CN102796903B - Method for preparing medical porous metal material capable of replacing bearing bone tissue - Google Patents

Method for preparing medical porous metal material capable of replacing bearing bone tissue Download PDF

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CN102796903B
CN102796903B CN 201110300386 CN201110300386A CN102796903B CN 102796903 B CN102796903 B CN 102796903B CN 201110300386 CN201110300386 CN 201110300386 CN 201110300386 A CN201110300386 A CN 201110300386A CN 102796903 B CN102796903 B CN 102796903B
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min
rate
vacuum
forming agent
pore
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CN102796903A (en )
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叶雷
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重庆润泽医药有限公司
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/047Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION, OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS, OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56Porous materials, e.g. foams or sponges
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • B22F3/11Making porous workpieces or articles
    • B22F3/1121Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1125Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02Alloys based on vanadium, niobium, or tantalum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

Abstract

一种制备替代承重骨组织的医用多孔金属材料的制备方法,钽粉与造孔剂、成型剂混合,再将混合粉末压制到有机泡沫体中成型、脱脂、烧结、冷却和热处理;压制成型压力50~100Mpa,脱脂过程以0.3℃/min~2℃/min的速率逐步升温至400~800℃,以氩气通入构成保护气氛并保温300min~360min;造孔剂为碳酸氢铵或双氧水,所述成型剂为硬脂酸、硬脂酸锌、石蜡、合成树脂中的一种或多种;在10-4Pa~10-3Pa下,以10~20℃/min升温至800~900℃、保温240~480min,再以2~5℃/min冷至400℃、保温120~300min,然后随炉冷却至室温。 A process for producing a medical material, a porous metal bearing bone tissue substitute prepared, tantalum powder and pore-forming agent, molding agent are mixed, then the mixed powder is pressed into the organic foam molding, debinding, sintering, heat treatment and cooling; press molding pressure 50 ~ 100Mpa, degreasing process at a rate of 0.3 ℃ / min ~ 2 ℃ / min and gradually warmed up to 400 ~ 800 ℃, into argon atmosphere constituted and incubated 300min ~ 360min; pore-forming agent is ammonium bicarbonate or hydrogen peroxide, the forming agent is stearic acid, zinc stearate, paraffin wax, synthetic resin, one or more; at 10-4Pa ~ 10-3Pa, at 10 ~ 20 ℃ / min was heated to 800 ~ 900 ℃, insulation 240 ~ 480min, then to 2 ~ 5 ℃ / min was cooled to 400 ℃, heat 120 ~ 300min, then furnace cooling to room temperature. 经过测试其杂质含量低于0.2%、密度达6.67~8.34g/cm3,孔隙度达50~60%,孔隙直径达150~450μm,弹性模量可达4.5~6.0Gpa,弯曲强度可达100~120Mpa。 Tested impurity content of less than 0.2%, a density of 6.67 ~ 8.34g / cm3, a porosity of 50% to 60%, pore diameter of 150 ~ 450μm, the modulus of elasticity of up to 4.5 ~ 6.0Gpa, the bending strength of up to 100 ~ 120Mpa.

Description

一种制备替代承重骨组织的医用多孔金属材料的方法 A process for preparing a porous metal material for medical alternative bearing bone tissue method

技术领域 FIELD

[0001] 本发明涉及一种多孔医用金属植入材料的制备方法,特别是涉及一种适用于替代承重部位骨组织的多孔医用植入金属材料的制备方法。 The method of preparation of porous medical implant metal material [0001] The present invention relates to a method for preparing metallic medical implant of porous material, particularly to a load-bearing portion of a suitable replacement for bone tissue.

背景技术 Background technique

[0002] 多孔医用金属植入材料具有治疗骨组织创伤、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] Porous medical implant material having a metallic treatment of bone tissue trauma, tissue necrosis femoral important and special purpose, such materials are now common metal porous stainless steel, porous titanium metal. 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 the porous implant material and bone tissue trauma treatment with femoral tissue necrosis, the porosity should be 30% to 80%, and preferably all of the pores communicates with a uniform distribution, or both so that the body tissue and bone growth as needed consistent with , 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/铌,由于它具有优秀的生物相容性,其多孔材料有望作为替代前述等传统医用金属生物材料。 [0003] and a refractory metal tantalum / niobium, due to its excellent biocompatibility, which porous material is expected as an alternative to the traditional metallic medical biomaterials. 由于金属钽/铌对人体的无害、无毒、无副作用,以及随着国内外医学的飞速发展,对钽/铌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/铌材料的需求变得越来越迫切,对其要求也越来越高。 Since the tantalum / niobium harmless to humans, non-toxic, no side effects, and with the rapid development of domestic medicine, tantalum / niobium as further in-depth knowledge of the human body implant materials, people on the human body with a porous metal implant demand for tantalum / niobium materials are becoming increasingly urgent, its requirements are also increasing. 其中作为多孔医用植入金属钽/铌,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,则其有望作为一种新型的骨组织替代材料。 Wherein the medical implant is a porous tantalum / niobium, if communication with high porosity and uniform distribution of mechanical properties compatible with the human body, it is expected as a new bone tissue substitute 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] As the porous metal material like a general medical implant of porous metal material such as a powder sintering method substantially as the main processing method, in particular to obtain a porous metal foam with pores in communication evenly distributed using a powder sintering method the metallic powder after drying the slurry in the impregnated organic foam body is re-sintered mostly referred foam impregnation method. 关于粉末烧结所获得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。 Porous metal material on the obtained sintered powder metal which is usually not very good mechanical properties, mainly on how the process is arranged to support the porous media and the elimination of the relationship, the problem collapse during sintering the metal powder. 而已知的文献报道中均没有很好的解决方法而放任自然。 And it is known in the literature are not a good solution and letting nature.

