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Número de publicaciónCN102796905 B
Tipo de publicaciónConcesión
Número de solicitudCN 201110301063
Fecha de publicación7 May 2014
Fecha de presentación29 Sep 2011
Fecha de prioridad29 Sep 2011
También publicado comoCN102796905A, WO2013044834A1
Número de publicación201110301063.7, CN 102796905 B, CN 102796905B, CN 201110301063, CN-B-102796905, CN102796905 B, CN102796905B, CN201110301063, CN201110301063.7
Inventores叶雷
Solicitante温州智创科技有限公司
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos:  SIPO, Espacenet
Method for preparing medical porous titanium implant material
CN 102796905 B
Resumen  traducido del chino
一种制备医用多孔钽植入材料的方法,有机粘结剂与分散剂配制成的溶液和钽粉制成钽粉浆料,浇注于有机泡沫体中,浸渍直至有机泡沫体孔隙注满钽粉浆料,干燥除去浇注有钽粉浆料的有机泡沫体中的分散剂,在惰性气体保护气氛下脱脂处理以除去有机粘结剂和有机泡沫体,真空下烧结制得多孔烧结体、冷却,真空退火及常规后处理制得多孔钽;所述烧结步骤是真空度为10-4Pa~10-3Pa,以10~20℃/min升温至1500~1800℃、保温120~240min、随炉冷至200~300℃,再以10~20℃/min升温至1500~1800℃、保温180~240min,以5~10℃/min升温至2000~2200℃、保温120~360min。 A medical method of porous tantalum implant materials prepared organic binder and a dispersing agent formulated as a solution made of tantalum powder and tantalum powder slurry, pouring in an organic foam, impregnated organic foam until the pores filled with tantalum powder slurry casting was removed and dried tantalum powder slurry in an organic foam dispersant, an inert gas atmosphere at a degreasing treatment to remove the organic binder and an organic foam, vacuum sintering a porous sintered body is cooled, vacuum annealing and conventional post-treatment a porous tantalum; said sintering step is a vacuum degree of 10-4Pa ~ 10-3Pa, to 10 ~ 20 ℃ / min heating up to 1500 ~ 1800 ℃, holding 120 ~ 240min, with furnace cooling to 200 ~ 300 ℃, then 10 ~ 20 ℃ / min was heated to 1500 ~ 1800 ℃, insulation 180 ~ 240min, to 5 ~ 10 ℃ / min was heated to 2000 ~ 2200 ℃, insulation 120 ~ 360min. 本发明制得的多孔钽材料不仅生物相容性、安全性好,而且力学性能特别强度高,非常适合用于替代人体承重部位的骨组织。 The present invention is prepared porous tantalum material is not only biocompatibility, safety, and high mechanical properties, especially strength, very suitable for load-bearing parts of the body to replace bone tissue.
Reclamaciones(6)  traducido del chino
1.一种制备医用多孔钽植入材料的方法,采用泡沫浸溃法烧结而成,其特征在于:用有机粘结剂与分散剂配制成的溶液和钽粉制成钽粉浆料,并浇注于有机泡沫体中,浸溃直至有机泡沫体孔隙注满钽粉浆料,然后干燥除去浇注有钽粉浆料的有机泡沫体中的分散剂,在惰性气体保护气氛下脱脂处理以除去有机粘结剂和有机泡沫体,真空下烧结制得多孔烧结体、冷却,再真空下退火热处理及常规后处理制得多孔钽;所述烧结步骤是真空度为KT4Pa ~l(T3Pa,以10 ~20°C /min 升温至1500 ~1800°C、保温120 ~240min、随炉冷至200~300°C,再以10~20°C /min升温至1500~1800°C、保温180~240min,以5~IO0C /min 升温至2000 ~2200°C、保温120 ~360min。 1. A method for preparing a medical porous tantalum implant materials, the use of foam impregnated sintering method, wherein: with an organic binder and a dispersing agent formulated as a solution made of tantalum powder and tantalum powder slurry, and pouring organic foam, impregnated organic foam pores until filled tantalum powder slurry, then dried to remove the tantalum powder slurry pouring organic foam dispersant degreasing treatment under an inert gas atmosphere to remove the organic binder and an organic foam, vacuum sintering a porous sintered body, cooling, and then annealing under vacuum and conventional post-treatment a porous tantalum; said sintering step is a vacuum degree of KT4Pa ~ l (T3Pa, 10 to 20 ° C / min heating up to 1500 ~ 1800 ° C, holding 120 ~ 240min, with furnace cooling to 200 ~ 300 ° C, then 10 ~ 20 ° C / min heating up to 1500 ~ 1800 ° C, holding 180 ~ 240min, In 5 ~ IO0C / min was raised to 2000 ~ 2200 ° C, holding 120 ~ 360min.
2.如权利要求1所述的方法,其特征在于:所述钽粉为平均粒径小于43 μ m、氧含量小于0.1%的金属钽粉;所述有机粘结剂为聚乙烯醇,所述分散剂为水,配制成聚乙烯醇水溶液与所述的钽粉制成钽粉浆料;所述有机泡沫体为孔径0.48~0.89mm,密度0.015 g/cm3~0.035g/cm3,硬度大于等于50°的聚氨酯泡沫。 2. The method according to claim 1, wherein: said tantalum powder to an average particle size of less than 43 μ m, an oxygen content of less than 0.1% of tantalum powder; the organic binder is polyvinyl alcohol, the said dispersant is water, formulated as an aqueous solution of polyvinyl alcohol and the tantalum powder made of tantalum powder slurry; the organic foam as pore size 0.48 ~ 0.89mm, density of 0.015 g / cm3 ~ 0.035g / cm3, hardness greater than equal to 50 ° of the polyurethane foam.
3.如权利要求2所述的方法,其特征在于:所述聚乙烯醇水溶液的重量百分比浓度为2~8% ;所述钽粉与聚乙烯醇水溶液得重量份比为6~9份:1份;所述聚氨酯泡沫孔径为0.56 ~0.72mm,密度0.025g/cm3,硬度50° ~80。 3. The method according to claim 2, wherein: the concentration by weight of the polyvinyl alcohol aqueous solution is from 2 to 8%; tantalum powder and the weight ratio of the polyvinyl alcohol aqueous solution was 6 to 9 parts: 1; the polyurethane foam pore size 0.56 ~ 0.72mm, density 0.025g / cm3, hardness 50 ° ~ 80. .
