CN103846443B - A suitable alternative to tantalum porous bone tissue of human teeth - Google Patents

A suitable alternative to tantalum porous bone tissue of human teeth Download PDF

Info

Publication number
CN103846443B
CN103846443B CN201410110916.2A CN201410110916A CN103846443B CN 103846443 B CN103846443 B CN 103846443B CN 201410110916 A CN201410110916 A CN 201410110916A CN 103846443 B CN103846443 B CN 103846443B
Authority
CN
China
Prior art keywords
min
rate
tantalum
vacuum
furnace
Prior art date
Application number
CN201410110916.2A
Other languages
Chinese (zh)
Other versions
CN103846443A (en
Inventor
叶雷
Original Assignee
重庆润泽医药有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 重庆润泽医药有限公司 filed Critical 重庆润泽医药有限公司
Priority to CN201110295867.02011.09.29 priority Critical
Priority to CN 201110295867 priority patent/CN102796893B/en
Publication of CN103846443A publication Critical patent/CN103846443A/en
Application granted granted Critical
Publication of CN103846443B publication Critical patent/CN103846443B/en

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
    • 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
    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/12Materials or treatment for tissue regeneration for dental implants or prostheses
    • 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

一种适用于替代人体牙骨组织多孔钽,钽粉与造孔剂、成型剂混合成混合粉末,造粒、注射入模具成型、脱模、脱脂、烧结和热处理制得;造孔剂为碳酸氢钠、尿素、氯化钠、甲基纤维素、乙基纤维素中的一种或多种,成型剂为聚乙烯醇、硬脂酸、硬脂酸锌、石蜡、合成橡胶中的一种或多种;脱脂过程是以0.5℃/min~3℃/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60min~240min,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 suitable alternative to bone tissue of human teeth porous tantalum, tantalum powder and pore-forming agent, molding agent is mixed into a mixed powder, granulated, injection molded into a mold, demolding, degreasing, sintering and heat treatment in the system; pore-forming agent is a carbonate sodium hydrogen a urea, sodium chloride, methyl cellulose, ethyl cellulose or more, forming agent is a polyvinyl alcohol, stearic acid, zinc stearate, paraffin wax, a synthetic rubber or more; debinding is 0.5 ℃ / min ~ 3 ℃ / min, gradually warmed to a rate of 400 ~ 800 ℃, into argon atmosphere constituted and incubated 60min ~ 240min, said sintering step is a vacuum of 10 -4Pa ~ 10-3Pa, at 10 ~ 20 ℃ / min was heated to 1500 ~ 1800 ℃, insulation 120 ~ 240min, with furnace cooling to 200 ~ 300 ℃, then at 10 ~ 20 ℃ / min was heated to 1500 ~ 1800 ℃, insulation 180 ~ 240min, at 5 ~ 10 ℃ / min was heated to 2000 ~ 2200 ℃, insulation 120 ~ 360min. 制得的多孔钽非常适合用于替代人体牙骨组织的医用植入材料。 The resulting porous tantalum is suitable for medical implantation replace bone tissue of human teeth.

Description

一种适用于替代人体牙骨组织的多孔钽 A suitable alternative to tantalum porous bone tissue of human teeth

[0001] 本发明申请是申请号201110295867. 0、申请日2011年09月29日,发明名称"一种适用于替代人体牙骨组织的多孔钽的制备方法"的分案申请。 [0001] The present invention has application Application No. 201110295867.0, filed on September 29, 2011, a divisional application entitled "Alternative Preparation suitable for porous tantalum body Dentin Organization".

技术领域 FIELD

[0002] 本发明涉及一种医用金属植入材料的制备方法,尤其是涉及一种适用于替代人体牙骨组织的医用多孔金属植入材料的制备方法。 [0002] The present invention relates to a method for preparing metallic medical implant material, particularly to a porous metal suitable for human alternative medical dental bone implant material preparation.

背景技术 Background technique

[0003] 多孔医用金属植入材料具有治疗骨组织创伤、股骨组织坏死和替代致密骨组织如牙骨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。 [0003] Porous medical implant material having a metallic treatment of bone tissue trauma, tissue necrosis and femoral cortical bone tissue substitute dental bone 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.

[0004] 而难熔金属钽,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。 [0004] and refractory metals Ta, due to its excellent biocompatibility, which porous material is expected as an alternative to the traditional metallic medical biomaterials. 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。 Because of tantalum metal harmless to the human body, non-toxic, no side effects, and with the rapid development of domestic medicine, tantalum implant material as a further in-depth knowledge of the human body, it is the human body with a porous tantalum implant material needs becoming 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,则其有望作为一种新型的骨组织替代材料。 Wherein the porous tantalum metal medical implant, 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.

