CN102978495A - Mg-Sr-Zn alloy and preparation method thereof - Google Patents
Mg-Sr-Zn alloy and preparation method thereof Download PDFInfo
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Abstract
本发明公开了一种Mg-Sr-Zn系合金及其制备方法。所述合金包括Mg、Sr和Zn;以重量百分比计,所述医用植入体中,Sr的含量为0~5%,但不为零,Zn的含量为0~2%,但不为零,余量为Mg。将所述Mg、Sr、Zn和微量元素按照下述1)~2)中任一种方式进行混合得到混合物:1)Mg、Sr和Zn;和2)Mg、Sr、Zn和微量元素;在CO2和SF6气氛保护下,将所述混合物进行熔炼,即得到所述合金。本发明的可降解吸收Mg-Sr-Zn系镁合金,选用人体必需金属元素,不含有害或潜在有害元素,其中的合金化元素Sr可促进成骨,抑制骨吸收,从而伴随Mg-Sr-Zn系合金降解促进组织愈合。The invention discloses a Mg-Sr-Zn alloy and a preparation method thereof. The alloy includes Mg, Sr and Zn; by weight percentage, in the medical implant, the content of Sr is 0-5%, but not zero, and the content of Zn is 0-2%, but not zero , the balance being Mg. Mix the Mg, Sr, Zn and trace elements according to any of the following 1) to 2) to obtain a mixture: 1) Mg, Sr and Zn; and 2) Mg, Sr, Zn and trace elements; in Under the protection of CO 2 and SF 6 atmosphere, the mixture is melted to obtain the alloy. The degradable and absorbable Mg-Sr-Zn series magnesium alloy of the present invention uses essential metal elements for the human body and does not contain harmful or potentially harmful elements. The alloying element Sr in it can promote bone formation and inhibit bone resorption, thereby accompanying Mg-Sr- Degradation of Zn-based alloys promotes tissue healing.
Description
技术领域technical field
本发明涉及一种Mg-Sr-Zn系合金及其制备方法,属于医用金属材料领域。The invention relates to a Mg-Sr-Zn alloy and a preparation method thereof, belonging to the field of medical metal materials.
背景技术Background technique
目前医用生物可降解材料主要为可降解高分子材料和可降解陶瓷材料。可降解高分子材料包括聚羟基乙酸(PGA)、聚乳酸(PLA)、聚乙酸内酯(PCL)及其共聚物、天然多糖类材料(纤维素、甲壳素)和天然蛋白质材料(胶原、纤维蛋白)等,虽然这种材料能够完全被人体吸收,但其强度低,很难提供结构支撑的功能,且其体内降解产物易引发炎症反应等问题。可降解陶瓷材料包括羟基磷灰石、α-磷酸三钙、β-磷酸三钙和磷酸氧四钙,但是这种材料的韧性差,无法协调变形。At present, medical biodegradable materials are mainly degradable polymer materials and degradable ceramic materials. Degradable polymer materials include polyglycolic acid (PGA), polylactic acid (PLA), polylactone (PCL) and their copolymers, natural polysaccharide materials (cellulose, chitin) and natural protein materials (collagen, Fibrin), etc., although this material can be completely absorbed by the human body, its strength is low, it is difficult to provide structural support, and its degradation products in the body can easily cause inflammatory reactions and other problems. Degradable ceramic materials include hydroxyapatite, α-tricalcium phosphate, β-tricalcium phosphate, and tetracalcium oxyphosphate, but this material has poor toughness and cannot coordinate deformation.
生物医用金属材料因其优良的力学性能、生物相容性和耐腐蚀性,在医疗器械领域广泛使用。目前生物医用金属材料主要为316L、317L、304V不锈钢、Co-Cr-Mo合金、纯钛、Ti-6Al-4V、TiNi合金等,其主要缺点是不可降解,在体内将永久性以“异体”形式存在。同时,不锈钢、Co-Cr-Mo合金和钛合金的力学性能尤其是弹性模量与骨组织不匹配,如不锈钢的弹性模量约为200GPa,钛合金约为100GPa,而骨组织的弹性模量只有10-40GPa,因此导致金属植入体植入后将承载几乎全部载荷,造成骨组织的应力遮挡现象,即植入体周围骨组织萎缩或疏松。Biomedical metal materials are widely used in the field of medical devices due to their excellent mechanical properties, biocompatibility and corrosion resistance. At present, biomedical metal materials are mainly 316L, 317L, 304V stainless steel, Co-Cr-Mo alloy, pure titanium, Ti-6Al-4V, TiNi alloy, etc. The main disadvantage is that it is not degradable, and it will be permanently "alien" in the body. form exists. At the same time, the mechanical properties of stainless steel, Co-Cr-Mo alloy and titanium alloy, especially the elastic modulus, do not match the bone tissue. For example, the elastic modulus of stainless steel is about 200GPa, and that of titanium alloy is about 100GPa. Only 10-40GPa, so the metal implant will bear almost all the load after implantation, causing the stress shielding phenomenon of bone tissue, that is, the bone tissue around the implant shrinks or loosens.
发明内容Contents of the invention
本发明的目的是提供一种Mg-Sr-Zn系合金及其制备方法,本发明提供的医用植入体为一种可降解吸收、力学性能与骨组织匹配、生物相容性与耐腐蚀性能良好的可降解吸收性Mg-Sr-Zn系合金医用植入体。The purpose of the present invention is to provide a Mg-Sr-Zn alloy and its preparation method. The medical implant provided by the present invention is a biodegradable, absorbable, mechanically compatible with bone tissue, biocompatible and corrosion resistant. Good degradable and absorbable Mg-Sr-Zn alloy medical implant.