4.如权利要求1、2或3所述的方法,其特征在于:所述干燥的真空度保持10_2~IPa真空度,然后在保护气氛下,真空度10_4~10_3Pa,温度400°C~800°C条件下进行除去有机粘结剂和有机泡沫体的脱脂处理;烧结处理:真空度为10_4Pa~10_3Pa,以12~15°C /min升温至1600~1800°C、保温180~200min、随炉冷至200~300°C,再以16~19°C /min升温至1500~1800°C、保温220~240min,以5~8°C /min升温至2000~2200°C、保温250~320min ;最后进行真空退火热处理,真空退火热处理是指经过真空烧结后继续保持温度处于1000~1250°C,保温时间I~4小时,真空度为10_4~10_3Pa。 4. A method as claimed in claim 2 or claim 3, wherein: the degree of vacuum drying 10_2 ~ IPa maintaining the degree of vacuum, and then under a protective atmosphere, vacuum degree 10_4 ~ 10_3Pa, a temperature of 400 ° C ~ 800 carried out under conditions of degreasing ° C to remove the organic binder and organic foam; sintering process: a vacuum degree of 10_4Pa ~ 10_3Pa, to 12 ~ 15 ° C / min heating up to 1600 ~ 1800 ° C, holding 180 ~ 200min, with furnace cooling to 200 ~ 300 ° C, then 16 ~ 19 ° C / min was heated to 1500 ~ 1800 ° C, holding 220 ~ 240min, to 5 ~ 8 ° C / min was heated to 2000 ~ 2200 ° C, holding 250 ~ 320min; final vacuum annealing, vacuum annealing refers maintained after vacuum sintering temperature is 1000 ~ 1250 ° C, holding time I ~ 4 hours, and the vacuum degree 10_4 ~ 10_3Pa. ` `
5.如权利要求1、2或3所`述的方法,其特征在于:所述脱脂处理条件为:以0.50C /min~5°C /min的速率逐步升温至400~800 °C,以IS气通入构成保护气氛并保温30min~120min ; 真空烧结条件为:真空度为KT4Pa~I(T3Pa,以13°C /min升温至1800°C、保温200min、随炉冷至200~300°C,再以17°C /min升温至1800°C、保温230min,以7°C /min升温至2000 ~2200。。、保温300min ; 真空烧结后的冷却条件为:真空度低于10_3Pa,以不高于25°C /min,不低于10°C /min渐降冷却速率方式,对烧结多孔体分段降温冷却至800°C,各段保温时间30min~90min,然后随炉冷却至常温; 真空退火热处理条件为:真空度低于10_4Pa,以不高于30°C /min的速率升至1000~1250°C,保温4h~6h ;再以先慢后快以不低于5°C /min但不高于30°C /min的冷却速率分段冷却至室温,各段的保温时间呈递减且不超过3h。 5. The method of 1, 2, or 3 'of said preceding claims, characterized in that: said degreasing treatment conditions are: a rate of 0.50C / min ~ 5 ° C / min gradually raised to 400 ~ 800 ° C, to IS includes protective gas into the atmosphere and incubated 30min ~ 120min; vacuum sintering conditions: a vacuum degree of KT4Pa ~ I (T3Pa, to 13 ° C / min heating up to 1800 ° C, insulation 200min, with furnace cooling to 200 ~ 300 ° C, then 17 ° C / min temperature was raised to 1800 ° C, holding 230min, to 7 ° C / min temperature was raised to 2000 to 2200 .., insulation 300min; cooling after vacuum sintering conditions: a vacuum of less than 10_3Pa, to not more than 25 ° C / min, not less than 10 ° C / min cooling rate gradually decreased manner, sintered porous body is cooled to sub-cooled 800 ° C, the holding time of each segment 30min ~ 90min, then the furnace was cooled to room temperature ; vacuum annealing conditions: a vacuum of less than 10_4Pa, not higher than 30 ° C / min rate rose to 1000 ~ 1250 ° C, holding 4h ~ 6h; then the first slow after the fast of not below 5 ° C / min but not higher than 30 ° C / min cooling rate segment cooled to room temperature, each segment of the holding time was not decreasing over 3h.
6.如权利要求1、2或3所述的方法,其特征在于:所述干燥的干燥温度60~100°C,干燥时间4~8小时;所述脱脂处理条件为:逐步升温至600~800°C,以99.9999%的纯净氩气通入构成保护气氛,以I~5°C /min的速率从室温升至400°C,保温30~60min,以0.5~`1.5°C /min的速率从400°C升至600~800°C,保温60~120min,真空烧结条件为:真空度为KT4Pa~l(T3Pa,以13。。/min升温至1800。。、保温200min、随炉冷至200~300。。,再以17°C /min 升温至1800°C、保温230min,以7°C /min 升温至2000 ~2200°C、保温300min ;真空烧结后的冷却条件为:真空度为10_4Pa~10_3Pa;以10~20°C /min的速率冷却至1500~1600°C,保温30~60min ;以12~20°C /min的速率冷却至1200~1250°C,保温60~90min ;以10~20°C /min的速率冷却至800°C,然后随炉冷却;真空退火热处理条件为:以15~30°C /min的速率升至1000~1250°C,保温240~480min,真空度为KT4Pa~l(T3Pa,再以5~10°C /min的速率冷却至1000°C,保温90~180min,真空度为KT4Pa~KT3Pa ;以10~20 0C /min的速率冷却至800°C,保温60~120min,真空度低于KT4Pa ;以20~30°C /min的速率冷却至室温,真空度为KT4Pa~l(T3Pa。 6. The method according to claim 2 or claim 3, wherein: the drying temperature drying 60 ~ 100 ° C, the drying time of 4 to 8 hours; the degreasing treatment conditions: gradually raised to 600 ~ 800 ° C, with 99.9999% pure argon gas atmosphere constituted fed, at a rate of I ~ 5 ° C / min from room temperature to 400 ° C, holding 30 ~ 60min, to 0.5 ~ `1.5 ° C / min The rate was raised from 400 ° C 600 ~ 800 ° C, insulation 60 ~ 120min, vacuum sintering conditions: a vacuum degree of KT4Pa ~ l (T3Pa, warmed to 13 ../ min to 1800 .., insulation 200min, with the furnace .. was cooled to 200 to 300, then 17 ° C / min temperature was raised to 1800 ° C, holding 230min, to 7 ° C / min was heated to 2000 ~ 2200 ° C, holding 300min; cooling after vacuum sintering conditions were: Vacuum degree 10_4Pa ~ 10_3Pa; at a rate of 10 ~ 20 ° C / min cooling to 1500 ~ 1600 ° C, holding 30 ~ 60min; at a rate of 12 ~ 20 ° C / min cooling to 1200 ~ 1250 ° C, for 60 ~ 90min; at a rate of 10 ~ 20 ° C / min cooling to 800 ° C, then cooling with the furnace; vacuum annealing conditions are as follows: at a rate of 15 ~ 30 ° C / min was raised to 1000 ~ 1250 ° C, holding 240 ~ 480min, vacuum degree KT4Pa ~ l (T3Pa, at a rate of 5 ~ 10 ° C / min cooling to 1000 ° C, holding 90 ~ 180min, vacuum degree KT4Pa ~ KT3Pa; at a rate of 10 ~ 20 0C / min cooling to 800 ° C, insulation 60 ~ 120min, vacuum of less than KT4Pa; at a rate of 20 ~ 30 ° C / min cooling to room temperature, a vacuum degree of KT4Pa ~ l (T3Pa.
Descripción  traducido del chino