[0005] 作为医用植入的多孔金属材料就像一股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渍后干燥再烧结简称泡沫浸渍法居多。 [0005] As the porous metal material as an medical implant of porous material such as a metal powder sintering method is substantially based on the main processing methods, especially the use of sintered powder to obtain pore connectivity of the porous metal foam structure with uniformly distributed method metal powder in the slurry was dried after impregnation on the organic foam and then sintered referred mostly 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.

[0006] 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。 [0006] The manufacture of porous tantalum metal powder sintering method reported rarely, in particular in the medical implant material is obtained for the purpose of porous tantalum 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。 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.

[0007] 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。 [0007] 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,塑性变形量15%。 Document further described, 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%. 但是将它作为致密骨组织如牙骨等医用植入材料的多孔钽,其材料的力学性能如延展性、抗压强度、弯曲强度等有明显不足之处,而且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。 However, the cortical bone tissue as porous tantalum implant materials medical dental bone, the mechanical properties such as ductility of the material, compressive strength, flexural strength and other significant deficiencies, but also will affect the subsequent porous tantalum processing of the material itself, for example, cutting the molded article and the like. 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.

发明内容 SUMMARY

[0008] 本发明的目的在于提供一种生物相容性、力学性能好的适用于替代人体牙骨组织的医用多孔钽。 [0008] The object of the present invention to provide a biocompatible, good mechanical properties suitable replacement for tantalum porous body for medical dental bone tissue.

[0009] 本发明的目的是通过如下技术手段实现的: [0009] The object of the present invention are achieved by the following technical means:

[0010] 一种适用于替代人体牙骨组织多孔钽的制备方法,将钽粉与造孔剂、成型剂混合成混合粉末,再经造粒、注射入模具成型、脱模、脱脂、烧结和热处理制得替代牙骨组织的医用多孔金属植入材料;其特征在于:所述造孔剂为碳酸氢钠、尿素、氯化钠、甲基纤维素、乙基纤维素中的一种或多种,所述成型剂为聚乙烯醇、硬脂酸、硬脂酸锌、石蜡、合成橡胶中的一种或多种;所述脱脂过程是以〇. 5°c/min~3°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60min~240min,所述烧结步骤是真空度为KT 4Pa~ KT3Pa,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。 [0010] An alternative method for preparing suitable porous tantalum body tooth bone, mixing tantalum powder and pore-forming agent, molding agent, a mixed powder, and then granulated, injection molded into a mold, demolding, degreasing, and sintering Alternatively a heat treatment to obtain a porous metal dental medical bone tissue implant material; characterized in that: said pore forming agent as a sodium bicarbonate, urea, sodium, methyl cellulose, ethyl cellulose or species, the forming agent is a polyvinyl alcohol, stearic acid, zinc stearate, paraffin wax, synthetic rubber, one or more; the degreasing process is square 5 ° c / min ~ 3 ° C /. min rate gradually warmed to 400 ~ 800 ° C, argon atmosphere into configuration and incubated 60min ~ 240min, said sintering step is a vacuum degree of KT 4Pa ~ KT3Pa, at 10 ~ 20 ° C / min temperature was raised to 1500 ~ 1800 ° C, holding 120 ~ 240min, cooled in the furnace to 200 ~ 300 ° C, then heated to 1500 ~ 1800 ° C at 10 ~ 20 ° C / min, holding 180 ~ 240min, at 5 ~ 10 ° C / min heated to 2000 ~ 2200 ° C, holding 120 ~ 360min.

[0011] 在医用多孔钽材料的研发过程中,制备路线众多,但发明人创造性地提出了采用上述工艺步骤制备致密医用多孔钽植入材料,特别是采用的上述烧结工艺,使得胚体成为了发热体,从而烧结得更均匀、透彻,在保证优异的生物相容性的同时还有效地提高了力学强度。 [0011] In the development of the medical porous tantalum material, many preparative route, the inventors creatively proposed a medical preparation of the compact porous tantalum implant materials using the above process steps, especially the use of the above-described sintering process, so that the embryo has become heat generation, so that more uniform sintering, thorough, ensuring excellent biocompatibility, while also effectively improving the mechanical strength.