本发明所提供的一种Mg-Sr-Zn系合金,包括Mg、Sr和Zn;A Mg-Sr-Zn alloy provided by the present invention includes Mg, Sr and Zn;
以重量百分比计,所述合金中,Sr的含量为0~5%,但不为零,Zn的含量为0~2%,但不为零,本发明提供的合金可为致密结构或多孔结构。In terms of weight percentage, in the alloy, the content of Sr is 0-5%, but not zero, and the content of Zn is 0-2%, but not zero. The alloy provided by the present invention can be dense structure or porous structure .
上述的合金中,所述合金还包括微量元素,所述微量元素具体可为锰、锆、锡、稀土和钇中至少一种;In the above alloy, the alloy further includes trace elements, and the trace elements may specifically be at least one of manganese, zirconium, tin, rare earth and yttrium;
所述合金中中,所述微量元素的质量百分含量可为0~2%,但不为零。In the alloy, the mass percentage of the trace elements may be 0-2%, but not zero.
上述的合金中,所述合金中,锰的质量百分含量不大于1.5%,锆的质量百分含量不大于1%,锡的质量百分含量不大于2%,稀土的质量百分含量不大于2%,以及钇的质量百分含量不大于1%。In the above alloy, in the alloy, the mass percentage of manganese is not more than 1.5%, the mass percentage of zirconium is not more than 1%, the mass percentage of tin is not more than 2%, and the mass percentage of rare earth is not more than 1.5%. More than 2%, and the mass percentage of yttrium is not more than 1%.
上述的合金中,所述合金的表面还涂覆可降解高分子涂层或可降解陶瓷涂层。In the above alloy, the surface of the alloy is further coated with a degradable polymer coating or a degradable ceramic coating.
上述的合金中的具体组成如下:由Mg、Sr和Zn组成,Sr的质量百分含量为2%~5%、Zn的质量百分含量为1%~2%和余量的Mg,具体可为97%的Mg、2%的Sr和1%的Zn或93%的Mg、5%的Sr和2%的Zn;由Mg、Sr、Zn和Sn组成,如95%的Mg、3%的Sr、1.5%的Zn和0.5%的Sn。The concrete composition in above-mentioned alloy is as follows: be made up of Mg, Sr and Zn, the mass percentage composition of Sr is 2% ~ 5%, the mass percentage composition of Zn is 1% ~ 2% and the Mg of balance, specifically can be 97% Mg, 2% Sr and 1% Zn or 93% Mg, 5% Sr and 2% Zn; composed of Mg, Sr, Zn and Sn, such as 95% Mg, 3% Sr, 1.5% Zn and 0.5% Sn.
上述的合金中,所述可降解高分子涂层可为聚羟基乙酸(PGA)、聚乳酸(PLA)、L-聚乳酸(PLLA)、聚己酸内酯(PCL)、聚氰基丙烯酸酯(PACA)、聚对二氧杂环己烷酮、聚酸酐、聚膦腈、氨基酸类聚合物、聚β-羟基丁酸酯和羟基戊酸酯或其共聚物中的一种或一种以上混合物;In the above alloys, the degradable polymer coating can be polyglycolic acid (PGA), polylactic acid (PLA), L-polylactic acid (PLLA), polycaprolactone (PCL), polycyanoacrylate One or more of (PACA), polydioxanone, polyanhydride, polyphosphazene, amino acid polymers, poly-β-hydroxybutyrate and hydroxyvalerate or their copolymers mixture;
所述可降解陶瓷涂层可为羟基磷灰石、含锶羟基磷灰石、含氟羟基磷灰石、α-磷酸三钙、β-磷酸三钙和磷酸氧四钙中的一种或一种以上混合物;The degradable ceramic coating can be one or one of hydroxyapatite, strontium-containing hydroxyapatite, fluorine-containing hydroxyapatite, α-tricalcium phosphate, β-tricalcium phosphate and oxytetracalcium phosphate more than one mixture;
所述可降解高分子涂层或可降解陶瓷涂层的厚度均可为0.01~5mm。The thickness of the degradable polymer coating or the degradable ceramic coating can be 0.01-5 mm.
本发明提供了上述的合金的制备方法,包括如下步骤:将所述Mg、Sr、Zn和微量元素按照下述1)~2)中任一种方式进行混合得到混合物:The present invention provides the above alloy preparation method, comprising the following steps: mixing the Mg, Sr, Zn and trace elements according to any one of the following 1) to 2) to obtain a mixture:
1)Mg、Sr和Zn;和1) Mg, Sr and Zn; and
2)Mg、Sr、Zn和微量元素;2) Mg, Sr, Zn and trace elements;
在CO2和SF6气氛保护下,将所述混合物进行熔炼,即得到所述合金,为致密结构。Under the protection of CO 2 and SF 6 atmosphere, the mixture is smelted to obtain the alloy with a dense structure.
上述的制备方法中,所述熔炼的温度可为700~850℃,所述熔炼的时间可为30min~4h,如在850℃下反应30min。In the above preparation method, the smelting temperature may be 700-850°C, and the smelting time may be 30min-4h, such as 30min at 850°C.
所述Sr可以Mg-Sr中间合金的形式进行添加。The Sr may be added in the form of a Mg-Sr master alloy.