一种制备医用多孔钽植入材料的方法 A medical porous tantalum implant material prepared

技术领域 Technical Field

[0001] 本发明涉及一种多孔医用金属植入材料,特别是涉及一种适于替代承重骨组织的医用多孔钽植入材料的制备方法。 [0001] The present invention relates to a porous metal medical implant materials, particularly to a suitable load-bearing bone substitute medical porous tantalum implant materials preparation.

背景技术 Background

[0002] 多孔医用金属植入材料具有治疗骨组织创伤和股骨组织坏死等重要而特殊的用途,现常见的这类材料有多孔金属不锈钢、多孔金属钛等。 [0002] The porous metal implant material having medical treatment femur bone tissue trauma and tissue necrosis and other important and special applications, now common such materials are porous metal stainless steel, porous titanium and other metals. 作为骨组织创伤和股骨组织坏死治疗使用的多孔植入材料,其孔隙度应达30~80%,而且孔隙最好全部连通与均匀分布,或根据需要孔隙部分连通与均匀分布,使之既与人体的骨组织生长相一致,又减轻了材料本身的重量,以适合人体植入使用。 As bone tissue trauma and the porous implant material used in the treatment of femoral necrosis, porosity should reach 30 to 80%, and preferably all communication with uniform pore distribution, or as needed communication with uniform pore portions, so that both the Human bone tissue growth is consistent, but also reduce the weight of the material itself, the use of implants to fit the human body.

[0003] 而难熔金属钽,由于它具有优秀的生物相容性和力学性能,其多孔材料有望作为替代前述等传统医用金属生物材料,成为主要作为骨组织坏死治疗的生物材料。 [0003] The refractory metals tantalum, due to its excellent biocompatibility and mechanical properties, the porous material is expected as an alternative to the foregoing and other traditional medical metallic biomaterials, become a major bone tissue necrosis treated biomaterial. 由于金属钽对人体的无害、无毒、无副作用,以及随着国内外医学的飞速发展,对钽作为人体植入材料认知的进一步深入,人们对人体植入用多孔金属钽材料的需求变得越来越迫切,对其要求也越来越高。 Since the metal tantalum harmless to humans, non-toxic, no side effects, and with the rapid development of domestic medicine, tantalum implant material as human cognition further, people, implantable porous tantalum material needs become more and more urgent, its requirements are also increasing. 其中作为多孔医用植入金属钽,如果能具有很高的均匀分布连通孔隙以及与人体相适应的物理机械性能,则是保证新生骨组织正常生长的重要连接件构成材料。 Wherein a porous medical implant metal tantalum, if uniformly distributed with high porosity and mechanical properties of communicating with the body to adapt, it is to ensure the normal growth of new bone tissue connecting member constitute an important material.

[0004] 作为医用植入的多孔金属材料就像一般的多孔金属材料那样基本上是以粉末烧结法为主要的加工方法,特别是为获取孔隙连通与均匀分布的多孔金属泡沫结构采用粉末烧结法中的金属粉末浆料在有机泡沫体上的浸溃后干燥再烧结简称泡沫浸溃法居多。 [0004] The medical implant as a porous metal material as the porous metallic material in general is a powder sintering method substantially as main processing method, in particular to obtain communication with the pore structure of the porous metal foam uniformly distributed by powder sintering method The metal powder paste after the impregnated organic foam is dried and then sintered dipping method called bubble majority. 关于粉末烧结所获得的孔隙连通与均匀分布的多孔金属材料通常其金属力学性能并不是很好,其主要原因是工艺上如何安排成孔介质的支撑与消除关系、金属粉末烧结过程中的塌陷问题。 About communicating pores obtained sintered powder and a uniform distribution of the porous metal material is usually not very good mechanical properties of the metal, the main reason is to support the process of how to arrange porous media relations and the elimination of the metal powder sintering process collapse problem . 而已知的文献报道中均没有很好的解决方法而放任自然。 The known literature reports are not a good solution and letting nature.

`[0005] 采用金属粉末烧结法制造多孔钽的文献报道很少,特别是以获得医用植入材料用为目的的多孔钽粉末烧结法文献报道几乎没有。 `[0005] The method for producing a porous sintered metal powder, tantalum rarely reported in the literature, especially in the medical implant material obtained for the purpose of porous tantalum powder sintering method reported in the literature almost nothing. 可以参考的是公开号为CN200510032174,名称“三维通孔或部分孔洞彼此相连多孔金属泡沫及其制备方法”以及CN200710152394,名称“一种新型多孔泡沫钨及其制备方法”。 You can refer to the publication number CN200510032174, the name "through-hole or three holes in part connected to each other porous metal foams and preparation methods," and CN200710152394, the name of "a new type of porous foam tungsten and its preparation method." 然而其所获得的多孔金属或是为过滤材料用,或是为航空航天及其它高温场合用而非作为医用金属植入材料使用,再者所加工的多孔金属也非多孔钽。 However, it has acquired or porous metal material is filtered, or for the aerospace and other high temperature applications for use as a medical rather than a metal implant materials, porous metal addition being processed is also a non-porous tantalum.

[0006] 关于多孔钽,US5282861公开了一种应用于松质骨植入体、细胞和组织感受器的开孔钽材料及其制备。 [0006] For the porous tantalum, US5282861 discloses a method applied in cancellous bone implants and cell and tissue receptors openings tantalum material and preparation. 这种多孔钽由纯商业钽制成,它以聚亚氨酯前体进行热降解得到的碳骨架为支架,该碳骨架呈多重的十二面体,其内为网格样结构,整体遍布微孔,孔隙率可高达98%,再将商业纯钽通过化学蒸气沉积、渗透的方法结合到碳骨架上以形成多孔金属微结构,简称为化学沉积法。 The porous tantalum from pure commercial tantalum, it polyurethane precursor obtained thermal degradation of the carbon skeleton of the stent, the carbon skeleton of the multi dodecahedron form, the grid-like structure which, throughout the whole micro- hole, the porosity can be up to 98%, then commercially pure tantalum by chemical vapor deposition, infiltration methods bound to the carbon skeleton to form a porous metal microstructure, referred to as chemical deposition method. 这种方法所获得的多孔钽材料其表面的钽层厚度在40~60 μ m之间;在整个多孔材料中,钽重约占99%,而碳骨架重量则占1%左右。 Porous tantalum material obtained by this method tantalum layer thickness of the surface thereof is between 40 ~ 60 μ m; the entire porous material, tantalum about 99 weight%, and the carbon skeleton accounted for about 1% by weight. 文献进一步记载,该多孔材料的抗压强度50~70MPa,弹性模量2.5~3.5GPa,抗拉强度63MPa,塑性变形量15%。 Further according to the literature, the compressive strength of the porous material 50 ~ 70MPa, the elastic modulus of 2.5 ~ 3.5GPa, the tensile strength of 63MPa, the amount of plastic deformation of 15%. 但是将它作为医用植入材料的多孔钽,其材料的力学性能如延展性有明显不足之处,会影响到后续的对多孔钽材料本身的加工,例如成型件的切割等。 But it as porous tantalum medical implant materials, mechanical properties such as ductility of the material has obvious shortcomings, it will affect the subsequent processing of porous tantalum material itself, such as molded parts of cutting. 同样在前述的金属粉末烧结法所获得的产品也均存在这样的不足。 Also in the aforementioned metal powder sintering method are obtained in the presence of such products are insufficient. 再由于其制备方法的局限,获得的成品纯度不够,有碳骨架残留物,导致生物安全性降低。 Then due to the limitations of the preparation method, the purity of the finished product obtained is insufficient, the residue carbon skeleton, leading to reduced biological safety.

发明内容 DISCLOSURE

[0007] 本发明的目的在于提供一种生物相容性好、力学强度高的医用多孔钽植入材料的制备方法。 [0007] The present invention is to provide a biocompatible, high mechanical strength of the preparation of porous tantalum material for medical implants.