[0012] 为了使制得的替代牙骨组织的多孔钽材料孔隙率合适、以使生物相容性优异,同时提高其材料的力学性能,上述造粒过程是在工作温度为450~650°C、工作压力为12~ 15MPa下将所述混合粉末造粒成粒径不高于20 μm的圆形颗粒,将所述圆形颗粒注射入模具的温度为380~540°C、压力为72~90MPa。 [0012] In order to make the porosity of the porous material made of tantalum alternative tooth bone tissue was appropriate, so that the excellent biocompatibility, while improving the mechanical properties of the material, the above-described granulation process operating temperature is 450 ~ 650 ° C , working pressure of 12 ~ 15MPa the mixed powder is granulated into a particle diameter of not more than 20 μm spherical particles, the spherical particles injected into the mold temperature of 380 ~ 540 ° C, a pressure of 72 ~ 90MPa.

[0013] 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。 [0013] 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KT4Pa~KT 3Pa 的真空条件。 The present invention is preferably a vacuum atmosphere the vacuum degree of vacuum of KT4Pa ~ KT 3Pa.

[0014] 在研发过程中发明人进一步研宄发现,若上述制备中控制不好,虽可制得如上所述适合用于替代牙骨的医用植入材料但产品合格率不高: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。 [0014] The inventors found further study based on the development process, if not properly controlled in the above preparation, may be prepared as described above, although suitable for use in dental bone substitute material for medical implants but not high production yield: such as powder pressing molding difficult, prone to part after compression hierarchical, non-uniform, some technical problems such as a crack occurs after degreasing.

[0015] 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,上述混合粉末中成型剂的用量为5~10%、造孔剂的用量为20~30%、余量为钽粉,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,在上述混合粉末称量中还是根据相应物质的密度计算出其对应的质量称量的),进一步优选为成型剂为石蜡占7~9%、造孔剂为乙基纤维素占26~29%、余量为钽粉,更进一步优选为石蜡占8%、乙基纤维素占27%、余量为钽粉,均以体积百分含量计;上述脱模时间优选为6~9S,进一步优选为7S。 [0015] 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 amount of the mixed powder forming agent is 5 to 10%, the amount of pore former is 20 ~ 30%, with the balance tantalum powder to the volume percentage basis (volume percentage content of the case by the final porous tantalum material directly calculating unit, is calculated from the density of the corresponding material in the mixed powder were weighed in its corresponding weighing mass), more preferably a paraffin-forming agent accounts for 7-9% of ethyl cellulose as a pore-forming agent accounts for 26 to 29%, the balance tantalum powder, and still more preferably paraffinic accounted 8 % ethyl cellulose, 27%, and the balance tantalum powder, percentages are on a volume basis; and the release time is preferably 6 ~ 9S, more preferably 7S.

[0016] 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、生产质量稳定性,在上述替代牙骨组织的多孔钽材料的制备中脱脂过程优选以2. 5~3°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150min~240min,更进一步优选以2. 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220min,最优选地,上述脱脂是以1~:TC / min的速率从室温升至400°C,保温60~120min,以L5~2.5°C / min的速率从400°C升至600~800°C,保温180~240min ;上述造粒过程优选的温度为510~535°C、工作压力为13MPa下将所述混合粉末造粒成粒径10~20 μm(更优选为13 μm)的圆形颗粒,将所述圆形颗粒注射成型的温度为祕5~49〇°C、压力为83~85MPa。 [0016] 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, production quality stability, porous tantalum material prepared in the above alternative bone tissue in the tooth degreasing process is preferably at a rate of 2. 5 ~ 3 ° C / min and gradually warmed up to 400 ~ 800 ° C, argon atmosphere into configuration and incubated 150min ~ 240min, further preferably 2. 5 ° C / min to rate gradually warmed to 400 ~ 800 ° C, argon atmosphere into configuration and incubated 220 min, and most preferably, the degreasing is 1: rate of TC / min was raised to 400 ° C from room temperature, for 60 ~ 120min, at a rate of L5 ~ 2.5 ° C / min from 400 ° C was raised to 600 ~ 800 ° C, insulation 180 ~ 240min; granulation process is preferably above a temperature of 510 ~ 535 ° C, working under a pressure of 13MPa the granulating said mixed powder to a particle size of 10 ~ 20 μm (more preferably 13 μm) spherical particles, the spherical particles secret injection molding temperature of 5 ~ 49〇 ° C, a pressure of 83 ~ 85MPa.

