mg-Zn-Ca-Fe alloy material, wherein wt percentage ratio Zn is 5.5%, and Ca is 0.4%, and Fe is 0.2%.The degree of purity of raw material Mg is more than or equal to 99.99%, and the degree of purity of Zn is more than or equal to 99.999%, and the degree of purity of Ca is more than or equal to 99.75%, and the degree of purity of Fe is more than or equal to 99.9%.After high-cleanness, high melting under argon shield and casting, after Overheating Treatment and deformation processing, make bar or tubing again.This material has excellent biological compatibility and mechanical property, and its tensile strength is 300MPa, and plasticity is 8%, can be in biological fluid or blood environment degraded and absorbed.
Embodiment 3
Polynary Mg-Zn-Ca-Fe alloy material, wherein wt percentage ratio Zn is 8%, and Ca is 2%, and Fe is 2%.The degree of purity of raw material Mg is more than or equal to 99.99%, and the degree of purity of Zn is more than or equal to 99.999%, and the degree of purity of Ca is more than or equal to 99.75%, and the degree of purity of Fe is more than or equal to 99.9%.After high-cleanness, high melting under argon shield and casting, after Overheating Treatment and deformation processing, make bar or tubing again.This material has excellent biological compatibility and mechanical property, and its tensile strength is 240MPa, and plasticity is 2%, can be in biological fluid or blood environment degraded and absorbed.
Claims (6)
1. organism absorbable Mg-Zn-Ca-Fe complex magnesium alloy material is characterized in that each component and percentage by weight are: Zn 1-8%, and Ca 0.1-2%, Fe 0.1-2%, surplus is Mg.
2. organism absorbable Mg-Zn-Ca-Fe complex magnesium alloy material according to claim 1, it is characterized in that each component and percentage by weight are: Zn 5.5 ± 0.5%, and Ca 0.4 ± 0.1%, and Fe 0.2 ± 0.1%, and surplus is Mg
3. according to claim 1 or 2 described organism absorbable Mg-Zn-Ca-Fe complex magnesium alloy materials, it is characterized in that the degree of purity of Mg is more than or equal to 99.99%.
4. according to claim 1 or 2 described organism absorbable Mg-Zn-Ca-Fe complex magnesium alloy materials, it is characterized in that the degree of purity of Zn is more than or equal to 99.999%.
5. according to claim 1 or 2 described organism absorbable Mg-Zn-Ca-Fe complex magnesium alloy materials, it is characterized in that the degree of purity of Ca is more than or equal to 99.75%.
6. organism absorbable Mg-Zn-Ca-Fe complex magnesium alloy material according to claim 1 is characterized in that the degree of purity of Fe is more than or equal to 99.9%.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2010503509A (en) * | 2006-09-22 | 2010-02-04 | ユー アンド アイ コーポレーション | Implant containing biodegradable metal and method for producing the same |
| AT508309A1 (en) * | 2009-05-19 | 2010-12-15 | Arc Leichtmetallkompetenzzentrum Ranshofen Gmbh | METHOD FOR PRODUCING A THIN-WALLED TUBE FROM A MAGNESIUM ALLOY |
| CN101658691B (en) * | 2009-07-31 | 2013-03-13 | 哈尔滨工业大学 | Method for plastically manufacturing high-purity magnesium alloy absorbable stent |
| CN101690676B (en) * | 2009-10-26 | 2011-03-23 | 上海交通大学 | Absorbable metal intramedullary nail and preparation method thereof |
| CN102294054B (en) * | 2010-06-24 | 2014-04-09 | 乐普（北京）医疗器械股份有限公司 | Bioabsorbable compound stent and preparation method thereof |
| CN102876958B (en) * | 2012-10-30 | 2014-07-16 | 重庆大学 | High-strength and high-ductility Mg-Zn-Ca/Fe particle composite material |
| CN104689369B (en) * | 2015-03-13 | 2017-06-30 | 西安爱德万思医疗科技有限公司 | A kind of tough Zn-Fe systems kirsite of the degradable corrosion-proof and high-strength of human body and its application |
| CN104689378B (en) * | 2015-03-13 | 2017-04-05 | 西安爱德万思医疗科技有限公司 | A kind of tough Zn-Fe-X systems kirsite of the degradable corrosion-proof and high-strength of human body and its application |
| CN111228577A (en) * | 2020-01-15 | 2020-06-05 | 太原科技大学 | Medical magnesium alloy capable of being degraded in short term and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1494440A (en) * | 2001-03-05 | 2004-05-05 | Composition of porous element for biomaterial | |
| CN1519387A (en) * | 2003-01-20 | 2004-08-11 | 中国科学院金属研究所 | Embedded material of austenitic stainless steel in medical use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1494440A (en) * | 2001-03-05 | 2004-05-05 | Composition of porous element for biomaterial | |
| CN1519387A (en) * | 2003-01-20 | 2004-08-11 | 中国科学院金属研究所 | Embedded material of austenitic stainless steel in medical use |
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