[0008] 本发明的目的是通过如下技术手段实现的: [0008] The object of the present invention is achieved by the following techniques:

[0009] 一种制备医用多孔钽植入材料的方法,采用泡沫浸溃法烧结而成,其特点在于用有机粘结剂与分散剂配制成的溶液和钽粉制成钽粉浆料,并浇注于有机泡沫体中,浸溃直至有机泡沫体孔隙注满钽粉浆料,然后干燥除去浇注有钽粉浆料的有机泡沫体中的分散剂,在惰性气体保护气氛下脱脂处理以除去有机粘结剂和有机泡沫体,真空下烧结制得多孔烧结体、冷却,再真空下退火及常规后处理制得多孔钽;所述烧结步骤是真空度为KT4Pa ~l(T3Pa,以10 ~20°C /min 升温至1500 ~1800°C、保温120 ~240min、随炉冷至200 ~300°C,再以10 ~20°C /min 升温至1500 ~1800°C、保温180 ~240min,以5 ~10°C /min 升温至2000 ~2200°C、保温120 ~360min。 A method of medical preparation of porous tantalum implant materials [0009], the use of foam impregnated sintering method, which is characterized by an organic binder and a dispersing agent formulated as a solution made of tantalum powder and tantalum powder slurry, and pouring organic foam, impregnated organic foam pores until filled tantalum powder slurry, then dried to remove the tantalum powder slurry pouring organic foam dispersant degreasing treatment under an inert gas atmosphere to remove the organic binder and an organic foam, vacuum sintering a porous sintered body, cooled, and then annealed under vacuum and the conventional post-treatment a porous tantalum; said sintering step is a vacuum degree of KT4Pa ~ l (T3Pa, 10 to 20 ° C / min heating up to 1500 ~ 1800 ° C, holding 120 ~ 240min, with furnace cooling to 200 ~ 300 ° C, then 10 ~ 20 ° C / min heating up to 1500 ~ 1800 ° C, holding 180 ~ 240min, to 5 ~ 10 ° C / min heating up to 2000 ~ 2200 ° C, holding 120 ~ 360min.

[0010] 采用本发明所述制备方法制得的多孔钽特别适用于作为承重骨组织创伤或骨缺损处的连结构件。 [0010] The preparation method of the present invention prepared porous tantalum is particularly suitable for use as load-bearing bone tissue trauma or bone defect connecting member. 再者,所述的制备方法工艺简单、易控;整个制备过程无害、无污染、无毒害粉尘,对人体无副作用。 Furthermore, the preparation process is simple, easy to control; the entire preparation process harmless, non-polluting, non-toxic dust, the human body without side effects. 而且在制备过程中优先采用在烧结过程中能够全部分解,没有残留的粘结剂、分散剂、有机泡沫体等,将有利于保证植入材料的生物相容性和生物安全性。 And during the preparation given priority during the sintering process can be fully decomposed, there is no residual adhesive, dispersant, organic foams, etc., will help ensure that the implant material biocompatibility and biological safety.

[0011] 所述的有机粘结剂优选聚乙烯醇,也可以采用淀粉、乙基纤维素等类似物质;所述的分散剂通常采用水、无水乙醇等,其中优选水。 [0011] The organic binder is preferably polyvinyl alcohol, starch may be used, ethyl cellulose and similar substances; said dispersant usually water, ethanol, etc., water being preferred. 所述的有机泡沫体优选聚氨酯泡沫,也可以是聚醚酯泡沫等类似物质。 The organic foam is preferably a polyurethane foam, the foam may be polyether ester and the like substances.

[0012] 本发明的进一步的特点是:采用其平均粒径小于43 μ m、氧含量小于0.1%的金属钽粉,采用聚乙烯醇水溶液为粘结剂和水为分散剂与所述的钽粉制成钽粉浆料,有机泡沫体为聚氨酯泡沫,然后真空干燥除去水,形成的多孔钽的孔隙度介于50~70%,孔隙直径150 ~600 μ mD [0012] A further feature of the present invention are: the use of an average particle size of less than 43 μ m, an oxygen content of less than 0.1% of tantalum metal powder, an aqueous solution of polyvinyl alcohol as a binder and water as the dispersant and the tantalum powder made of tantalum powder slurry organic foams of polyurethane foam, and then vacuum dried to remove water, the porosity of the formation of a porous tantalum is between 50 to 70%, pore diameter of 150 ~ 600 μ mD

[0013] 其中,将聚乙烯醇用蒸馏水加热至溶解,采用重量百分比2~8% (优选4~5%)聚乙烯醇水溶液与金属钽粉制成钽粉浆料,其中,将重量为6~9份(优选7份)的金属钽粉加入重量为1份的所述聚乙烯醇水溶液中,搅拌均匀制成浆糊状;并浇注于孔径为0.48~0.89mm,密度0.015g/cm3~0.035g/cm3,硬度大于50。 [0013] wherein, the distilled water was heated to dissolve the polyvinyl alcohol, the use of 2 to 8% by weight (preferably 4-5%) aqueous solution of polyvinyl alcohol made from tantalum powder of metal tantalum powder slurry, wherein the weight 6 The aqueous polyvinyl alcohol solution to 9 parts (preferably 7 parts) of tantalum powder was added 1 part by weight, the stir into a paste-like; and pouring in a pore size of 0.48 ~ 0.89mm, density 0.015g / cm3 ~ 0.035g / cm3, hardness greater than 50. (优选孔径为0.56~0.72臟,密度0.0258/0113,硬度50°~80。)的聚氨酯泡沫中。 (Preferably a pore size of 0.56 to 0.72 dirty, density 0.0258 / 0113, the hardness of 50 ° ~ 80.) Polyurethane foam.

[0014] 优先选择平均粒径小于43 μ m、氧含量小于0.1 %的金属钽粉有助于减少杂质的含量,保证材料具有较好的力学性能;选择孔径为0.48~0.89mm,密度0.025g/cm3~0.035g/cm3,硬度大于50°的聚氨酯泡沫有助于保证多孔钽的孔隙度与孔隙直径。 [0014] preferred average particle size of less than 43 μ m, an oxygen content of less than 0.1% of tantalum powder to help reduce levels of impurities, ensuring the material has good mechanical properties; choose a pore size of 0.48 ~ 0.89mm, density 0.025g /cm3~0.035g/cm3, hardness greater than 50 ° of the polyurethane foam helps to ensure that the porosity and pore diameter of the porous tantalum. 本发明这样的技术处理优化了工艺条件,将保证植入多孔钽材料的生物相容性和生物安全性。 Technical process of the invention that optimizes the process conditions, will ensure the safety of the implant biocompatible and porous tantalum material.