[0017] 为了使得胚体烧结得更均匀、透彻,使制得的医用多孔钽材料强度更高,上述烧结步骤优选为真空度为KT 4Pa~KT3Pa,以12~15°C / min升温至1500~1800°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 ~10°C / min 升温至2000 ~2200°C、保温250 ~320min。 [0017] In order to make more uniform sintered embryo, thoroughly, so that a higher strength of the porous tantalum medical material made of the sintering step is preferably a vacuum degree of KT 4Pa ~ KT3Pa, to 12 ~ 15 ° C / min temperature was raised to 1500 ~ 1800 ° C, holding 180 ~ 200min, cooled in the furnace to 200 ~ 300 ° C, then heated to 1500 ~ 1800 ° C to 16 ~ 19 ° C / min, holding 220 ~ 240min, at 5 ~ 10 ° C / min heated to 2000 ~ 2200 ° C, holding 250 ~ 320min.

[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:逐步升温至600~ 8〇〇°C,具体是以纯净氩气(99. 9999% )通入构成保护气氛,以1~3°C / min的速率从室温升至400°C,保温60~120min,以L 5~2. 5°C / min的速率从400°C升至600~800°C, 保温180~240min ;所述真空烧结条件还包括有: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 ;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;所述热处理条件还包括有:以15~30°C / min的速率升至1000~1250°C,保温240~480min,真空度为KT4Pa~l(T 3Pa,再以5~10°C / min的速率冷 [0018] On this basis, further characterized by: the conditions of the degreasing treatment further comprising: gradually heating to 600 ~ 8〇〇 ° C, in particular in a pure argon gas (99.9999%) composed of the protective atmosphere into , at a rate of 1 ~ 3 ° C / min from room temperature to the 400 ° C, thermal insulation 60 ~ 120min, at a rate of L 5 ~ 2. 5 ° C / min was raised to 600 ~ 800 ° C from 400 ° C, insulation 180 ~ 240min; the vacuum sintering conditions further comprises: a vacuum degree of KT4Pa ~ 10_3Pa, at 13 ° C / min temperature increase to 1800 ° C, holding 200min, cooled in the furnace to 200 ~ 300 ° C, then to 17 ° C / min temperature increase to 1800 ° C, holding 230min, to 7 ° C / min was heated to 2000 ~ 2200 ° C, holding 300min; cooling conditions after the vacuum sintering further comprising: a vacuum degree of KT4Pa ~ KT3Pa; 10 to 20 rate ° C / 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; to 10 ~ 20 ° C / min the rate of cooling to 800 ° C, then cooling with the furnace; the heat-treatment conditions further comprises: a rate of 15 ~ 30 ° C / min was raised to 1000 ~ 1250 ° C, holding 240 ~ 480min, vacuum degree of KT4Pa ~ l (T 3Pa, at a rate of 5 ~ 10 ° C / min in the cold 至1000°C,保温90~180min,真空度为KT4Pa~KT3Pa ;以10~20°C / min的速率冷却至800°C,保温60~120min,真空度为KT4Pa ;以20~30°C / min的速率冷却至室温,真空度为KT4Pa~l(T3Pa。 To 1000 ° C, holding 90 ~ 180min, vacuum degree of KT4Pa ~ KT3Pa; at a rate of 10 ~ 20 ° C / min, cooled to 800 ° C, thermal insulation 60 ~ 120min, degree of vacuum KT4Pa; to 20 ~ 30 ° C / min rate cooled to room temperature, a vacuum degree of KT4Pa ~ l (T3Pa.

[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] 本发明多孔金属材料制备方法采用了注射成型法,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;对本发明造粒、注射成型、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,特别是采用的上述烧结工艺,使得胚体成为了发热体, 从而烧结得更均匀、透彻,力学强度大幅提高。 [0020] The method of preparing the porous metal material of the present invention employs an injection molding method, the content of such impurities in the final porous tantalum material is extremely low, effectively improving the biocompatibility and biological safety; granulated present invention, injection molding, debinding , sintering and annealing process conditions optimization 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, the tissue more uniform porous tantalum material, to to further improve the mechanical properties such as strength of the porous tantalum, and toughness are improved at the same time, in particular using a sintering process described above, so that the heat generation becomes embryo, thereby more uniformly sintered, thorough, substantial increase in mechanical strength. 众所周知,产品的合格率、生产稳定性由人为操作因素决定和工艺路线本身决定、人为操作终归会处于高标准化趋于正常水平,因此生产质量稳定性主要由本身工艺决定,本发明制备工艺其成品合格率高、生产稳定,产品合格率高达92. 5 %~95. 0 %。 Is well known, the yield of the product, the production stability is determined by manual operation factors and the routing decision itself, after all human operator will be in a high normalized tends to normal levels, so production stability is mainly determined by the quality of the process itself, the finished preparation process of the invention pass rate, stable production, product qualification rate up to 92.5% ~ 95.0%. 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。 Finished porosity porous tantalum was prepared according to the present invention, distribution and communication, good biocompatibility. 经过测试其杂质含量可低于0.2%、密度可达11. 67~13. 34g / cm3,孔隙度可达20~ 30%,孔隙直径可达12~25 μ m、弹性模量可达4. 5~6. OGpa、延伸率达12. O~13. 8 %、弯曲强度可达160~180Mpa、抗压强度可达115~130Mpa ;其非常适合用于替代人体牙骨组织的医用植入材料。 Tested impurities which may be less than 0.2%, a density of up to 11. 67 ~ 13. 34g / cm3, a porosity of up to 20 to 30%, pore diameter of up to 12 ~ 25 μ m, the modulus of elasticity of up to 4. . 5 ~ 6 OGpa, extending rate of 12. O ~ 13 8%, the bending strength of up to 160 ~ 180Mpa, the compressive strength of up to 115 ~ 130Mpa;. which is very suitable material for the medical implant bone tissue substitute human teeth .