[0005] 采用金属粉末烧`结法制造多孔钽/铌的文献报道很少,特别是以获得医用植入材料用为目的的多孔钽/铌粉末烧结法文献报道几乎没有。 [0005] The metal powder producing firing `knot porous tantalum / niobium few reports in the literature, in particular in obtaining a porous tantalum implant materials for medical purposes / niobium powder sintering method almost no literature. 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”。 Reference may be Publication No. CN200510032174, the name "three-dimensional part of the through hole or holes connected to each other and a porous metal foam preparation method" and CN200710152394, the name "tungsten, and a novel method for preparing porous foam." 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/铌。 However, it has acquired the porous metal material or a filter, or other high-temperature aerospace applications and with the metal rather than as a medical implant material used, the porous metal addition processing nor the porous tantalum / niobium.

[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 an implant applied to cancellous bone, tissue and cell receptors openings tantalum material and its 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。 Such commercial porous tantalum made of pure tantalum, it polyurethane precursor is obtained by thermal degradation of the carbon skeleton of the stent, the carbon backbone is multiple dodecahedron, the grid-like structure which, throughout the entire micro holes, porosity may be up to 98%, then the commercially pure tantalum deposition by chemical vapor infiltration method for bound to the carbon skeleton to form a porous metal microstructure, simply referred to as a 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 which is between 40 ~ 60 μ m; the entire porous material, about 99% of the weight of tantalum and 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。 Document further described, the compressive strength of the porous material 50 ~ 70MPa, the elastic modulus of 2.5 ~ 3.5GPa, a tensile strength of 63MPa. 但是将它作为替代承重骨组织如颅骨等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 as an alternative it bearing cranial bone tissue and other medical porous tantalum implant materials, the mechanical properties such as ductility of the material has significant shortcomings, will affect subsequent processing of the porous tantalum material itself, such as molded parts 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 product of the metal powder sintering method were also obtained in the presence of such deficiencies. 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。 Again because of the limitations of the preparation method, the purity of the finished product is not obtained, the carbon skeleton of the residue, leading to reduced biological safety.

发明内容 SUMMARY

[0007] 本发明的目的在于提供一种韧性好的适用于替代承重部位骨组织的多孔金属材料的制备方法。 [0007] The object of the present invention is to provide a method for preparing good toughness suitable replacement for bone tissue load-bearing parts of the porous metal material.

[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 are achieved by the following technical means:

[0009] 一种制备替代承重骨组织的医用多孔金属材料的制备方法,其特征在于:由钽粉与造孔剂、成型剂混合,再经压制成型、脱脂、烧结、冷却和热处理制得该多孔金属材料;所述压制成型是将混合粉末压制到有机泡沫体中,其压力为50~lOOMpa,所述脱脂过程是以0.30C /min~2V /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300min~360min ;所述造孔剂为碳酸氢铵或双氧水,所述成型剂为硬脂酸、硬脂酸锌、石蜡、合成树脂(优选为丁苯橡胶或异戊橡胶)中的一种或多种;所述热处理是真空度为KT4Pa ~l(T3Pa,以10 ~20°C /min 升温至800 ~900°C、保温240 ~480min,再以2 ~5°C /min冷至400°C、保温120~300min,然后随炉冷却至室温。 [0009] A method for preparing a medical preparation alternative to the porous metal material bearing bone tissue, comprising: a tantalum powder with a pore-forming agent, molding agent are mixed, and then press molding, debinding, sintering, heat treatment and cooling to obtain the porous metal material; press molding the mixed powder is pressed into the organic foam at a pressure of 50 ~ lOOMpa, the degreasing process is 0.30C / min ~ 2V / min and gradually warmed up to a rate of 400 ~ 800 ° C , argon atmosphere into configuration and incubated 300min ~ 360min; the pore-forming agent is ammonium bicarbonate or hydrogen peroxide, the forming agent is stearic acid, zinc stearate, paraffin wax, a synthetic resin (preferably a styrene-butadiene one or more rubber or isoprene rubber) of; the degree of vacuum heat treatment KT4Pa ~ l (T3Pa, at 10 ~ 20 ° C / min was heated to 800 ~ 900 ° C, insulation 240 ~ 480min, then to 2 ~ 5 ° C / min and cooled to 400 ° C, insulation 120 ~ 300min, then furnace cooling to room temperature.

[0010] 在医用多孔金属材料的研发过程中,医用多孔金属材料作为替代承重骨组织的材料,要求其孔隙率较大、这样人体组织才易长入、生物相容性好从而充分地发挥其作用,但孔隙率越大、孔径越大,力学性能如强度、韧性就得不到保证;反之,力学性能好了又易使孔隙率过小、生物相容性不好、密度也过大引起不舒适感;医用多孔钽的制备路线众多,但发明人创造性地提出了采用上述步骤、工艺制备医用多孔钽植入材料,有效防止了采用浸浆法易出现的堵孔、浸浆过程难控制、制得的产品质量不均匀等问题;特别是采用的上述热处理工艺,充分地消除了内应力、使多孔钽材料的组织更均匀、大大提高了所制得的多孔钽材料的韧性、且工艺快捷简单;其制得的多孔钽材料经过测试其杂质含量可低于0.2%、其生物相容性与生物安全性好,密度可达6.67~ [0010] In the development of the porous metal medical material, medical material is used as the porous metal bearing bone tissue substitute material, which requires large porosity, so that it is easy to human tissue ingrowth, biocompatibility to sufficiently exhibit its effect, but the porosity, the larger the aperture, the mechanical properties such as strength, toughness can not be guaranteed; the other hand, good mechanical properties also easy to make the porosity is too small, good biocompatibility, caused by excessive density discomfort; many medical porous tantalum preparative route, the inventors creatively made using the above steps, a medical preparation of porous tantalum implant materials, the use of effectively preventing clogging prone to leaching process slurry, slurry dipping process difficult to control , the resulting product quality problems such as uneven; in particular, the heat treatment process is employed, substantially eliminates the internal stress, the tissue is more uniform porous tantalum material, greatly improving the toughness of the porous tantalum material obtained, and the process quick and easy; its porous tantalum material obtained can be tested impurity content less than 0.2%, its biocompatibility and biological safety, and density of up to 6.67 ~ 8.34g/cm3,孔隙度可达50~60%,孔隙直径可达150~450 μ m ;弹性模`量可达4.5~6.0Gpa、延伸率达10.5~11.7%、弯曲强度可达100~120Mpa、抗压强度可达60~70Mpa,其生物相容性、强韧性均优异,接近人体承重骨组织,本发明多孔钽非常适合用于替代承重骨组织的医用植入材料。 8.34g / cm3, a porosity of up to 50% to 60%, pore diameter of up to 150 ~ 450 μ m; elastic modulus of up to `4.5 ~ 6.0Gpa, extending rate of 10.5 to 11.7%, the bending strength of up to 100 ~ 120Mpa , the compressive strength of up to 60 ~ 70Mpa, biocompatibility, excellent in toughness, load-bearing bone tissue close to the body, the porous tantalum present invention is very suitable to replace load-bearing material of a medical implant bone tissue.