上述的制备方法中,所述方法还包括将所述合金进行机械加工的步骤;所述机械加工为轧制、锻造、挤压和快速凝固中的一种或一种以上加工方法;In the above preparation method, the method further includes the step of machining the alloy; the machining is one or more of rolling, forging, extrusion and rapid solidification;
所述轧制包括如下步骤:将所述合金进行固溶处理,然后依次经粗轧、中轧和精轧;如在300~500℃下固溶处理2~20小时,然后在400~500℃进行粗轧,道次压下量为10~15%;在350~400℃进行中轧,道次压下量30~60%;在200~350℃进行精轧,道次压下量5~10%;The rolling includes the following steps: subjecting the alloy to solution treatment, and then sequentially undergoing rough rolling, intermediate rolling and finish rolling; for example, solution treatment at 300-500°C for 2-20 hours, and then at 400-500°C Rough rolling is carried out with a pass reduction of 10~15%; intermediate rolling is carried out at 350~400°C with a pass reduction of 30~60%; finish rolling is carried out at 200~350°C with a pass reduction of 5~ 10%;
所述锻造的温度可为200~400℃,锻造速率可为200mm/s~400mm/s,锻造率可为5%~15%;The forging temperature may be 200-400°C, the forging rate may be 200mm/s-400mm/s, and the forging rate may be 5%-15%;
所述挤压的温度可为200~400℃,如270℃,挤压速率可为0.1~50mm/min,如2mm/min,挤压比可为10~100,如25;The extrusion temperature may be 200-400°C, such as 270°C, the extrusion rate may be 0.1-50mm/min, such as 2mm/min, and the extrusion ratio may be 10-100, such as 25;
所述快速凝固是采用高真空快淬系统在Ar气保护下制成快速凝固薄带,其中加料量为2~8g,感应加热功率为3~7kW,喷嘴与辊间距为0.8mm,喷射压力为0.05~0.2MPa,辊轮转速为500~5000r/min,喷嘴狭缝尺寸为1film×8mm×6mm;然后将薄带破碎成粉末状,200~350℃真空热压为1~24h,制成Mg-Sr-Zn系合金挤压坯,然后于200~400℃范围内挤压,挤压比为10~60。The rapid solidification is made of a rapid solidification thin strip under the protection of Ar gas by using a high-vacuum rapid quenching system, wherein the feeding amount is 2-8g, the induction heating power is 3-7kW, the distance between the nozzle and the roller is 0.8mm, and the injection pressure is 0.05~0.2MPa, the speed of the roller is 500~5000r/min, the size of the nozzle slit is 1film×8mm×6mm; then the thin strip is crushed into powder, and vacuum hot pressed at 200~350℃ for 1~24h to make Mg -Sr-Zn series alloy extruded blank, then extruded in the range of 200~400℃, the extrusion ratio is 10~60.
本发明还提供了另一种上述的合金的制备方法,包括如下步骤:将所述Mg、Sr、Zn和微量元素按照下述1)~2)中任一种方式进行混合得到混合物:The present invention also provides another method for preparing the above-mentioned alloy, which includes the following steps: mixing the Mg, Sr, Zn and trace elements according to any of the following 1) to 2) to obtain a mixture:
1)Mg、Sr和Zn;和1) Mg, Sr and Zn; and
2)Mg、Sr、Zn和微量元素;2) Mg, Sr, Zn and trace elements;
将所述混合物进行烧结,然后经冷却即得到所述合金,即为多孔结构;Sintering the mixture, and then cooling to obtain the alloy, which is a porous structure;
所述烧结为下述任一种方法:元素粉末混合烧结法、预合金粉烧结法和自蔓延高温合成法。The sintering is any one of the following methods: element powder mixing sintering method, pre-alloy powder sintering method and self-propagating high-temperature synthesis method.
所述元素粉末混合烧结法包括如下步骤:在Ar气保护气氛的条件下进行烧结,以2~4℃/min的速率升温至200~500℃后,接着以30℃/min的速率升温至650℃,烧结1~12小时,然后炉冷降温,得到多孔结构的医用植入体。The element powder mixing sintering method includes the following steps: sintering under the condition of an Ar gas protective atmosphere, raising the temperature to 200-500°C at a rate of 2-4°C/min, and then raising the temperature to 650°C at a rate of 30°C/min. ℃, sintering for 1 to 12 hours, and then furnace cooling to obtain a medical implant with a porous structure.
所述预合金粉烧结法包括如下步骤:将所述混合物置于300~650℃的条件下进行热处理1~12小时,如在650℃的条件下热处理4小时得到多孔结构的合金。The pre-alloy powder sintering method includes the following steps: placing the mixture under the condition of 300-650° C. for heat treatment for 1-12 hours, such as heat-treating under the condition of 650° C. for 4 hours to obtain an alloy with a porous structure.
所述自蔓延高温合成法包括如下步骤:在惰性气体保护下,气体压力1×103-1×105Pa,200~700℃下点燃所述混合物进行自蔓延高温合成,得到多孔结构的合金。The self-propagating high-temperature synthesis method includes the following steps: under the protection of an inert gas, the gas pressure is 1×10 3 -1×10 5 Pa, and the mixture is ignited at 200-700° C. for self-propagating high-temperature synthesis to obtain an alloy with a porous structure .
上述的制备方法中,所述方法还包括向所述合金的表面涂覆所述可降解高分子涂层或可降解陶瓷涂层的步骤;In the above preparation method, the method further includes the step of coating the surface of the alloy with the degradable polymer coating or the degradable ceramic coating;
通过提拉法或匀胶法涂覆所述可降解高分子涂层;Coating the degradable polymer coating by pulling method or glue leveling method;
通过离子喷涂、电沉积或阳极氧化方法涂覆所述可降解陶瓷涂层;Coating the degradable ceramic coating by ion spraying, electrodeposition or anodic oxidation;
所述可降解高分子涂层和可降解陶瓷涂层的厚度可为5~50微米,如10~30微米。The thickness of the degradable polymer coating and the degradable ceramic coating may be 5-50 microns, such as 10-30 microns.