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 :称取石蜡、平均粒径小于43微米氧含量小于0. 1 %的钽粉和乙基纤维素混合均匀成混合粉末,其中石蜡占8%、乙基纤维素占27%、钽粉占65%,均以体积百分含量计。 [0022] Example 1: Paraffin weighed an average particle size less than 43 microns is less than 0.1 percent oxygen content of the tantalum powder and ethyl cellulose mixed into a mixed powder, wherein the paraffin 8%, ethyl cellulose is 27 %, the tantalum powder 65%, percentages are on a volume basis. 造粒:在工作温度为510~520°C、工作压力为12~13MPa下将所述混合粉末造粒成粒径10~13 μπι的圆形颗粒。 Granulation: operating temperature is 510 ~ 520 ° C, working under a pressure of 12 ~ 13MPa the mixed powder is granulated into spherical particles the particle size of 10 ~ 13 μπι. 注射成型:将所述圆形颗粒注射入模具的温度为465~ 490°C、压力为83~85MPa。 Injection molding: The spherical particles injected into the mold temperature of 465 ~ 490 ° C, a pressure of 83 ~ 85MPa. 脱模时间:6~7S。 Demolding time: 6 ~ 7S. 脱脂处理:真空度KT 4Pa,以1~3°C / min的速率从室温升至400°C,保温60~120min,以1. 5~2. 5°C / min的速率从400°C升至600~800°C,保温180~240min。 Degreasing treatment: vacuum degree KT 4Pa, to 1 ~ 3 ° C / min from room temperature to a rate of 400 ° C, thermal insulation 60 ~ 120min, to 1. 5 ~ 2 5 ° C / min from 400 ° C at a rate of raised to 600 ~ 800 ° C, insulation 180 ~ 240min. 真空烧结:真空度为KT4Pa~KT 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,烧结过程充氩气保护,取出产品后去除表面灰尘及污物,制得多孔钽成品。 Vacuum sintering: a vacuum degree of KT4Pa ~ KT 3Pa, at 13 ° C / min temperature increase to 1800 ° C, holding 200min, with furnace cooling to 200 ~ 300 ° C, and then at 17 ° C / min temperature increase to 1800 ° C, insulation 230 min, to 7 ° C / min was heated to 2000 ~ 2200 ° C, holding 300min, argon gas protection of the sintering process, to remove surface dust and dirt after the removal of the product, obtain a porous tantalum products.

[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12. 54g / cm3,孔隙率25%,孔隙平均直径23 μπι,弹性模量5. OGPa,延伸率12. 3%,弯曲强度172MPa,抗压强度120MPa。 [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 of 12. 54g / cm3, a porosity of 25%, an average pore diameter of 23 μπι, elastic modulus 5. OGPa, elongation of 12.3%, flexural strength of 172MPa, 120MPa compressive strength . 该多孔钽非常适合用于替代人体牙骨组织的医用植入材料。 The porous tantalum material is very suitable for alternative medical implant bone tissue of human teeth.