[0015] 本发明另一方面的进一步的特点是:干燥的真空度保持10_2~IPa真空度,然后在保护气氛下,例如真空度10_4~10_3Pa,温度400°C~800°C条件下进行除去有机粘结剂和有机泡沫体的脱脂处理;烧结处理:真空度为10_4Pa~10_3Pa,以12~15°C /min升温至1600~1800°C、保温180~200min、随炉冷至200~300°C,再以16~19°C /min升温至1500 ~1800°C、保温220 ~240min,以5 ~8°C /min 升温至2000 ~2200°C、保温250 ~320min,烧结过程保温时可以充惰性气体保护代替真空保护;最后进行真空退火处理,其中真空退火处理是指经过真空烧结后继续保持温度处于1000~1250°C,保温时间I~4小时,真空度为低于10_4~10_3Pa。 [0015] A further aspect of the invention is characterized: dry vacuum level 10_2 ~ IPa vacuum, then under protective atmosphere, such as vacuum degree 10_4 ~ 10_3Pa, temperature of 400 ° C ~ 800 ° C to be removed degreasing organic binder and organic foam; sintering process: a vacuum degree of 10_4Pa ~ 10_3Pa, to 12 ~ 15 ° C / min heating up to 1600 ~ 1800 ° C, holding 180 ~ 200min, with furnace cooling to 200 ~ 300 ° C, then 16 ~ 19 ° C / min was heated to 1500 ~ 1800 ° C, holding 220 ~ 240min, to 5 ~ 8 ° C / min was heated to 2000 ~ 2200 ° C, holding 250 ~ 320min, when the heat sintering process can be filled with inert gas in place of vacuum protection; finally vacuum annealing, vacuum annealing treatment wherein after vacuum sintering means to maintain the temperature at 1000 ~ 1250 ° C, holding time I ~ 4 hours, and the degree of vacuum is lower than 10_4 ~ 10_3Pa .

[0016] 上述脱脂处理条件还包括有:以0.5°C /min~5°C /min的速率逐步升温至400~800°C,以氩气通入构成保护气氛并保温30min~120min ; [0016] Degreasing treatment conditions described above further includes: to 0.5 ° C / min ~ 5 ° C / min rate and gradually raised to 400 ~ 800 ° C, with argon gas introduced into the protective atmosphere constituted and incubated 30min ~ 120min;

[0017] 真空烧结条件为:真空度为KT4Pa~10_3Pa,以13°C /min升温至1800°C、保温200min、随炉冷至200 ~300°C,再以17°C /min 升温至1800°C、保温230min,以7°C /min 升温至2000 ~2200°C、保温300min ; [0017] The vacuum sintering conditions: a vacuum degree of KT4Pa ~ 10_3Pa, to 13 ° C / min heating up to 1800 ° C, insulation 200min, with furnace cooling to 200 ~ 300 ° C, then 17 ° C / min heating up to 1800 ° C, insulation 230min, to 7 ° C / min heating up to 2000 ~ 2200 ° C, insulation 300min;

[0018] 真空烧结后的冷却条件还包括有:真空度低于10_3Pa,以不高于25°C /min,不低于IO0C /min渐降冷却速率方式,对烧结多孔体分段降温冷却至800°C,各段保温时间30min~90min,然后随炉冷却至常温; [0018] After cooling vacuum sintering conditions further comprises: a vacuum of less than 10_3Pa, not higher than 25 ° C / min, not less than IO0C / min cooling rate gradually decreased manner, the porous sintered body is cooled to a sub-cooled 800 ° C, the holding time of each segment 30min ~ 90min, then cooled to room temperature in the furnace;

[0019] 真空退火条件还包括有:真空度低于10_4Pa,以不高于30°C /min的速率升至1000~1250°C,保温4h~6h ;再以先慢后快以不低于5°C /min但不高于30°C /min的冷却速率分段冷却至室温,各段的保温时间呈递减且不超过1.5h~3h内选择。 [0019] vacuum annealing conditions further comprising: a vacuum of less than 10_4Pa, not higher than 30 ° C / min rate rose to 1000 ~ 1250 ° C, holding 4h ~ 6h; then after the first slow-fast with not less than 5 ° C / min but not higher than 30 ° C / min cooling rate segment cooled to room temperature, each segment of the holding time was not more than 1.5h ~ 3h decreasing the selection.

[0020] 在此基础上更进一步的特点是:所述真空干燥的干燥温度60~100 °C,干燥时间4~8小时;所述脱脂处理条件还包括有:逐步升温至600~800°C,以纯净氩气(99.9999% )通入构成保护气氛,以I~5°C /min的速率从室温升至400°C,保温30~60min,以0.5~1.5°C /min的速率从400°C升至600~800°C,保温60~120min,所述真空烧结条件为:空度为KT4Pa~10_3Pa,以13°C /min升温至1800°C、保温200min、随炉冷至200~300°C,再以17°C /min升温至1800°C、保温230min,以7°C /min升温至2000~2200°C、保温300min ; [0020] On this basis, further characterized by: the vacuum drying drying temperature 60 ~ 100 ° C, the drying time of 4 to 8 hours; the degreasing process condition further comprises: gradually raised to 600 ~ 800 ° C , in pure argon (99.9999%) pass into the constitution to protect the atmosphere, at the rate I ~ 5 ° C / min from room temperature to 400 ° C, holding 30 ~ 60min, to 0.5 ~ 1.5 ° C / min rate from 400 ° C rose to 600 ~ 800 ° C, insulation 60 ~ 120min, the vacuum sintering conditions: air degree KT4Pa ~ 10_3Pa, to 13 ° C / min heating up to 1800 ° C, insulation 200min, with furnace cooling to 200 ~ 300 ° C, then 17 ° C / min heating up to 1800 ° C, insulation 230min, to 7 ° C / min heating up to 2000 ~ 2200 ° C, insulation 300min;

[0021] 真空烧结后的冷却条件还包括有:真空度为KT4Pa~KT3Pa ;以10~20°C /min的速率冷却至1500~1600°C,保温30~60min ;以12~20°C /min的速率冷却至1200~1250°C,保温60~90min ;以10~20°C /min的速率冷却至800°C,然后随炉冷却;所述真空退火条件还包括有:以15~30°C /min的速率升至1000~1250°C,保温240~480min,真空度为KT4Pa~l(T3Pa,再以5~10°C /min的速率冷却至1000°C,保温90~180min,真空度为IO4Pa~KT3Pa ;以10~20°C /min的速率冷却至800°C,保温60~120min,真空度低于KT4Pa ;以20~30°C /min的速率冷却至室温,真空度为KT4Pa~10_3Pa。 [0021] After cooling vacuum sintering conditions further comprises: a vacuum degree of KT4Pa ~ KT3Pa; at a rate of 10 ~ 20 ° C / min cooling to 1500 ~ 1600 ° C, holding 30 ~ 60min; to 12 ~ 20 ° C / min cooling rate to 1200 ~ 1250 ° C, holding 60 ~ 90min; at a rate of 10 ~ 20 ° C / min cooling to 800 ° C, then cooling with the furnace; the vacuum annealing conditions further comprising: 15 to 30 ° C / min rate was increased to 1000 ~ 1250 ° C, holding 240 ~ 480min, vacuum degree KT4Pa ~ l (T3Pa, at a rate of 5 ~ 10 ° C / min cooling to 1000 ° C, holding 90 ~ 180min, vacuum degree IO4Pa ~ KT3Pa; to 10 ~ 20 ° C / min cooling rate to 800 ° C, insulation 60 ~ 120min, vacuum of less than KT4Pa; to 20 ~ 30 ° C / min rate was cooled to room temperature, the degree of vacuum is KT4Pa ~ 10_3Pa.

[0022] 其中对真空干燥、脱脂处理等是有助于减少多孔钽中杂质的含量,提高生物相容性和生物安全性好及力学性能;对有机泡沫体材料的优化以解决烧结过程中泡沫骨架的不易塌陷问题;对烧结及退火步骤的工艺条件优化,进一步提高多孔钽的力学性能如延展性、减小烧结颈的断裂率。 [0022] wherein vacuum drying, degreasing treatment is to help reduce the content of porous tantalum impurities, improve biocompatibility and good safety and mechanical properties; optimization of organic foam material to address the foam during sintering skeleton easy to collapse problem; sintering and annealing step optimization process conditions to further improve the mechanical properties of porous tantalum such as ductility, reduced sintering neck fracture rate.