所述提拉法包括如下步骤:将Mg-Sr-Zn系合金进行酸洗,同时将所述可降解高分子涂层的材料溶解在有机溶剂中制成高分子材料胶体,然后将酸洗后的Mg-Sr-Zn系合金在高分子材料胶体中浸涂后匀速拉出进行离心处理,得到表面涂覆有可降解高分子涂层的可降解吸收性Mg-Sr-Zn系合金医用植入体。所述有机溶剂优选三氯乙烷。The pulling method includes the following steps: pickling the Mg-Sr-Zn alloy, and dissolving the degradable polymer coating material in an organic solvent to make a polymer material colloid, and then pickling the The Mg-Sr-Zn alloy is dip-coated in the polymer material colloid and pulled out at a uniform speed for centrifugation to obtain a degradable and absorbable Mg-Sr-Zn alloy medical implant coated with a degradable polymer coating. body. The organic solvent is preferably trichloroethane.
所述匀胶法包括如下步骤:将Mg-Sr-Zn系合金进行酸洗,同时将所述可降解高分子涂层的材料溶解在有机溶剂中制成高分子材料胶体,然后将高分子材料胶体滴在合金表面,利用匀胶机高速旋转使胶体铺展到合金上形成薄层,干燥以去除多余溶剂,多次涂覆以达到最佳效果,得到表面涂覆有可降解高分子涂层的可降解吸收性Mg-Sr-Zn系合金医用植入体。所述有机溶剂优选三氯乙烷。The colloid leveling method includes the following steps: pickling the Mg-Sr-Zn alloy, and simultaneously dissolving the material of the degradable polymer coating in an organic solvent to make a polymer material colloid, and then dissolving the polymer material The colloid is dropped on the surface of the alloy, and the colloid is spread on the alloy to form a thin layer by using the high-speed rotation of the glue homogenizer, dried to remove excess solvent, and coated several times to achieve the best effect, and the surface is coated with a degradable polymer coating. A biodegradable and absorbable Mg-Sr-Zn alloy medical implant. The organic solvent is preferably trichloroethane.
所述等离子体喷涂采用的等离子气体主气为Ar 30~100scfh,次气为H25~20scfh,喷涂电流:400~800A,喷涂电压:40~80V,喷涂距离100~500mm。The main plasma gas used in the plasma spraying is Ar 30-100 scfh, the secondary gas is H 2 5-20 scfh, the spraying current is 400-800A, the spraying voltage is 40-80V, and the spraying distance is 100-500mm.
所述电沉积,是以Mg-Sr-Zn系合金为阴极,在含钙、磷、氟或锶盐的电解液中,电流密度为0.5~30mA/cm2,温度为25~85℃,处理10~60min后,清洗干燥得到所述医用植入体。The electrodeposition is to use the Mg-Sr-Zn alloy as the cathode, in the electrolyte solution containing calcium, phosphorus, fluorine or strontium salt, the current density is 0.5~30mA/cm 2 , the temperature is 25~85°C, the treatment After 10-60 minutes, wash and dry to obtain the medical implant.
所述阳极氧化方法,是将Mg-Sr-Zn系合金在钙、磷、氟或锶盐的电解液中,200~500V下氧化5~30min。The anodic oxidation method is to oxidize the Mg-Sr-Zn alloy in the electrolytic solution of calcium, phosphorus, fluorine or strontium salt at 200-500V for 5-30min.
本发明还提供了上述Mg-Sr-Zn系合金在制备医用植入体中的应用,如在骨组织修复支架中的应用。The present invention also provides the application of the above-mentioned Mg-Sr-Zn alloy in the preparation of medical implants, such as the application in bone tissue repair brackets.
本发明提供的合金能够作为医用植入体的原理为:(1)从生物相容性的角度来看,镁是人体的必需元素,因此肾功能正常者每天用4~6g镁,一般不会引起毒副作用;从材料学角度来看,镁合金密度(1.75~1.85g/cm3)与人体密致组织(1.75g/cm3)相近,弹性模量约为45GPa,不到医用钛合金弹性模量(109-112GPa)的1/2,能有效缓解骨科植入物的应力遮挡效应;而且,镁合金化学性质活泼,在含有Cl-的人体体液环境中可腐蚀降解。(2)锶是人体的微量元素,99%存在于骨和牙齿;Sr盐可以促进骨组织形成,抑制骨吸收,从而增加骨量和提高骨强度,治疗骨质疏松。从材料学角度来看,适量添加Sr可以提高镁合金的室温和高温强度,改善镁合金的高温蠕变性能和抗热裂性,提高镁合金的耐腐蚀性能。(3)锌是人体的必需微量元素。机体内的锌几乎全部是以结合到细胞蛋白质的Zn2+形式存在。冶金学上,锌在镁中的最大固溶度为6.2%,具有固溶强化和时效强化的作用,可显著提高镁合金室温强度,提高镁合金的耐腐蚀性。The principle that the alloy provided by the present invention can be used as a medical implant is as follows: (1) From the perspective of biocompatibility, magnesium is an essential element for the human body, so people with normal renal function use 4-6g of magnesium per day, generally not Cause toxic and side effects; From the perspective of material science, the density of magnesium alloy (1.75~1.85g/cm 3 ) is similar to that of human dense tissue (1.75g/cm 3 ), and the elastic modulus is about 45GPa, which is less than that of medical titanium alloy. 1/2 of the modulus (109-112GPa), can effectively alleviate the stress shielding effect of orthopedic implants; moreover, magnesium alloys are chemically active and can be corroded and degraded in the environment of human body fluids containing Cl-. (2) Strontium is a trace element in the human body, 99% of which exists in bones and teeth; Sr salt can promote the formation of bone tissue and inhibit bone resorption, thereby increasing bone mass and improving bone strength, and treating osteoporosis. From the perspective of materials science, adding Sr in an appropriate amount can improve the room temperature and high temperature strength of magnesium alloys, improve the high temperature creep properties and thermal cracking resistance of magnesium alloys, and improve the corrosion resistance of magnesium alloys. (3) Zinc is an essential trace element for the human body. Zinc in the body is almost exclusively in the form of Zn 2+ bound to cellular proteins. In metallurgy, the maximum solid solubility of zinc in magnesium is 6.2%, which has the effects of solid solution strengthening and aging strengthening, which can significantly improve the room temperature strength of magnesium alloys and improve the corrosion resistance of magnesium alloys.