[0011] 本发明采用的原料钽粉的平均粒径小于43微米、氧含量小于0.1%,为市售产品;上述造孔剂、成型剂也均为市售产品。 [0011] The average particle size of the tantalum powder of the present invention, the raw material employed is less than 43 m, an oxygen content of less than 0.1%, a commercially available product; and the pore-forming agent, molding agents are also commercially available products. 本发明真空环境优选采用真空度为10_4Pa~10_3Pa的真空条件。 The present invention is preferably a vacuum atmosphere the vacuum degree of the vacuum 10_4Pa ~ 10_3Pa. 上述有机泡沫体优选聚氨酯泡沫,进一步优选为孔径0.48~0.89mm,密度0.015g/cm3 ~0.035g/cm3,硬度大于50。 The organic foams preferably polyurethane foams described above, the aperture is more preferably 0.48 ~ 0.89mm, density 0.015g / cm3 ~ 0.035g / cm3, a hardness greater than 50. (最优选孔径为0.56 ~0.72mm,密度0.025g/cm3,硬度50°~80° )的聚氨酯泡沫中。 (Most preferably a pore size of 0.56 ~ 0.72mm, density 0.025g / cm3, the hardness of 50 ° ~ 80 °) polyurethane foam.

[0012] 在研发过程中发明人进一步研究发现,若上述制备中控制不好,虽可制得如上所述适合用于替代承重骨组织的医用植入材料但产品质量稳定性不理想、合格率不高:如粉末压制成型难、在压制后部分易出现分层、不均匀,脱脂后部分会出现裂纹等技术问题。 [0012] The inventors have further found that in the development process, control is not good if the above preparation, may be prepared as described above, although suitable for use in alternative medical implant material bearing bone tissue, but not over the product quality stability, yield of not high: press molding powder as hard, part prone to delamination after pressing, uneven, some technical problems such as a crack occurs after degreasing.

[0013] 为了使粉末压制过程中成型更容易,从而提高成品率、成品孔隙均匀性、使制备过程更稳定,上述造孔剂的用量为15~25%、成型剂的用量为7~12%、余量为钽粉,均以体积百分含量计(以体积百分含量计是通过最终多孔钽材料的情况直接推算的单位,在上述造孔剂、成型剂的称量中固体粉末还是根据相应物质的密度计算出其对应的质量称量的、当然若为液体物质则直接采用体积称量),进一步优选为造孔剂为双氧水占18%、成型剂为硬脂酸锌占11%、余量为钽粉、以体积百分含量计;上述压制成型过程中的压力优选为75 ~87Mpa。 [0013] In order to make the powder during pressing molding easier, thereby improving the yield finished pore uniformity, to make the manufacturing process more stable, the above-described pore-forming agent in an amount of 15 to 25%, the amount of forming agent is 7 to 12% , the balance tantalum powder, percentages are on a volume basis (volume percentage content of the case by the final porous tantalum material directly calculating unit, in the above-described pore-forming agent were weighed, forming agent or solid powder according to the calculated density of the respective material quality corresponding weighing, of course, if the liquid substance is employed directly weighing volume), more preferably a pore-forming agent is 18% hydrogen peroxide, zinc stearate forming agent is 11%, balance tantalum powder to the volume percentage basis; and the press-forming process pressure is preferably 75 ~ 87Mpa.

[0014] 为了使脱脂过程中胚体更稳定、减少易出现的部分胚体变形、孔径不均匀,从而进一步提高成品率、质量稳定性,上述脱脂过程是以0.3°C /min~1°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330min~350min ;进一步优选以0.8°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340min。 [0014] In order to skim more stable during the embryo, the embryo reducing portion prone to deformation, non-uniform pore size, thereby further improving the yield, quality stability, the degreasing process is 0.3 ° C / min ~ 1 ° C rate / min and gradually warmed up to 400 ~ 800 ° C, with argon gas introduced into constituting the protective atmosphere and incubated for 330min ~ 350min; more preferably at a rate of 0.8 ° C / min and gradually warmed up to 400 ~ 800 ° C, to iS gas was constituting the atmosphere and incubated 340min.

[0015] 为了更充分地消除材料的内应力、韧性更好,上述热处理步骤是真空度为KT4Pa ~10¾,以15。 [0015] In order to more fully eliminate the internal stress, toughness better, the heat treatment step is a vacuum degree of KT4Pa ~ 10¾, 15. . /min 升温至800 ~900°C、保温260 ~320min,再以3°C /min 冷至400°C、保温120min,再以18°C /min~23°C /min冷却至室温。 / Min was heated to 800 ~ 900 ° C, insulation 260 ~ 320min, then at 3 ° C / min and cooled to 400 ° C, insulation 120min, then to 18 ° C / min ~ 23 ° C / min cooling to room temperature.

[0016] 本发明真空烧结条件包括有:真空度10_3Pa,以10~20°C /min的升温速率从室温升至1200°C~1500°C,保温Ih~2h后;再以低于20°C /min的升温速率升温至2000~2200°C,至少保温2h~4h。 [0016] The present invention is a vacuum sintering conditions including: a degree of vacuum 10_3Pa, at a heating rate of 10 ~ 20 ° C / min was raised to 1200 ° C ~ 1500 ° C from room temperature, Ih ~ 2h after incubation; and then to less than 20 heating rate ° C / min temperature increase to 2000 ~ 2200 ° C, holding at least 2h ~ 4h.