[0024] 实施例2 :称取聚乙烯醇、平均粒径小于43微米氧含量小于0. 1 %的钽粉和碳酸氢钠混合均匀成混合粉末,其中聚乙烯醇占6%、碳酸氢钠占29 %、钽粉占65 %,均以体积百分含量计。 [0024] Example 2: Weigh a polyvinyl alcohol, the average particle size of less than 43 microns is less than 0.1 percent oxygen content of the tantalum powder and mixed into a mixed powder of sodium bicarbonate, wherein 6% polyvinyl alcohol, sodium bicarbonate 29%, 65% of the tantalum powder, percentages are on a volume basis. 造粒:在工作温度为450°C、工作压力为15MPa下将所述混合粉末造粒成粒径20 μπι的圆形颗粒。 Granulation: operating temperature is 450 ° C, working under a pressure of 15MPa the mixed powder granulated to granules of particle size 20 μπι. 注射成型:将所述圆形颗粒注射入模具的温度为540°C、压力为90MPa。 Injection molding: The spherical particles injected into the mold temperature of 540 ° C, a pressure of 90MPa. 脱模时间:9S。 Stripping time: 9S. 脱脂处理:真空度l(T 4Pa,以1°C / min的升温速率从室温升温至400°C、保温60min ;再以2. 5°C / min的升温速率从400°C升温至800°C,保温时间180分钟。真空烧结:真空度为KT4Pa,以12°C / min升温至1500°C、保温200min、随炉冷至200~300°C, 再以16°C / min升温至1800°C、保温220min,以5°C / min升温至2000~2200°C、保温320min,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。 Degreasing treatment: degree of vacuum of l (T 4Pa, at 1 ° C / min heating rate from room temperature to 400 ° C, incubated 60min; then a ramp rate of 2. 5 ° C / min temperature increase from 400 ° C to 800 ° C, holding time of 180 minutes in a vacuum sintering: degree of vacuum KT4Pa, at 12 ° C / min temperature increase to 1500 ° C, holding 200min, with furnace cooling to 200 ~ 300 ° C, and then at 16 ° C / min temperature was raised to 1800 ° C, 220 min incubation, at 5 ° C / min was heated to 2000 ~ 2200 ° C, holding 320min, argon gas protection of the sintering process, to remove surface dust and dirt, and the obtained product sample was taken out and then subjected to conventional post-treatment A porous tantalum products.

[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11. 74g / cm3,孔隙率30%,孔隙平均直径24 μ m,弹性模量4. 5GPa,延伸率12. 8%,弯曲强度160MPa,抗压强度117MPa。 [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 of 11. 74g / cm3, a porosity of 30%, an average pore diameter of 24 μ m, 4. 5 GPa elastic modulus, elongation 12.8%, the bending strength of 160MPa, anti compressive strength 117MPa. 该多孔钽非常适合用于替代人体牙骨组织的医用植入材料。 The porous tantalum material is very suitable for alternative medical implant bone tissue of human teeth.

[0026] 实施例3 :称取硬脂酸锌、平均粒径小于43微米氧含量小于0. 1%的钽粉和甲基纤维素混合均匀成混合粉末,其中硬脂酸锌占10%、甲基纤维素占23%、钽粉占67%,均以体积百分含量计。 [0026] Example 3: zinc stearate was weighed, average particle size less than 43 microns is less than 0.1 percent oxygen content of the tantalum powder and methyl cellulose mixed into a mixed powder, wherein 10% of zinc stearate, methyl cellulose, 23%, 67% tantalum powder, percentages are on a volume basis. 造粒:在工作温度为650°C、工作压力为12MPa下将所述混合粉末造粒成粒径10 ym的圆形颗粒。 Granulation: operating temperature is 650 ° C, working under a pressure of 12MPa the mixed powder granulated to granules of a particle size 10 ym. 注射成型:将所述圆形颗粒注射入模具的温度为380°C、压力为72MPa。 Injection molding: The spherical particles injected into the mold temperature of 380 ° C, a pressure of 72MPa. 脱模时间:6S。 Stripping time: 6S. 脱脂处理:真空度10_ 4Pa,以3°C / min的升温速率从室温升温至400°C、保温120min ;再以I. 5°C / min的升温速率从400°C升温至750°C,保温时间240分钟。 Degreasing: the degree of vacuum 10_ 4Pa, to 3 ° C / min heating rate from room temperature to 400 ° C, insulation 120min; then a ramp rate I. 5 ° C / min temperature increase from 400 ° C to 750 ° C, incubation time of 240 minutes. 真空烧结:真空度为KT3Pa,以15°C / min升温至1800°C、保温200min、随炉冷至200~ 3〇〇°C,再以19°C / min 升温至1600°C、保温240min,以10°C / min 升温至2000 ~2200°C、 保温320min,烧结过程充氩气保护,冷却出炉,去除产品表面灰尘及污物,制得的样品再进行常规的后处理得多孔钽成品。 Vacuum sintering: a vacuum degree of KT3Pa, at 15 ° C / min temperature increase to 1800 ° C, holding 200min, cooled in the furnace to 200 ~ 3〇〇 ° C, then to 19 ° C / min temperature increase to 1600 ° C, holding 240min to 10 ° C / min was heated to 2000 ~ 2200 ° C, holding 320min, argon gas protection of the sintering process, furnace cooling, remove the product surface dust and dirt, then the sample prepared hole tantalum much finished conventional post treatment .