本发明与现有技术相比具有如下优点和效果:Compared with the prior art, the present invention has the following advantages and effects:
(1)本发明的可降解吸收Mg-Sr-Zn系镁合金,选用人体必需金属元素,不含有害或潜在有害元素,其中的合金化元素Sr可促进成骨,抑制骨吸收,从而伴随Mg-Sr-Zn系合金降解促进组织愈合。(1) The degradable and absorbable Mg-Sr-Zn magnesium alloy of the present invention uses essential metal elements for the human body and does not contain harmful or potentially harmful elements. The alloying element Sr in it can promote bone formation and inhibit bone resorption, thereby accompanying Mg -Sr-Zn alloy degradation promotes tissue healing.
(2)本发明的Mg-Sr-Zn系镁合金的制备方法,工艺简单,通过成分设计和制备工艺的配合,实现调控医用植入体的力学性能和降解速度,获得最佳的力学性能和耐腐蚀性能。(2) The preparation method of the Mg-Sr-Zn series magnesium alloy of the present invention has a simple process, and through the cooperation of the composition design and the preparation process, the mechanical properties and degradation speed of the medical implant can be adjusted to obtain the best mechanical properties and Corrosion resistance.
附图说明Description of drawings
图1为实施例1制备的铸态Mg-Sr-Zn合金显微组织。Figure 1 is the microstructure of the as-cast Mg-Sr-Zn alloy prepared in Example 1.
图2为实施例1铸态Mg-Sr-Zn合金和实施例2制备的轧态Mg-Sr-Zn合金室温拉伸性能。Fig. 2 shows the tensile properties at room temperature of the as-cast Mg-Sr-Zn alloy in Example 1 and the rolled Mg-Sr-Zn alloy prepared in Example 2.
图3为实施例2制备的轧态Mg-Sr-Zn合金植入小鼠骨髓腔4周后的X射线图。Fig. 3 is an X-ray image of the as-rolled Mg-Sr-Zn alloy prepared in Example 2 implanted into the bone marrow cavity of a mouse for 4 weeks.
图4为实施例2制备的轧态Mg-Sr-Zn合金植入小鼠骨髓腔4周后的micro-CT 3D重建图。Figure 4 is a micro-CT 3D reconstruction image of the rolled Mg-Sr-Zn alloy prepared in Example 2 implanted into the bone marrow cavity of a mouse for 4 weeks.
图5为实施例2制备的轧态Mg-Sr-Zn合金植入小鼠骨髓腔4周后的micro-CT 2D图。Figure 5 is a micro-CT 2D image of the rolled Mg-Sr-Zn alloy prepared in Example 2 implanted into the bone marrow cavity of a mouse for 4 weeks.
具体实施方式Detailed ways
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。The experimental methods used in the following examples are conventional methods unless otherwise specified.
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。The materials and reagents used in the following examples can be obtained from commercial sources unless otherwise specified.
实施例1、制备铸态Mg-Sr-Zn合金及其拉伸性能Embodiment 1, preparation as-cast Mg-Sr-Zn alloy and its tensile properties
试验原料采用纯Mg(99.95wt.%)、纯Zn和Mg-Sr中间合金,按照配比:Sr 2%、Zn 1%和余量为Mg称取原料:Mg、Mg-Sr中间合金和Zn。The test raw materials are pure Mg (99.95wt.%), pure Zn and Mg-Sr master alloy, according to the proportion: Sr 2%, Zn 1% and the balance is Mg, and the raw materials are weighed: Mg, Mg-Sr master alloy and Zn .
在CO2和SF6气氛保护下熔化纯镁锭,温度升高至750℃加入Mg-Sr中间合金,待其熔化后搅拌10min,随后加入Zn,搅拌10min,使合金化元素Sr和Zn均匀化。升温至750℃后保温30min,将熔体浇注到预热至300℃的模具中进行重力铸造,制得Mg-Sr-Zn铸锭。Melt the pure magnesium ingot under the protection of CO 2 and SF 6 atmosphere, raise the temperature to 750°C, add the Mg-Sr master alloy, stir for 10 minutes after it melts, then add Zn, stir for 10 minutes to make the alloying elements Sr and Zn homogeneous . After raising the temperature to 750°C and keeping it warm for 30 minutes, the melt was poured into a mold preheated to 300°C for gravity casting to obtain a Mg-Sr-Zn ingot.
本实施例制备的铸态Mg-Sr-Zn合金显微组织如图1所示,由该图可得之,本实施例制备的铸态Mg-Sr-Zn合金晶粒直径小于100μm,在晶粒内部有二次相析出。The microstructure of the as-cast Mg-Sr-Zn alloy prepared in this example is shown in Figure 1, and it can be obtained from this figure that the grain diameter of the as-cast Mg-Sr-Zn alloy prepared in this example is less than 100 μm. There is secondary phase precipitation inside the particle.