[0023] 上述方法制得的多孔钽材料,经过测试其杂质含量低于0.5% ;该多孔钽成品孔隙分布均匀且连通,密度5.00~8.33g/cm3,孔隙度50~70%,孔隙直径150~600 μ m,弹性模量2.5~4.0GPa,弯曲强度130~150MPa,抗压强度75~88MPa,延伸率9.3%~10.2%。 [0023] The method described above prepared porous tantalum material tested impurity content is less than 0.5%; the porous tantalum refined and uniformly distributed pores communicating, density 5.00 ~ 8.33g / cm3, a porosity of 50 to 70%, pore diameter 150 ~ 600 μ m, the elastic modulus of 2.5 ~ 4.0GPa, bending strength 130 ~ 150MPa, compressive strength of 75 ~ 88MPa, elongation of 9.3% to 10.2%. 本发明多孔钽材料不仅生物相容性、安全性好,而且力学性能特别强度高,非常适合用于替代人体承重部位的骨组织。 The present invention is not only porous tantalum material biocompatibility, safety, and high mechanical properties, especially strength, very suitable for load-bearing parts of the body to replace bone tissue. 附图说明 Brief Description

[0024] 图1是本发明所述制备方法制备的多孔钽结构的扫描电子显微镜分析图(SEM图); [0024] FIG. 1 is a scanning electron microscope analysis diagram of the present invention prepared by the method for preparing a porous tantalum structure (SEM image);

[0025] 从附图可观察到:本发明所述多孔钽高孔隙,孔隙分布均匀连通。 [0025] can be observed from the figures: high-porosity porous tantalum to the present invention, the pore distribution communication. 从附图中可看出本发明所述的多孔钽连通孔隙有利于成骨细胞粘附、分化和生长,促进骨的长入,可加强植入体与骨之间的连接,利于实现生物固定。 As can be seen from the figures interconnected pores of porous tantalum present invention facilitates osteoblast adhesion, differentiation and growth, and promote bone ingrowth, can reinforce the connection between the implant and the bone, which will help achieve biological fixation .

具体实施方式 DETAILED DESCRIPTION

[0026] 下面通过实施例对本发明进行具体的描述,有必要在此指出的是以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术人员可以根据上述本发明内容对本发明作出一些非本质的改进和调整。 [0026] The following examples of the present invention will be specifically described, it is necessary to point out that the following examples are only used for the present invention will be further explained, can not be construed as limiting the scope of the present invention, the skilled in the art can the contents of the present invention to make some improvements and adjustments nonessential present invention.

[0027] 实施例1:称取聚乙烯醇12.5g,放入装有240ml蒸馏水的容器中;将其放在电炉上加温并搅拌使之成为聚乙烯醇水溶液。 [0027] Example 1: Weigh polyvinyl alcohol 12.5g, containing 240ml of distilled water into the container; it will be placed on electric heating and stirring to form an aqueous solution of polyvinyl alcohol. 用200g天平称量平均粒径小于43微米、氧含量小于0.1 %的钽粉60g,加入50ml冷却的聚乙烯醇水溶液,搅拌混合均匀,使之成为钽粉浆料。 With an average particle size of less than 200g weighing scales 43 m, an oxygen content of less than 0.1% tantalum powder 60g, 50ml aqueous polyvinyl alcohol solution was added a cooled, stirred and mixed evenly, making tantalum powder slurry. 选用10 X 10 X 30mm多孔聚氨酯泡沫(平均孔径为0.48mm,密度0.025g/cm3,硬度50° )放入其中浇注,直至聚氨酯泡沫孔隙注满钽粉浆料,用夹子夹出吸满钽粉浆料的聚氨酯泡沫放入瓷盘中。 Selection of 10 X 10 X 30mm porous polyurethane foam (average pore diameter of 0.48mm, density 0.025g / cm3, hardness 50 °) into which the casting until the pores filled with polyurethane foam tantalum powder slurry, clip-out suck tantalum powder polyurethane foam slurry into the vat. 在真空干燥箱中干燥,干燥温度60°C,干燥时间8小时,真空度保持IPa。 Dried in a vacuum oven, drying temperature 60 ° C, the drying time of 8 hours, the degree of vacuum maintained IPa. 脱脂处理:真空度低于10_4Pa,温度600°C,保温时间120分钟。 Degreasing treatment: the vacuum is below 10_4Pa, temperature 600 ° C, the holding time 120 minutes. 真空烧结:所述烧结步骤是真空度为KT4Pa~l(T3Pa,以13。。/min升温至1800。。、保温200min、随炉冷至200~300。。,再以17°C /min 升温至1800°C、保温230min,以7°C /min 升温至2000 ~2200°C、保温300min ;烧结过程充氩气保护,取出产品后去除表面灰尘及污物,制得的样品再进行常规的后处理得多孔钽成品。 Vacuum sintering: the sintering step is a vacuum degree of KT4Pa ~ l (T3Pa, warmed to 13 ../ min to 1800 .., insulation 200min, with furnace cooling to 200 ~ 300 .., and then to 17 ° C / min heating to 1800 ° C, insulation 230min, to 7 ° C / min heating up to 2000 ~ 2200 ° C, insulation 300min; sintering process filled with argon protection, after removing the product to remove surface dust and dirt, then sample prepared routine After much treatment hole tantalum products.

[0028]发明人按 GB/T5163-2006、GB/T5249-1985、GB/T6886-2001 等标准对上述多孔钽成品的多孔材料密度、孔隙率、孔径及各种力学性能进行检测:其杂质含量低于0.5%的成品,其孔隙分布均匀且连通,密度6.7`g/cm3,孔隙率56%,孔隙平均直径300 μ m,弹性模量3.0GPa,弯曲强度150MPa,抗压强度82MPa,延伸率9.8 %。 [0028] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and a variety of mechanical properties of the porous tantalum finished product for testing: impurity content less than 0.5% of the finished product, and a communicating pore distribution, density 6.7`g / cm3, a porosity of 56%, an average pore diameter of 300 μ m, the elastic modulus of 3.0GPa, flexural strength 150MPa, compressive strength 82MPa, elongation 9.8%.