[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13. 30g / cm3,孔隙率20%,孔隙平均直径20 μ m,弹性模量5. OGPa,延伸率12. 05%,弯曲强度178MPa,抗压强度125MPa。 [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 of 13. 30g / cm3, a porosity of 20%, an average pore diameter of 20 μ m, the elastic modulus of 5. OGPa, 12.05% elongation, the bending strength of 178MPa, compressive strength 125MPa. 该多孔钽非常适合用于替代人体牙骨组织的医用植入材料。 The porous tantalum material is very suitable for alternative medical implant bone tissue of human teeth.

[0028] 实施例4 :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,聚乙烯醇和碳酸氢钠混合粉为原料,再经造粒、注射成型、脱模、脱脂处理、真空烧结、真空退火处理制得。 [0028] Example 4: A porous tantalum, it size of less than 43 μ m, an oxygen content of less than 0.1% of tantalum powder, polyvinyl alcohol and sodium hydrogencarbonate were mixed powder as raw material, and then pelletized, injection forming, stripping, degreasing, vacuum sintering, vacuum annealing system.

[0029] 其中,聚乙烯醇占7%、碳酸氢钠占20%、金属钽粉占73%,以体积百分含量计; [0029] wherein, 7% polyvinyl alcohol, 20% sodium bicarbonate, tantalum powder 73%, by volume percentage basis;

[0030] 造粒:在工作温度为520°C、工作压力为HMPa下将所述混合粉末造粒成粒径16 μm的圆形颗粒; [0030] Granulation: operating temperature is 520 ° C, working under a pressure of the mixed powder HMPa granulated into spherical particles of 16 μm diameter;

[0031] 注射成型及脱模:将所述圆形颗粒注射入模具的温度为468°C、压力为76MPa。 [0031] Injection molding and release: the spherical particles injected into the mold temperature of 468 ° C, a pressure of 76MPa. 脱模时间:8S ; Stripping time: 8S;

[0032] 随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1.5°C / min的速率从室温升至400°C,保温88min,氩气通入量0. 5L / min;以2. (TC / min的速率从400°C升至800°C,保温195min,氩气通入量IL / min;再关闭电源,脱脂后的样品随炉冷却,氩气通入量IL / min,直至冷却至室温时关闭氩气; [0032] The mixed powder was then placed in a non-oxidizing atmosphere furnace at a constant heating rate was raised to 800 ° C, atmosphere argon is 99.999% degreasing, into which the first pure argon for at least 30min before heating to exclude air furnace, temperature control process: a rate of 1.5 ° C / min from room temperature to the 400 ° C, insulation 88min, the amount of argon passed into 0. 5L / min; to 2. (TC / min rate from 400 ° C was raised to 800 ° C, insulation 195min, the amount of argon introduced into IL / min; then turn off the power, the samples were degreased furnace cooling, the amount of argon introduced into IL / min, until the close of argon was cooled to room temperature gas;

[0033] 对于脱脂处理后的样品随钨器置于高真空高温烧结炉内真空度为KT4Pa~ KT3Pa,以13°C / min 升温至1680°C、保温190min、随炉冷至200 ~300°C,再以17°C / min 升温至1600°C、保温230min,以8°C / min升温至2000~2200°C、保温270min ;烧结完毕, 真空度为KT3Pa,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; [0033] For the samples degreased with tungsten placed under high vacuum degree of the vacuum sintering furnace temperature KT4Pa ~ KT3Pa, at 13 ° C / min temperature increase to 1680 ° C, holding 190min, with furnace cooling to 200 ~ 300 ° C, and then heated to 17 ° C / min to 1600 ° C, incubated 230 min, at 8 ° C / min was heated to 2000 ~ 2200 ° C, holding 270min; sintering is completed, a vacuum degree of KT3Pa, at 10 ~ 15 ° C / min cooling rate to 1600 ° C, incubated for 30 min; at a rate of 12 ° C / min, cooled to 1200 ° C, incubated 60min; at a rate of 10 ° C / min, cooled to 800 ° C, then cooling with the furnace;