将本实施例制备的铸态Mg-Sr-Zn合金按照ASTM拉伸标准线切割加工成拉伸标准样,SiC耐水砂纸打磨至2000#,利用通用拉伸试验机进行室温拉伸实验进行室温拉伸试验,拉伸速度为1mm/min。The as-cast Mg-Sr-Zn alloy prepared in this example is processed into a tensile standard sample according to the ASTM tensile standard wire cutting, and the SiC water-resistant sandpaper is polished to 2000#, and the room temperature tensile test is carried out by using a general tensile testing machine. Tensile test, the tensile speed is 1mm/min.
本实施例制备的铸态Mg-Sr-Zn合金的室温拉伸性能如图2所示(黑色柱状图)。The room temperature tensile properties of the as-cast Mg-Sr-Zn alloy prepared in this example are shown in Figure 2 (black bar graph).
实施例2、制备轧态Mg-Sr-Zn合金及其拉伸性能Embodiment 2, preparation rolled state Mg-Sr-Zn alloy and its tensile properties
按照实施例1中的步骤制备铸态Mg-Sr-Zn合金,然后将该铸态Mg-Sr-Zn合金加工成5mm厚板材,砂纸打磨至无明显缺陷,于400℃的条件下固溶处理3小时,进行轧制:依次进行粗轧、中轧和精轧:在450℃下进行粗轧,道次压下量为10%,在400℃下进行中轧,道次压下量为50%,在350℃下进行粗轧,道次压下量为10%,最终轧制到2mm厚薄板。The as-cast Mg-Sr-Zn alloy was prepared according to the steps in Example 1, and then the as-cast Mg-Sr-Zn alloy was processed into a 5mm thick plate, sanded until there were no obvious defects, and solution treated at 400°C Rolling for 3 hours: rough rolling, intermediate rolling and finish rolling in sequence: rough rolling at 450°C, with a reduction of 10% per pass, intermediate rolling at 400°C, with a reduction of 50 passes %, rough rolling is carried out at 350°C, the reduction in each pass is 10%, and finally rolled to a 2mm thick sheet.
将本实施例制备的轧态Mg-Sr-Zn合金按照ASTM拉伸标准线切割加工成拉伸标准样,SiC耐水砂纸打磨至2000#,利用通用拉伸试验机进行室温拉伸实验,拉伸速度为1mm/min。The rolled Mg-Sr-Zn alloy prepared in this embodiment is processed into a tensile standard sample according to the ASTM tensile standard wire cutting, and the SiC water-resistant sandpaper is polished to 2000#, and the tensile test at room temperature is carried out using a general tensile testing machine. The speed is 1mm/min.
本实施例制备的轧态Mg-Sr-Zn合金的室温拉伸性能如图2所示(灰色柱状图),由该图可得知,轧态Mg-Sr-Zn合金的屈服强度和拉伸强度举要明显高于铸态,但是二者断裂伸长率差别不大,但铸态合金断裂伸长率要稍长一些。The room temperature tensile properties of the as-rolled Mg-Sr-Zn alloy prepared in this example are shown in Figure 2 (gray histogram), from which it can be known that the yield strength and tensile properties of the as-rolled Mg-Sr-Zn alloy The strength is significantly higher than that of the as-cast alloy, but the elongation at break is not much different between the two, but the elongation at break of the as-cast alloy is slightly longer.
将本实施例制备的轧态Mg-Sr-Zn合金加工成Φ0.7mm和长5mm的棒材,打磨抛光至2000#砂纸,环氧乙烷消毒。选择8只3个月C57BL/6小鼠,随机分为两组,每组4只。其中一组麻醉并对左侧膝盖备皮并消毒,股骨远端钻直径为0.7mm圆孔,将合金棒植入孔内并缝合。另外一组小鼠左侧股骨钻孔作为空白对照。术后定期观察没有发现植入体引起周围组织发炎等异物反应。术后4周发现成骨反明显,骨小梁密度高于对照组,外骨膜和内骨膜成骨均高于对照组。Process the as-rolled Mg-Sr-Zn alloy prepared in this example into rods with a diameter of 0.7 mm and a length of 5 mm, grind and polish to 2000# sandpaper, and sterilize with ethylene oxide. Eight 3-month-old C57BL/6 mice were selected and randomly divided into two groups with 4 mice in each group. In one group, the left knee was anesthetized and the skin was prepared and disinfected. A 0.7mm diameter hole was drilled in the distal femur, and an alloy rod was implanted in the hole and sutured. Another group of mice was drilled in the left femur as a blank control. Periodic observation after the operation did not reveal foreign body reactions such as inflammation of the surrounding tissue caused by the implant. After 4 weeks, it was found that the osteogenesis was significantly reversed, the density of trabecular bone was higher than that of the control group, and the osteogenesis of the outer periosteum and inner periosteum were higher than that of the control group.
采用本实施例得到的轧态Mg-Sr-Zn合金植入小鼠骨髓腔4周后的X射线和micro-CT观察结果如图3、图4和图5所示,由这些结果可得知,在植入小鼠骨髓腔4周后,合金植入物已经有部分降解,在降解部位有新骨生成。The X-ray and micro-CT observation results of the rolled Mg-Sr-Zn alloy obtained in this embodiment were implanted into the bone marrow cavity of mice for 4 weeks, as shown in Figure 3, Figure 4 and Figure 5, and can be known from these results , 4 weeks after being implanted into the bone marrow cavity of mice, the alloy implants had been partially degraded, and new bone was formed at the degraded sites.