[0017] 真空烧结后的冷却条件还包括有:真空度不低于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。 [0017] The cooling condition after vacuum sintering further comprises: a vacuum degree of not less than 10_3Pa, not higher than 25 ° C / min, not less than 10 ° C / min cooling rate ramp down mode, the sintered porous body segment cooled down to 800 ° C, holding time segments 30min ~ 90min, then cooled in the furnace to room temperature.

[0018] 在此基础上更进一步的特点是:所述脱脂处理条件还包括有:以I~2°C /min的速率从室温升至400°C,保温300~330min,以0.3~0.8°C/min的速率从400°C升至600~800°C,保温340~360min ;所述真空烧结条件还包括有:以10~15°C /min的速率从室温升至1200~1250°C,保温30~60min,真空度为KT4Pa~KT3Pa ;以10~20°C /min的速率升至1500°C,保温30~60min,真空度为KT4Pa~l(T3Pa,以6~20°C /min的速率升至2000~2200°C,保温120~2`40min,真空度为KT4Pa~KT3Pa ;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10~200C /min的速率冷却至800°C,然后随炉冷却;所述真空退火条件为:真空度为10_4Pa~10¾,以15°C /min 升温至800 ~900°C、保温260 ~320min,再以3°C /min 冷至400°C、保温120min,再以18°C /min~23°C /min冷却至室温。 [0018] On this basis, further characterized by: the conditions of the degreasing treatment further comprising: a rate of I ~ 2 ° C / min was raised to 400 ° C from room temperature, heat 300 ~ 330min, 0.3 to 0.8 ° C / min rate was raised from 400 ° C 600 ~ 800 ° C, insulation 340 ~ 360min; the vacuum sintering conditions further comprises: at 10 ~ 15 ° C / min to a rate of from room temperature to 1200 to 1250 ° C, incubated 30 ~ 60min, vacuum degree of KT4Pa ~ KT3Pa; at a rate of 10 ~ 20 ° C / min was raised to 1500 ° C, holding 30 ~ 60min, vacuum degree of KT4Pa ~ l (T3Pa, to 6 ~ 20 ° C / min was raised at a rate of 2000 ~ 2200 ° C, holding 120 ~ 2`40min, vacuum degree of KT4Pa ~ KT3Pa; cooling conditions after the vacuum sintering further comprising: a vacuum degree of KT4Pa ~ KT3Pa; to 10 ~ 20 ° C / rate min, cooled to 1500 ~ 1600 ° C, holding 30 ~ 60min; at a rate of 12 ~ 20 ° C / min, cooled to 1200 ~ 1250 ° C, holding 60 ~ 90min; at a rate of 10 ~ 200C / min, cooled to 800 ° C, then cooling with the furnace; the vacuum annealing conditions: a vacuum degree of 10_4Pa ~ 10¾, at 15 ° C / min was heated to 800 ~ 900 ° C, insulation 260 ~ 320min, then at 3 ° C / min cooling to 400 ° C, insulation 120min, then to 18 ° C / min ~ 23 ° C / min cooling to room temperature.

[0019] 金属钽和铌的性质极类似,上述方法同样也适合医用多孔铌材料的制备。 [0019] The properties of tantalum and niobium metal electrode similar to the above-described method of preparing the same niobium porous medical material are also suitable.

[0020] 本发明多孔钽制备方法采用了纯物理模压法,使得最终多孔钽材料中杂质的含量极低,有效地提高了生物相容性和生物安全性;对本发明压制成型、脱脂、烧结及退火步骤的工艺条件优化,使得成品率高、成品孔径均匀性更好、使制备过程更稳定、质量稳定性好,有效地消除了热应力、使多孔钽材料的组织更均匀,以进一步提高多孔钽的力学性能如强度、韧性同时都得到提高,特别是其韧性得到大大提高,同时密度还得到有效地控制、使其作为人体承重骨组织替代材料的舒适感好,本发明制备工艺使得成品合格率高、生产稳定,产品合格率可高达94%。 [0020] The porous tantalum production method of the present invention uses a purely physical compression molding, so that the content of impurities in the final porous tantalum material is extremely low, effectively improving the biocompatibility and biological safety; press molding of the present invention, degreasing, and sintering optimized process conditions the annealing step, so that the high yield, uniformity and better finished hole, making the manufacturing process more stable, good quality and stability, effectively eliminating thermal stress, tissue porous tantalum material is more uniform, to further enhance the porous tantalum mechanical properties such as strength and toughness are improved at the same time, in particular its toughness is greatly improved, while also effectively controlling the density, load bearing body so as good as bone substitute material comfort, the present invention enables preparation of qualified products high, stable production, product qualification rate can be as high as 94%. 本发明制得的多孔钽成品孔隙分布均匀且连通,生物相容性好,经过测试其杂质含量可低于0.2%、密度可达6.67~8.34g/cm3,孔隙度可达50~60%,孔隙直径可达150~450 μ m,弹性模量可达4.5~6.0Gpa、延伸率达10.5~11.7%,弯曲强度可达100~120Mpa、抗压强度可达60~70Mpa,有效解决了作为替代承重部位的医用多孔钽材料既要求其孔隙率较大、又要求力学性能好的矛盾,本发明多孔钽非常适合用于作为替代承重骨组织的医用植入材料。 The present invention is finished porous tantalum pore distribution obtained and communicated, good biocompatibility, which is tested may be less than 0.2% impurities, density of up to 6.67 ~ 8.34g / cm3, a porosity of up to 50% to 60%, pore diameter of up to 150 ~ 450 μ m, the modulus of elasticity of up to 4.5 ~ 6.0Gpa, extending rate of 10.5 to 11.7%, the bending strength of up to 100 ~ 120Mpa, the compressive strength of up to 60 ~ 70Mpa, effective solution as an alternative medical porous tantalum material required to load-bearing parts of both large porosity, and good mechanical properties contradictory requirements, the present invention is well suited for porous tantalum bearing bone tissue substitute material as a medical implant.