[0029] 实施例2:称取聚乙烯醇10g,放入装有200ml蒸馏水的容器中;将其放在电炉上加温并搅拌使之成为聚乙烯醇水溶液。 [0029] Example 2: Weigh polyvinyl alcohol 10g, containing 200ml distilled water into the container; it will be placed on electric heating and stirring to form an aqueous solution of polyvinyl alcohol. 用200g天平称量平均粒径小于43微米、氧含量小于0.1%的钽粉40g,加入32ml聚乙烯醇水溶液,搅拌混合均匀,使之成为钽粉浆料。 With an average particle size of less than 200g weighing scales 43 m, an oxygen content of less than 0.1% tantalum powder 40g, 32ml aqueous polyvinyl alcohol solution was added, stirred and mixed evenly, making tantalum powder slurry. 选用10 X 10 X 25mm多孔聚氨酯泡沫(平均孔径为0.56mm,密度0.030g/cm3,硬度60° )放入其中浇注,直至聚氨酯泡沫孔隙注满钽粉浆料,用夹子夹出吸满钽粉浆料的聚氨酯泡沫放入瓷盘中。 Selection 10 X 10 X 25mm porous polyurethane foam (average pore diameter of 0.56mm, density 0.030g / cm3, hardness 60 °) into which the casting until pore polyurethane foam filled tantalum powder slurry, a clip-suck tantalum powder polyurethane foam slurry into the vat. 在真空干燥箱中干燥,干燥温度100°c,干燥时间4小时,真空度保持10_2Pa。 Dried in a vacuum oven, drying temperature 100 ° c, drying time 4 hours, the degree of vacuum maintained 10_2Pa. 脱脂处理:真空度10_4Pa,温度800°C,保温时间120分钟。 Degreasing treatment: vacuum degree 10_4Pa, temperature 800 ° C, the holding time 120 minutes. 真空烧结:所述烧结步骤是真空度为KT4Pa~l(T3Pa,以10°C /min升温至1600。。、保温240min、随炉冷至200~300。。,再以200C /min 升温至1500°C、保温180min,以5°C /min 升温至2000 ~2200°C、保温360min,烧结过程充氩气保护,取出产品后去除表面灰尘及污物,制得的样品再进行常规的后处理得多孔组成品。 Vacuum sintering: the sintering step is a vacuum degree of KT4Pa ~ l (T3Pa, to 10 ° C / min to 1600 .. heating, insulation 240min, with furnace cooling to 200 ~ 300 .., and then to 200C / min heating up to 1500 ° C, insulation 180min, to 5 ° C / min heating up to 2000 ~ 2200 ° C, insulation 360min, the sintering process argon protection, surface dust and dirt, and the resulting product is removed after the removal of the sample and then subjected to conventional treatment composed of a porous product.

[0030]发明人按 GB/T5163-2006、GB/T5249-1985、GB/T6886-2001 等标准对上述多孔钽成品的多孔材料密度、孔隙率、孔径及各种力学性能进行检测:其杂质含量低于0.5%的成品,其孔隙分布均匀且连通,密度8.0g/cm3,孔隙率66%,孔隙平均直径400 μ m,弹性模量 [0030] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and a variety of mechanical properties of the porous tantalum finished product for testing: impurity content less than 0.5% of the finished product, and a communicating pore distribution, density 8.0g / cm3, a porosity of 66%, an average pore diameter of 400 μ m, the elastic modulus

3.5GPa,弯曲强度140MPa,抗压强度75MPa,延伸率10.1 %。 3.5GPa, flexural strength 140MPa, compressive strength 75MPa, elongation of 10.1%.

[0031] 实施例3:称取聚乙烯醇llg,放入装有220ml蒸馏水的容器中;将其放在电炉上加温并搅拌使之成为聚乙烯醇水溶液。 [0031] Example 3: Weigh polyvinyl llg, equipped with 220ml of distilled water into the container; it will be placed on electric heating and stirring to form an aqueous solution of polyvinyl alcohol. 用200g天平称量平均粒径小于43微米、氧含量小于0.1%的钽粉45g,加入36ml聚乙烯醇水溶液,搅拌混合均匀,使之成为钽粉浆料。 With an average particle size of less than 200g weighing scales 43 m, an oxygen content of less than 0.1% tantalum powder 45g, 36ml aqueous polyvinyl alcohol solution was added, stirred and mixed evenly, making tantalum powder slurry. 选用8X8X25mm多孔聚氨酯泡沫(平均孔径为0.70mm,密度0.035g/cm3,硬度70° )放入其中浇注,直至聚氨酯泡沫孔隙注满钽粉浆料,用夹子夹出吸满钽粉浆料的聚氨酯泡沫放入瓷盘中。 Selection 8X8X25mm porous polyurethane foam (average pore diameter of 0.70mm, density 0.035g / cm3, hardness 70 °) into which the casting until the pores filled with polyurethane foam tantalum powder slurry, clip-out suck tantalum powder slurry of polyurethane foam into the vat. 在真空干燥箱中干燥,干燥温度80°C,干燥时间6小时,真空度保持KT1Pa15脱脂处理:真空度10_3Pa,温度700°C,保温时间90分钟。 Dried in a vacuum oven, drying temperature 80 ° C, drying time 6 hours, the degree of vacuum maintained KT1Pa15 degreasing treatment: vacuum degree 10_3Pa, temperature 700 ° C, holding time 90 minutes. 真空烧结:所述烧结步骤是真空度为10_4Pa~10¾,以200C /min 升温至1800。 Vacuum sintering: the sintering step is a vacuum degree of 10_4Pa ~ 10¾, to 200C / min to warm to 1800. . 、保温120min、随炉冷至200 ~300。 Insulation 120min, with furnace cooling to 200 to 300. . ,再以10°C /min 升温至1800°C、保温240min,以10°C /min升温至2000~2200°C、保温120min,烧结过程充氩气保护,取出产品后去除表面灰尘及污物,制得的样品再进行常规的后处理得多孔钽成品。 , Then 10 ° C / min temperature was raised to 1800 ° C, holding 240min, to 10 ° C / min was heated to 2000 ~ 2200 ° C, holding 120min, argon gas protection of the sintering process, the removal of the product surface after removing dust and dirt , prepared samples subjected to conventional post-treatment and then a porous tantalum products.

[0032]发明人按 GB/T5163-2006、GB/T5249-1985、GB/T6886-2001 等标准对上述多孔钽成品的多孔材料密度、孔隙率、孔径及各种力学性能进行检测:其杂质含量低于0.5%的成品,其孔隙分布均匀且连通,密度5.0g/cm3,孔隙率70%,孔隙平均直径450 μ m,弹性模量 [0032] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and a variety of mechanical properties of the porous tantalum finished product for testing: impurity content less than 0.5% of the finished product, and a communicating pore distribution, density 5.0g / cm3, a porosity of 70%, an average pore diameter of 450 μ m, the elastic modulus

5.5GPa,弯曲强度130MPa,抗压强度86MPa,延伸率9.5%。 5.5GPa, flexural strength 130MPa, compressive strength 86MPa, elongation of 9.5%.