实施例3、挤压态Mg-Sr-Zn-Sn合金的制备及其生物相容性与可降解性Example 3, Preparation of Extruded Mg-Sr-Zn-Sn Alloy and Its Biocompatibility and Degradability
试验原料采用纯Mg(99.95wt.%)、Mg-Sr中间合金、纯Zn和纯Sn,按照配比:Sr 3%、Zn 1.5%、Sn 0.5%和余量为Mg称取原料:Mg、Mg-Sr中间合金、Zn和Sn。The test raw materials are pure Mg (99.95wt.%), Mg-Sr master alloy, pure Zn and pure Sn, according to the proportion: Sr 3%, Zn 1.5%, Sn 0.5% and the balance is Mg, and the raw materials are weighed: Mg, Mg-Sr master alloy, Zn and Sn.
在CO2和SF6气氛保护下熔化纯镁锭,温度升高至750℃加入Mg-Sr中间合金,待其熔化后搅拌10min,随后加入Zn和Sn,搅拌10min,使合金化元素Sr、Zn和Sn均匀化。升温至750℃后保温30min,将熔体浇注到预热至300℃的模具中进行重力铸造,制得Mg-Sr-Zn-Sn铸锭。将制得的铸锭400℃保温3小时,进行挤压,挤压速率为2mm/min,挤压比25:1,挤压温度270℃。Melt the pure magnesium ingot under the protection of CO 2 and SF 6 atmosphere, raise the temperature to 750°C, add the Mg-Sr master alloy, stir for 10 min after it melts, then add Zn and Sn, and stir for 10 min to make the alloying elements Sr, Zn and Sn homogenization. After raising the temperature to 750°C and keeping it warm for 30 minutes, pour the melt into a mold preheated to 300°C for gravity casting to obtain a Mg-Sr-Zn-Sn ingot. The prepared ingot was kept at 400° C. for 3 hours, and then extruded at an extrusion rate of 2 mm/min, an extrusion ratio of 25:1, and an extrusion temperature of 270° C.
取上述方法制得的挤压态Mg-Sr-Zn-Sn合金加工成螺钉植入18只新西兰白兔左侧股骨,对侧植入纯Ti螺钉。术后1个、6个和12个月分别处死实验动物,18只兔子均没有发现植入体引起周围组织发炎等异物反应,术后12个月Mg-Sr-Zn-Sn合金植入体体积减少58%,降解处均被新骨填充。The extruded Mg-Sr-Zn-Sn alloy prepared by the above method was processed into screws and implanted into the left femurs of 18 New Zealand white rabbits, and pure Ti screws were implanted on the opposite side. The experimental animals were sacrificed at 1 month, 6 months and 12 months after operation. No foreign body reaction such as inflammation of the surrounding tissue caused by the implant was found in 18 rabbits. The volume of the Mg-Sr-Zn-Sn alloy implant at 12 months after operation The reduction was 58%, and the degraded parts were filled with new bone.
实施例4、制备多孔结构的Mg-Sr-Zn合金及其骨组织匹配性能Example 4. Preparation of Mg-Sr-Zn alloy with porous structure and its bone tissue matching properties
将纯Mg(纯度为99.95%)、纯Sr(纯度为99.9%)和纯Zn(纯度为99.999%)按质量比为93:5:2的比例,混合均匀,压制成坯,在真空烧结炉(VSF系列(通用型)真空烧结炉,沈阳真空技术研究所)中烧结,具体烧结的步骤为:以2℃/min慢速升温至300℃后,接着以30℃/min快速升温至650℃,然后在此温度下保持4h,最后,炉冷降温,用预合金粉烧结法得到多孔结构的Mg-Sr-Zn合金。Mix pure Mg (purity 99.95%), pure Sr (purity 99.9%) and pure Zn (purity 99.999%) in a mass ratio of 93:5:2, mix them evenly, press them into billets, and heat them in a vacuum sintering furnace (VSF series (general-purpose) vacuum sintering furnace, Shenyang Vacuum Technology Research Institute), the specific sintering steps are: after slowly heating up to 300°C at 2°C/min, then rapidly raising the temperature to 650°C at 30°C/min , and then kept at this temperature for 4h, and finally, the furnace was cooled, and the porous structure of Mg-Sr-Zn alloy was obtained by pre-alloy powder sintering method.
经排水法测量空隙率为50%,将该多孔结构的Mg-Sr-Zn合金经切割制备成尺寸为5×5×5mm3的立方体,即得到医用植入体-骨组织修复支架。The porosity was measured to be 50% by the drainage method, and the porous Mg-Sr-Zn alloy was cut into a cube with a size of 5×5×5 mm 3 to obtain a medical implant-bone tissue repair scaffold.
将按照上述方法制备的骨组织修复支架植入体12个,分别利用手术埋植于12只家兔的股骨内,首先用手钻在家兔股骨处钻孔后将植入体埋植入左侧股骨,术后注射青霉素钾15mg/kg,实验以316L不锈钢(西北有色金属研究院)支架作为对照;术后1个、5个月分别处死实验动物。术后1个月,micro-CT观察家兔股骨处该合金材料由于腐蚀降解体积逐步减小,材料周围的骨组织修复受损骨且接触紧密。骨组织修复支架植入体植入5月后,均完全降解,而316L不锈钢支架周围组织发炎。Twelve bone tissue repair scaffold implants prepared according to the above method were respectively implanted in the femurs of 12 rabbits by surgery. After drilling a hole in the femur of a rabbit with a hand drill, the implant was embedded in the left femur, and 15 mg/kg of penicillin potassium was injected after the operation. The 316L stainless steel (Northwest Nonferrous Metals Research Institute) stent was used as a control in the experiment; The experimental animals were sacrificed at 5 months respectively. One month after operation, micro-CT observed that the volume of the alloy material at the femur of the rabbit gradually decreased due to corrosion degradation, and the bone tissue around the material repaired the damaged bone and was in close contact. Five months after implantation of the bone tissue repair stent implants, they were completely degraded, while the surrounding tissues of the 316L stainless steel stents were inflamed.