具体实施方式 Detailed ways

[0021] 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。 [0021] Next, by the present invention will be specifically described embodiments, it is necessary to point out that the following examples are only for the present invention is further illustrated not to be construed as limiting the scope of the present invention, the skilled in the art can SUMMARY of the present invention to make some non-essential modifications and adaptations of the present invention.

[0022] 实施例1:称量硬脂酸锌、平均粒径小于43微米氧含量小于0.1 %的钽粉和双氧水混合均匀,其中硬脂酸锌占11%,双氧水占18%、钽粉占71%,均以体积百分含量计。 [0022] Example 1: powders of zinc stearate, mean particle size less than 43 microns an oxygen content less than 0.1% hydrogen peroxide and mixed tantalum powder, wherein zinc stearate, 11%, 18% hydrogen peroxide, the tantalum powder accounting 71%, percentages are on a volume basis. 加压成型:将上述混合粉末加入注塑成型机中在SOMpa下压制到聚氨酯泡沫体(孔径0.48~0.89臟,密度0.0158/0113~0.0358/0113,硬度大于50° )中成型。 Press molding: The injection molding the mixed powder was added to the press machine polyurethane foam (pore diameter of 0.48 to 0.89 dirty, density of 0.0158 / 0.0358 ~ 0113/0113, a hardness greater than 50 °) molded at SOMpa. 脱脂处理:真空度10_4Pa,以1.30C /min的升温速率从室温升温至400°C、保温324min ;再以0.7V /min的升温速率从400°C升温至650°C,保温时间340分钟。 Degreasing: the degree of vacuum 10_4Pa, at a heating rate of 1.30C / min from room temperature to 400 ° C, insulation 324min; heating rate and then to 0.7V / min heated from 400 ° C to 650 ° C, holding time of 340 minutes. 真空烧结:在真空炉中烧结,烧结温度2000°C,保温2小时,真空度10_4Pa,烧结过程充氩气保护,取出产品后去除表面灰尘及污物,再进行常规冷却处理。 Vacuum sintering: sintering in a vacuum furnace, sintering temperature 2000 ° C, for 2 hours, the degree of vacuum 10_4Pa, argon gas protection of the sintering process, to remove surface dust and dirt after the product is removed, and then subjected to conventional cooling process. 热处理:是真空度为10_4Pa~10_3Pa,以15°C /min升温至800~900°C、保温260~320min,再以3°C /min冷至400°C、保温120min,以18~23°C /min冷却至室温。 Heat treatment: vacuum degree 10_4Pa ~ 10_3Pa, at 15 ° C / min was heated to 800 ~ 900 ° C, insulation 260 ~ 320min, then cooled to 400 ° C at 3 ° C / min, incubated 120min, to 18 ~ 23 ° C / min cooling to room temperature.

[0023]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0.2%,其孔隙分布均匀,密度6.69g/cm3,孔隙率57%,孔隙平均直径330 μ m,弹性模量6.0Gpa、延伸率11.33%,弯曲强度20MPa,抗压强度67MPa。 [0023] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and various mechanical properties of the porous tantalum finished detected: impurities. less than 0.2%, a uniform pore distribution, density 6.69g / cm3, a porosity of 57%, an average pore diameter of 330 μ m, the elastic modulus of 6.0 GPa, 11.33% elongation, 20 MPa or flexural strength, compressive strength 67MPa.

[0024] 实施例2:称取丁苯橡胶、平均粒径小于43微米氧含量小于0.1 %的钽粉和碳酸氢铵混合均匀成混合粉末,其中丁苯橡胶占11.5%、碳酸氢铵占17%、钽粉占71.5%,均以体积百分含量计。 [0024] Example 2: Weigh styrene-butadiene rubber, particle size less than 43 microns average oxygen content of less than 0.1% of tantalum powder and ammonium bicarbonate mixed into a mixed powder, wherein the styrene 11.5%, ammonium bicarbonate for 17 %, 71.5%, of tantalum powder, percentages are on a volume basis. 加压成型:将上述混合粉末加入注塑成型机中在64Mpa下压制到聚氨酯泡沫体(孔径0.48~0.89mm,密度0.015g/cm3~0.035g/cm3,硬度大于50° )中成型。 Press molding: The injection molding the mixed powder was added to the press machine polyurethane foam (pore diameter of 0.48 ~ 0.89mm, density 0.015g / cm3 ~ 0.035g / cm3, a hardness greater than 50 °) molded at 64Mpa. 脱脂处理:真空度10_4Pa,以1.`20C /min的升温速率从室温升温至700°C、保温332min。 Degreasing: the degree of vacuum 10_4Pa, at a heating rate of 1.`20C / min from room temperature to 700 ° C, insulation 332min. 真空烧结:在真空炉中烧结,烧结温度2100°C,保温4小时,真空度10_4Pa,烧结过程充氩气保护,取出产品后去除表面灰尘及污物,再进行常规冷却处理。 Vacuum sintering: sintering in a vacuum furnace, sintering temperature 2100 ° C, for 4 hours, the degree of vacuum 10_4Pa, argon gas protection of the sintering process, to remove surface dust and dirt after the product is removed, and then subjected to conventional cooling process. 热处理:是真空度为10_3Pa,以14°C /min 升温至800 ~900°C、保温400min,再以4°C /min 冷至400°C、保温200min,以21°C /min冷却至室温。 Heat treatment: vacuum degree 10_3Pa, at 14 ° C / min was heated to 800 ~ 900 ° C, insulation 400min, then cooled to 400 ° C to 4 ° C / min, incubated 200min, at 21 ° C / min cooling to room temperature .

[0025]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0.2%,其孔隙分布均匀,密度7.3g/cm3,孔隙率53%,孔隙平均直径209 μ m,弹性模量5.3Gpa、延伸率11.54%,弯曲强度IlOMPa,抗压强度66MPa。 [0025] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and various mechanical properties of the porous tantalum finished detected: impurities. less than 0.2%, a uniform pore distribution, density 7.3g / cm3, a porosity of 53%, an average pore diameter of 209 μ m, the elastic modulus of 5.3 GPa, 11.54% elongation, flexural strength IlOMPa, the compressive strength of 66MPa.