[0033] 实施例4:称取聚乙烯醇12g,放入装有230ml蒸馏水的容器中;将其放在电炉上加温并搅拌使之成为聚乙烯醇水溶液。 [0033] Example 4: Weigh polyvinyl alcohol 12g, containing 230ml distilled water into the container; it will be placed on electric heating and stirring to form an aqueous solution of polyvinyl alcohol. 用200g天平称量平均粒径小于43微米、氧含量小于0.1%的钽粉50g,加入40ml聚乙烯醇水溶液,搅拌混合均匀,使之成为钽粉浆料。 With an average particle size of less than 200g weighing scales 43 m, an oxygen content of less than 0.1% tantalum powder 50g, 40ml aqueous polyvinyl alcohol solution was added, stirred and mixed evenly, making tantalum powder slurry. 选用12 X 12 X 30mm多孔聚氨酯泡沫(孔径为0.60mm,密度0.027g/cm3,硬度80° )放入其中浇注,直至聚氨酯泡沫孔隙注满钽粉浆料,用夹子夹出吸满钽粉浆料的聚氨酯泡沫放入瓷盘中。 Selection of 12 X 12 X 30mm porous polyurethane foam (pore size 0.60mm, density 0.027g / cm3, hardness 80 °) into which the casting until the pores filled with polyurethane foam tantalum powder slurry, clip-out suck tantalum slip polyurethane foam material into the porcelain dish. 在真空干燥箱中干燥,干`燥温度90°C,干燥时间5小时,真空度保持IPa。 Dried in a vacuum oven, dry 'drying temperature 90 ° C, the drying time of 5 hours, and vacuum level IPa. 脱脂处理:真空度10_4~10_3Pa,温度500°C,保温时间120分钟。 Degreasing treatment: vacuum degree 10_4 ~ 10_3Pa, temperature 500 ° C, the holding time 120 minutes. 真空烧结:所述烧结步骤是真空度为KT4Pa~l(T3Pa,以13。。/min升温至1700。。、保温210min、随炉冷至200~300。。,再以15°C /min 升温至1600°C、保温210min,以8°C /min 升温至2000 ~2200°C、保温260min,烧结过程充氩气保护,取出产品后去除表面灰尘及污物,制得的样品再进行常规的后处理得多孔组成品。 Vacuum sintering: the sintering step is a vacuum degree of KT4Pa ~ l (T3Pa, warmed to 13 ../ min to 1700 .., insulation 210min, with furnace cooling to 200 ~ 300 .., and then to 15 ° C / min heating to 1600 ° C, insulation 210min, to 8 ° C / min heating up to 2000 ~ 2200 ° C, insulation 260min, the sintering process is filled with argon protection, after removing the product to remove surface dust and dirt, then sample prepared routine After much treatment hole composition products.

[0034]发明人按 GB/T5163-2006、GB/T5249-1985、GB/T6886-2001 等标准对上述多孔钽成品的多孔材料密度、孔隙率、孔径及各种力学性能进行检测:其杂质含量低于0.5%的成品,其孔隙分布均匀且连通,密度8.33g/cm3,孔隙率50%,孔隙平均直径350 μ m,弹性模量 [0034] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and a variety of mechanical properties of the porous tantalum finished product for testing: impurity content less than 0.5% of the finished product, and a communicating pore distribution, density 8.33g / cm3, a porosity of 50%, an average pore diameter of 350 μ m, the elastic modulus

2.7GPa,弯曲强度142MPa,抗压强度81MPa,延伸率9.8%。 2.7GPa, flexural strength 142MPa, compressive strength of 81MPa, elongation of 9.8%.

[0035] 实施例5:一种多孔钽,它以粒径小于43 μ m、氧含量小于0.1 %的金属钽粉为原料,以聚乙烯醇水溶液为粘结剂溶液制成钽粉浆料,并浇注于聚氨酯泡沫载体中;然后真空干燥、脱脂处理、真空烧结、真空退火及常规后处理制得。 [0035] Example 5: A porous tantalum, it is to a particle size of less than 43 μ m, an oxygen content of less than 0.1% of tantalum powder as raw material, polyvinyl alcohol solution as a binder solution made of tantalum powder slurry and cast in polyurethane foam carrier; then dried under vacuum degreasing treatment, vacuum sintering, vacuum annealing and conventional post-treatment system.

[0036] 其中,选用的聚氨酯泡沫,其孔径为0.72~0.56mm,密度0.025g/cm3,硬度50°~80。 [0036] wherein the selected polyurethane foam, a pore size of 0.72 ~ 0.56mm, density 0.025g / cm3, hardness 50 ° ~ 80. ;

[0037] 真空干燥:真空度保持10_2~IPa,以除去注满钽粉浆料的聚氨酯泡沫中的水分; [0037] Vacuum drying: vacuum was maintained 10_2 ~ IPa, to remove the tantalum powder slurry filled polyurethane foam water;

[0038] 脱脂处理:在惰性气体保护气氛下或真空度10_4~10_3Pa,温度400°C~800°C,并保温时间30~120分钟以除去其中的聚乙烯醇及聚氨酯泡沫; [0038] Degreasing treatment: In an inert gas atmosphere or under a vacuum degree 10_4 ~ 10_3Pa, a temperature of 400 ° C ~ 800 ° C, and the holding time of 30 to 120 minutes to remove the polyvinyl alcohol and polyurethane foam;

[0039] 真空烧结:所述烧结步骤是真空度为KT4Pa~I(T3Pa,以16°C /min升温至1650°C、保温190min、随炉冷至200~300°C,再以18°C /min升温至1800°C、保温200min,以6°C /min 升温至2000 ~2200。。、保温270min ; [0039] vacuum sintering: the sintering step is a vacuum degree of KT4Pa ~ I (T3Pa, to 16 ° C / min heating up to 1650 ° C, insulation 190min, with furnace cooling to 200 ~ 300 ° C, then 18 ° C / min heating to 1800 ° C, insulation 200min, to 6 ° C / min heating to 2000 to 2200 .., insulation 270min;

[0040] 真空退火:经过真空烧结后继续保持温度处于1000~1250°C,保温时间I~4小时,真空度为10_4~10_3Pa,以进行去应力退火处理;制得的样品再进行常规的后处理得多孔组成品。 [0040] vacuum annealing: After vacuum sintering temperature is maintained at 1000 ~ 1250 ° C, holding time I ~ 4 hours, and a vacuum degree of 10_4 ~ 10_3Pa, in order to de-stress annealing; prepared specimen was then subjected to conventional Processing a porous composition products.

[0041]发明人按 GB/T5163-2006、GB/T5249-1985、GB/T6886-2001 等标准对上述多孔钽成品的多孔材料密度、孔隙率、孔径及各种力学性能进行检测:其杂质含量低于0.5%的成品,其孔隙分布均匀且连通,密度6.3g/cm3,孔隙率62%,孔隙平均直径220 μ m,弹性模量 [0041] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and a variety of mechanical properties of the porous tantalum finished product for testing: impurity content less than 0.5% of the finished product, and a communicating pore distribution, density 6.3g / cm3, a porosity of 62%, an average pore diameter of 220 μ m, the elastic modulus

3.3GPa,弯曲强度136MPa,抗压强度84MPa,延伸率10.2%。 3.3GPa, flexural strength 136MPa, compressive strength of 84MPa, elongation of 10.2%.

[0042] 在上述实施例5给出的方法中,我们还可以对其中的各种条件作其他选择同样能得到本发明所述的多孔钽。 [0042] In the method described in Example 5 shows, we can also make a variety of conditions in which other options can also obtain a porous tantalum to the present invention.

[0043] [0043]

Figure CN102796905BD00091
Figure CN102796905BD00101

[0046] [0046]

Figure CN102796905BD00111

[0047] 所得多孔钽成品按前述方法检测: [0047] The resultant porous tantalum finished by the aforementioned method to detect:

[0048] [0048]

Figure CN102796905BD00112
Citas de patentes
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CN101549175A15 May 20097 Oct 2009中南大学Method for preparation of pore heterogeneous distribution bionic bone material
US528286111 Mar 19921 Feb 1994UltrametOpen cell tantalum structures for cancellous bone implants and cell and tissue receptors
Otras citas
Referencia
1节云峰等.烧结温度对泡沫铌力学性能及微观组织的影响.《中国有色金属学报》.2010,第20卷(第10期),第2014-2018页.
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Clasificación internacionalC22C1/08, C22C27/02, A61L27/56, A61L27/04
Clasificación cooperativaC22C27/02, B22F3/1021, A61L2400/08, A61L2430/02, A61L27/56, B22F3/24, B22F3/1137, A61L27/047
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