实施例5、表面涂覆L-聚乳酸(PLLA)的轧态Mg-Sr-Zn合金的制备及其可降解性能Example 5. Preparation and degradability of as-rolled Mg-Sr-Zn alloy coated with L-polylactic acid (PLLA) on the surface
按照实施例2中的方法制备轧态Mg-Sr-Zn合金,然后按照下述提拉法在其表面涂覆PLLA涂层,厚度为10~30μm,制备PLLA表面改性骨固定板:Prepare the rolled Mg-Sr-Zn alloy according to the method in Example 2, and then coat the PLLA coating on its surface according to the following pulling method, with a thickness of 10-30 μm, to prepare the PLLA surface modified bone fixation plate:
(1)使用浓硝酸、氢氟酸配置酸洗液,将骨固定板酸洗5~20min。(1) Use concentrated nitric acid and hydrofluoric acid to prepare pickling solution, and pickle the bone fixation plate for 5-20 minutes.
(2)在10ml三氯乙烷中溶解0.5gPLLA(分子量:80~200kDa)。(2) Dissolve 0.5g PLLA (molecular weight: 80~200kDa) in 10ml trichloroethane.
(3)将酸洗后的合金植入体放入胶体中浸泡30分钟后匀速提拉取出,真空室温干燥过夜。(3) Soak the pickled alloy implant in the colloid for 30 minutes, pull it out at a constant speed, and dry it overnight in vacuum at room temperature.
(4)消毒处理,准备待用。(4) Disinfect and prepare for use.
将制得的PLLA表面改性Mg-Sr-Zn骨固定板固定于狗的股骨中。通过定期的观察没有发现植入体引起周围组织发炎等异物反应。观察发现随着植入时间的延长,PLLA逐渐溶解,骨固定板尺寸变小,同时与连接骨处连接紧密。7个月后,植入骨固定板完全降解。The prepared PLLA surface modified Mg-Sr-Zn bone fixation plate was fixed in the femur of dogs. No foreign body reaction such as inflammation of the surrounding tissue caused by the implant was found through regular observation. It was observed that with the prolongation of implantation time, PLLA gradually dissolved, the size of the bone fixation plate became smaller, and it was closely connected with the connecting bone. After 7 months, the implanted bone fixation plate degraded completely.
实施例6、表面涂覆钙磷涂层的轧态Mg-Sr-Zn合金的制备及其可降解性能
按照实施例2中的方法制备轧态Mg-Sr-Zn合金—骨固定板,用800#、1500#和2000#砂纸打磨骨固定板,然后按照阳极氧化方法在其表面涂覆钙磷,厚度为10~30μm:以0.04Mβ-甘油磷酸钠和0.2M醋酸钙作为电解液:Prepare the rolled Mg-Sr-Zn alloy-bone fixation plate according to the method in Example 2, polish the bone fixation plate with 800#, 1500# and 2000# sandpaper, then apply calcium phosphorus on its surface according to the anodic oxidation method, the thickness 10~30μm: use 0.04M β-sodium glycerophosphate and 0.2M calcium acetate as the electrolyte:
(1)骨固定板在pH:10~11电解液中350V阳极氧化10min。(1) The bone fixation plate was anodized at 350V for 10 minutes in pH: 10~11 electrolyte.
(2)清洗后将样品置于高压反应釜中130℃保温4h。(2) After cleaning, place the sample in a high-pressure reactor at 130°C for 4 hours.
(3)消毒处理,准备待用。(3) Disinfect and prepare for use.
将制得的阳极氧化和水热合成共同表面改性骨固定板固定于狗的股骨中。通过定期的观察没有发现植入体引起周围组织发炎等异物反应。观察发现随着植入时间的延长,表面涂层逐渐与骨融合,骨固定板尺寸变小。12个月后,植入骨固定板完全降解。The as-prepared anodized and hydrothermally synthesized co-surface modified bone fixation plates were fixed in dog femurs. No foreign body reaction such as inflammation of the surrounding tissue caused by the implant was found through regular observation. It was observed that as the implantation time prolongs, the surface coating gradually fuses with the bone, and the size of the bone fixation plate becomes smaller. After 12 months, the implanted bone fixation plate degraded completely.
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CN103276264A (en) * | 2013-06-21 | 2013-09-04 | 中国兵器工业第五九研究所 | Low-cost and high-heat-strength wrought magnesium alloy and preparation method thereof |
CN103725942A (en) * | 2013-12-31 | 2014-04-16 | 重庆大学 | Mg-Zn-Sr-Ca system magnesium alloy and preparation method thereof |
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CN104911427A (en) * | 2015-06-19 | 2015-09-16 | 北京大学 | Mg-Ca-Sr-Zn magnesium alloy as well as preparation method and application thereof |
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CN110016599A (en) * | 2019-04-23 | 2019-07-16 | 中国海洋大学 | A kind of biomedical magnesium alloy with high corrosion resistance and uniform degradation and preparation method thereof |
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CN110484794A (en) * | 2019-09-23 | 2019-11-22 | 苏州市美新迪斯医疗科技有限公司 | A kind of medical magnesium alloy and preparation method thereof |
CN116024471A (en) * | 2022-12-01 | 2023-04-28 | 中南大学 | High-strength plastic multi-water-soluble channel magnesium alloy and preparation method thereof |
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