[0026] 实施例3:称取石蜡、平均粒径小于43微米氧含量小于0.1 %的钽粉和双氧水混合均匀,其中石蜡占7%、双氧水占15%、钽粉占78%,均以体积百分含量计。 [0026] Example 3: Paraffin weighed an average particle size of less than 43 m oxygen content of less than 0.1% hydrogen peroxide and mixed tantalum powder, wherein the paraffin 7%, 15% hydrogen peroxide, 78% of the tantalum powder, are on a volume the percentage of dollars. 加压成型:将上述混合粉末加入注塑成型机中在52Mpa下压制到聚氨酯泡沫体(孔径0.48~0.89mm,密度0.015g/cm3~0.035g/cm3,硬度大于50。)中成型。 Press molding: The injection molding the mixed powder was added to the press machine polyurethane foam (pore diameter of 0.48 ~ 0.89mm, density 0.015g / cm3 ~ 0.035g / cm3, hardness greater than 50.) molded at 52Mpa. 脱脂处理:真空度10¾,以2°C /min的升温速率从室温升温至800°C、保温300min。 Degreasing: the degree of vacuum 10¾, at 2 ° C / min heating rate from room temperature to 800 ° C, insulation 300min. 真空烧结:在真空炉中烧结,烧结温度2200°C,保温2.5小时,真空度10_3Pa,烧结过程充氩气保护,冷却出炉,去除产品表面灰尘及污物,再进行常规冷却处理。 Vacuum sintering: sintering in a vacuum furnace, sintering temperature 2200 ° C, for 2.5 hours, the degree of vacuum 10_3Pa, argon gas protection of the sintering process, furnace cooling, remove the product surface dust and dirt, then a conventional cooling process. 热处理:是真空度为10_4Pa,以20°C /min升温至800~900°C、保温240min,再以5°C /min冷至40CTC、保温300min,以23°C /min冷却至室温。 Heat treatment: vacuum degree 10_4Pa, at 20 ° C / min was heated to 800 ~ 900 ° C, insulation 240min, then to 5 ° C / min and cooled to 40CTC, insulation 300min, at 23 ° C / min cooling to room temperature.

[0027]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0.2%,其孔隙分布均匀,密度6.67g/cm3,孔隙率51 %,孔隙平均直径430 μ m,弹性模量4.7Gpa、延伸率10.6%,弯曲强度102MPa,抗压强度60MPa。 [0027] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and various mechanical properties of the porous tantalum finished detected: impurities. less than 0.2%, a uniform pore distribution, density 6.67g / cm3, a porosity of 51%, an average pore diameter of 430 μ m, the elastic modulus of 4.7 GPa, elongation 10.6%, the bending strength of 102MPa, compressive strength of 60MPa.

[0028] 实施例4:称取硬脂酸、平均粒径小于43微米氧含量小于0.1 %的铌粉和碳酸氢铵混合均匀,其中硬脂酸占12%、碳酸氢铵占25%、铌粉占63%,均以体积百分含量计。 [0028] Example 4: Weigh stearate, average particle size less than 43 microns an oxygen content of less than 0.1% of niobium powder and mixed ammonium bicarbonate, wherein the stearic acid 12%, 25% ammonium bicarbonate, niobium powder 63%, are on a volume percentage basis. 加压成型:将上述混合粉末加入注塑成型机中在96Mpa下压制到聚氨酯泡沫体(孔径0.48~0.89臟,密度0.0158/0113~0.0358/0113,硬度大于50° )中成型。 Press molding: The injection molding the mixed powder was added to the press machine polyurethane foam (pore diameter of 0.48 to 0.89 dirty, density of 0.0158 / 0.0358 ~ 0113/0113, a hardness greater than 50 °) in the molded 96Mpa. 脱脂处理:真空度10_4Pa,以0.80C /min的升温速率从室温升温至740°C、保温340min。 Degreasing: the degree of vacuum 10_4Pa, at a heating rate of 0.80C / min from room temperature to 740 ° C, insulation 340min. 真空烧结:在真空炉中烧结,烧结温度2150°C,保温2小时,真空度10_4Pa,烧结过程充氩气保护,冷却出炉,去除产品表面灰尘及污物,再进行常规冷却处理。 Vacuum sintering: sintering in a vacuum furnace, sintering temperature 2150 ° C, for 2 hours, the degree of vacuum 10_4Pa, argon gas protection of the sintering process, furnace cooling, remove the product surface dust and dirt, then a conventional cooling process. 热处理:是真空度为10_3Pa,以10°C /min升温至800 ~900°C、保温480min,再以2°C /min 冷至400°C、保温120min,以18°C /min 冷却至室温。 Heat treatment: vacuum degree 10_3Pa, at 10 ° C / min was heated to 800 ~ 900 ° C, insulation 480min, then to 2 ° C / min and cooled to 400 ° C, insulation 120min, at 18 ° C / min cooling to room temperature .

[0029]发明人按 GB/T5163-2006、GB/T5249-1985、GB/T6886-2001 等标准对上述多孔铌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0.2%,其孔隙分布均匀,密度3.86g/cm3,孔隙率55%,孔隙平均直径450 μ m,弹性模量3.0Gpa、延伸率11.6%,弯曲强度78MPa,抗压强度52MPa。 [0029] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and various mechanical properties of the porous niobium finished detected: impurities. less than 0.2%, a uniform pore distribution, density 3.86g / cm3, a porosity of 55%, an average pore diameter of 450 μ m, the elastic modulus of 3.0 GPa, elongation 11.6%, the bending strength of 78MPa, the compressive strength of 52MPa.

[0030] 实施例5:—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,硬脂酸锌和碳酸氢铵混合粉为原料,再经压制成型、脱脂处理、真空烧结、真空退火及常规后处理制得。 [0030] Example 5: - porous tantalum species, it is less than the particle size of 43 μ m, an oxygen content of less than 0.1% of tantalum powder, zinc stearate and ammonium bicarbonate as raw material mixed powder, and then by pressing, degreasing process, vacuum sintering, vacuum annealing and conventional post-treatment system.

[0031] 其中,硬脂酸锌`占9%、碳酸氢铵占20%、金属钽粉占71%,以体积百分含量计; [0031] wherein `9% zinc stearate, ammonium bicarbonate, 20%, 71% tantalum powder to volume percentage basis;

[0032] 压制成型:将原料混合粉末加入注塑成型机中在69Mpa下压制到聚氨酯泡沫体(孔径0.48~0.89mm,密度0.015g/cm3~0.035g/cm3,硬度大于50° )中成型; [0032] The press molding: The raw material mixed powder was added in an injection molding machine to press the polyurethane foam (pore diameter of 0.48 ~ 0.89mm, density 0.015g / cm3 ~ 0.035g / cm3, a hardness greater than 50 °) at 69Mpa molding;

[0033] 压制成型后将混合粉末放入非氧化气氛炉中以一定的升温速率升温至800°C,保护气氛为99.999%氩气进行脱脂处理,其在升温之前先通入纯净氩气至少30min以排除炉内空气,控温过程:以1.50C /min的速率从室温升至400°C,保温300min,氩气通入量0.51/min ;以0.60C /min的速率从400°C升至800°C,保温340min,氩气通入量lL/min ;再关闭电源,脱脂后的样品随炉冷却,氩气通入量lL/min,直至冷却至室温时关闭氩气; [0033] The press molding in a non-oxidizing atmosphere furnace at a constant heating rate was raised to 800 ° C, atmosphere argon 99.999% degreasing, into which the first pure argon before heating the mixed powder was placed after the at least 30min to exclude air furnace, temperature control process: a rate of 1.50C / min of from room temperature to 400 ° C, 300min incubation, the amount of argon bubbled through 0.51 / min; at a rate of 0.60C / min rise from 400 ° C to 800 ° C, insulation 340min, the amount of argon passed into lL / min; then turn off the power, the samples were degreased furnace cooling, the amount of argon passed into lL / min, argon until cool off to room temperature;

[0034] 对于脱脂处理后的样品随钨器置于高真空高温烧结炉内以一定的升温速率升温至2200°C进行真空烧结,在升温之前烧结炉的真空度至少要达到10_4Pa,以10~15°C /min的速率从室温升至1200°C,保温30min,真空度为10_4Pa ;以10°C /min的速率升至1500°C,保温30min,真空度为KT4Pa~KT3Pa ;以6°C /min的速率升至2200°C,保温120min,真空度为KT3Pa ;烧结完毕,真空度为10_3Pa,以10~15°C /min的速率冷却至1600°C,保温30min ;以12°C /min的速率冷却至1200°C,保温60min ;以10°C /min的速率冷却至800°C,然后随炉冷却; [0034] For the samples degreased tungsten is placed under high vacuum with a high temperature sintering furnace at a constant heating rate was raised to 2200 ° C vacuum sintering at a degree of vacuum sintering furnace prior to heating to achieve at least 10_4Pa, 10 to rate 15 ° C / min from room temperature to the 1200 ° C, incubated 30min, degree of vacuum 10_4Pa; at a rate of 10 ° C / min was raised to 1500 ° C, incubated 30min, vacuum degree of KT4Pa ~ KT3Pa; 6 to ° C / min to a rate of 2200 ° C, 120min incubation, the degree of vacuum is KT3Pa; sintering is completed, a vacuum degree of 10_3Pa, at a rate of 10 ~ 15 ° C / min, cooled to 1600 ° C, incubated for 30 min; at 12 ° C / min cooling rate to 1200 ° C, incubated 60min; at a rate of 10 ° C / min, cooled to 800 ° C, then cooling with the furnace;

[0035] 对于真空烧结冷却后的样品随刚玉容器置于真空退火炉中以一定的升温速率升温去应力退火处理,在升温之前退火炉内的真空度至少要达到10_4Pa,是真空度为10_4Pa~10¾,以17°C /min 升温至800 ~900°C、保温300min,再以4.5 V /min 冷至400°C、保温220min,以19~21 °C /min冷却至室温。 [0035] For the samples were cooled with vacuum sintering alumina container was placed in a vacuum annealing furnace heated at a constant heating rate of stress relief annealing treatment, the degree of vacuum prior to heating in an annealing furnace to reach at least 10_4Pa, vacuum degree 10_4Pa ~ 10¾, at 17 ° C / min was heated to 800 ~ 900 ° C, insulation 300min, then at 4.5 V / min and cooled to 400 ° C, insulation 220min, to 19 ~ 21 ° C / min cooling to room temperature. 最后进行常规后处理制得多孔钽。 Finally, after conventional treatment obtain a porous tantalum.

[0036]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0.2%,其孔隙分布均匀,密度7.5g/cm3,孔隙率67%,孔隙平均直径300 μ m,弹性模量5.25Gpa、延伸率11.32%,弯曲强度11010^,抗压强度6510^。 [0036] The inventors by GB / T5163-2006, GB / T5249-1985, GB / T6886-2001 standards porous material density, porosity, pore size and various mechanical properties of the porous tantalum finished detected: impurities. less than 0.2%, a uniform pore distribution, density 7.5g / cm3, a porosity of 67%, an average pore diameter of 300 μ m, the elastic modulus 5.25Gpa, 11.32% elongation, bending strength 11010 ^ 6510 ^ compressive strength. 经计算该制备工艺产品合格率达92.4%。 The preparation process product pass rate was calculated to 92.4%.

[0037] 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 [0037] In the method of the above-described embodiments given in Example 5, we can make a variety of other conditions which can select the same

得到本发明所述的多孔钽或多孔铌。 A porous tantalum or niobium of the present invention is porous.

[0038] [0038]

Figure CN102796903BD00081

[0040] [0040]

Figure CN102796903BD00091

[0041] 所得多孔钽或多孔铌成品按前述方法检测: [0041] The resulting finished porous tantalum or niobium porous detection as previously described:

[0042] [0042]

Figure CN102796903BD00092

[0043] [0043]

Figure CN102796903BD00101

Claims (8)

  1. 1.一种制备替代承重骨组织的医用多孔金属材料的制备方法,其特征在于:由钽粉与造孔剂、成型剂混合,再经压制成型、脱脂、烧结、冷却和热处理制得该多孔金属材料;所述压制成型是将混合粉末压制到有机泡沫体中成型,压制成型压力为50~lOOMPa,所述脱脂过程是以0.3°C/min~2°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300min~360min ;所述造孔剂为碳酸氢铵或双氧水,所述成型剂为硬脂酸、硬脂酸锌、石蜡、合成树脂中的一种或多种;所述热处理是真空度为KT4Pa~10_3Pa,以10~20°C/min升温至800~900°C、保温240~480min,再以2~5°C /min冷至400°C、保温120~300min,然后随炉冷却至室温。 1. A process for preparing a medical alternative method for preparing porous metal material is bearing bone tissue, comprising: a tantalum powder with a pore-forming agent, molding agent are mixed, and then press molding, debinding, sintering, cooling, and heat treating the obtained porous metallic material; press molding the mixed powder is pressed into the organic foam molding, press molding pressure of 50 ~ lOOMPa, the debinding process at a rate of 0.3 ° C / min ~ 2 ° C / min and gradually warmed up to 400 ~ 800 ° C, argon atmosphere into configuration and incubated 300min ~ 360min; the pore-forming agent is ammonium bicarbonate or hydrogen peroxide, the forming agent is stearic acid, zinc stearate, paraffin wax, synthetic resin one or more; the degree of vacuum heat treatment KT4Pa ~ 10_3Pa, at 10 ~ 20 ° C / min was heated to 800 ~ 900 ° C, insulation 240 ~ 480min, then to 2 ~ 5 ° C / min and cooled to 400 ° C, insulation 120 ~ 300min, then furnace cooling to room temperature.
  2. 2.如权利要求1所述的医用多孔金属材料的制备方法,其特征在于:原料钽粉的平均粒径小于43微米、氧含量小于0.1% ;所述合成树脂为丁苯橡胶或异戊橡胶;所述有机泡沫体为孔径0.56~0.72mm,密度0.025g/cm3,硬度50°~80°的聚氨酯泡沫。 2. The method of preparation of porous medical metallic material according to claim 1, wherein: the average particle diameter of raw tantalum powder is less than 43 m, an oxygen content of less than 0.1%; the synthetic resin is a styrene-butadiene rubber or isoprene rubber ; the organic foam of a pore size 0.56 ~ 0.72mm, density 0.025g / cm3, the hardness of 50 ° ~ 80 ° polyurethane foam.
  3. 3.如权利要求1或2所述的制备方法,其特征在于:所述造孔剂的用量为15~25%、所述成型剂的用量为7~12%、余量为钽粉,均以体积百分含量计;所述压制成型过程中的压力为75~87MPa。 3. The production method of claim 1 or claim 2, wherein: the pore-forming agent is used in an amount of 15 to 25%, the amount of forming agent 7-12% and the balance tantalum powder, were in a volume percentage basis; molding process the pressing pressure is 75 ~ 87MPa.
  4. 4.如权利要求3所述的制备方法,其特征在于:所述造孔剂为双氧水占18%、所述成型剂为硬脂酸锌占11%、余量为钽粉、以体积百分含量计。 4. The method as recited in claim 3, wherein: the pore-forming agent is 18% hydrogen peroxide, the forming agent is 11% zinc stearate, the balance tantalum powder, percent by volume content meter.
  5. 5.如权利要求1或2所述的制备方法,其特征在于:所述脱脂过程是以0.3°C /min~IV /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330min~350min。 5. The production method of claim 1 or claim 2, wherein: said debinding process at a rate of 0.3 ° C / min ~ IV / min and gradually warmed up to 400 ~ 800 ° C, in order to constitute a gas into IS atmosphere and incubated 330min ~ 350min.
  6. 6.如权利要求3所述的制备方法,其特征在于:所述脱脂过程是以0.3°C /min~1°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330min~350min。 6. The method as recited in claim 3, wherein: said debinding process at a rate of 0.3 ° C / min ~ 1 ° C / min and gradually warmed up to 400 ~ 800 ° C, in order to constitute a gas into IS atmosphere and incubated 330min ~ 350min. ` `
  7. 7.如权利要求4所述的制备方法,其特征在于:所述脱脂过程是以0.3°C /min~1°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330min~350min。 7. The method as claimed in claim 4, wherein: said debinding process at a rate of 0.3 ° C / min ~ 1 ° C / min and gradually warmed up to 400 ~ 800 ° C, in order to constitute a gas into IS atmosphere and incubated 330min ~ 350min.
  8. 8.如权利要求1或2所述的制备方法,其特征在于:真空烧结条件为:以10~15°C /min的速率从室温升至1200~1250°C,保温30~60min,真空度为KT4Pa~KT3Pa ;以10~200C /min的速率升至1500°C,保温30~60min,真空度为KT4Pa~l(T3Pa,以6~20°C /min的速率升至2000~2200°C,保温120~240min,真空度为KT4Pa~KT3Pa ;真空烧结后的冷却条件为: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。 8. The production method of claim 1 or claim 2, wherein: vacuum sintering conditions were as follows: 10 ~ 15 ° C / min to a rate of 1200 ~ 1250 ° C from room temperature, incubated 30 ~ 60min, vacuum degree KT4Pa ~ KT3Pa; at a rate of 10 ~ 200C / min was raised to 1500 ° C, holding 30 ~ 60min, vacuum degree of KT4Pa ~ l (T3Pa, at a rate of 6 ~ 20 ° C / min was raised to 2000 ~ 2200 ° C, holding 120 ~ 240min, vacuum degree of KT4Pa ~ KT3Pa; cooling condition after vacuum sintering was: the degree of vacuum is KT4Pa ~ KT3Pa; at a rate of 10 ~ 20 ° C / min, cooled to 1500 ~ 1600 ° C, held for 30 - 60min; at a rate of 12 ~ 20 ° C / min, cooled to 1200 ~ 1250 ° C, holding 60 ~ 90min; at a rate of 10 ~ 20 ° C / min, cooled to 800 ° C, then cooling with the furnace.
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