[0034] 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至1250°C进行去应力退火处理,在升温之前退火炉内的真空度至少要达到KT4Pa,以15°C / min的速率从室温升至1250°C,保温240min,真空度为KT4Pa~KT3Pa ;再以5°C / min的速率冷却至l〇〇〇°C,保温180min,真空度为KT4Pa~KT3Pa ;以10°C / min的速率冷却至800°C,保温120min,真空度为KT4Pa ;以20°C / min的速率冷却至室温,真空度为l(T4Pa。最后进行常规后处理制得多孔钽。 [0034] For the samples were cooled with vacuum sintering alumina container was placed in a vacuum annealing furnace heated at a constant heating rate to 1250 ° C for stress relief annealing treatment, the degree of vacuum prior to heating in an annealing furnace to reach at least KT4Pa, to 15 ° C / min to a rate of from room temperature to 1250 ° C, holding 240min, vacuum degree of KT4Pa ~ KT3Pa; at a rate of 5 ° C / min to a cooled l〇〇〇 ° C, insulation 180min, degree of vacuum KT4Pa ~ KT3Pa; at a rate of 10 ° C / min, cooled to 800 ° C, insulation 120min, degree of vacuum KT4Pa; at a rate of 20 ° C / min cooling to room temperature, the degree of vacuum of l (T4Pa after the last routine treatment. obtain a porous tantalum.

[0035]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12. 87g / cm3,孔隙率23 %,孔隙平均直径20 μ m,弹性模量5. 8GPa,弯曲强度167MPa,抗压强度123MPa。 [0035] 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 of 12. 87g / cm3, a porosity of 23%, an average pore diameter of 20 μ m, the elastic modulus of 5. 8GPa, 167MPa flexural strength, compressive strength 123MPa. 经长期测试,该制备工艺产品合格率高达95. 4%。 The long-term test, the preparation of the product passing rate as high as 95.4%. 该多孔钽非常适合用于替代人体牙骨组织的医用植入材料。 The porous tantalum material is very suitable for alternative medical implant bone tissue of human teeth.

[0036] 在上述实施例4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。 [0036] In the method of the above-described embodiments given in Example 4, we can make a variety of other conditions which select the same porous tantalum can be obtained according to the present invention.

Figure CN103846443BD00081

Figure CN103846443BD00091

Figure CN103846443BD00101

[0043] 以上制得多孔钽非常适用于作为替代人体牙骨组织的医用植入材料。 [0043] The above prepared hole tantalum is much more suitable as an alternative to bone tissue of human teeth medical implant material.

Claims (1)

1. 一种适用于替代人体牙骨组织的多孔钽,其特征在于:它以粒径小于35 ym、氧含量小于0. 1%的金属钽粉,硬脂酸锌和尿素、碳酸氢钠混合粉为原料,再经造粒、注射成型、脱模、脱脂处理、真空烧结、真空退火处理制得;其中,硬脂酸锌占7%、尿素和碳酸氢钠占26%、 金属钽粉占67%,以体积百分含量计; 造粒:在工作温度为650°C、工作压力为13MPa下将所述混合粉末造粒成粒径15 ym的圆形颗粒; 注射成型及脱模:将所述圆形颗粒注射入模具的温度为380°C、压力为72MPa,脱模时间为5. 8S ; 随后将混合粉末放入非氧化气氛炉中升温至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I. 2°C / min的速率从室温升至400°C,保温60min,氩气通入量0. 5L/min ;以I. 5°C /min的速率从400°C升至600°C,保温230min, A suitable replacement for tantalum porous bone tissue of human teeth, characterized in that: it is smaller than the diameter 35 ym, the oxygen content is less than 0.1% of tantalum powder, zinc stearate and mixing urea, sodium bicarbonate powder as raw material, and then pelletized, injection molding, mold release, degreasing, vacuum sintering, vacuum annealing in the system; wherein the zinc stearate 7% urea and 26% sodium bicarbonate, tantalum powder accounted 67%, by volume percentage basis; granulating: at an operating temperature of 650 ° C, the working pressure of 13MPa mixed powder is granulated into spherical particles of diameter of 15 ym; injection molding and demolding of: the spherical particles injected into the mold temperature of 380 ° C, a pressure of 72MPa, demold time 5. 8S; mixed powder was then placed in a non-oxidizing atmosphere furnace was heated to 800 ° C, atmosphere is 99.999 degreasing% argon, to which pure argon gas into the at least 30min before heating to exclude air furnace, temperature control process: the rate I. 2 ° C / min was raised to 400 ° C from room temperature for 60min , the amount of argon passed into 0. 5L / min; rate I. 5 ° C / min from 400 ° C was raised to 600 ° C, 230 min incubation, 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; 对于脱脂处理后的样品随钨器置于高真空高温烧结炉内真空度为l〇_3Pa,以11°C /min 升温至1580°C、保温200min、随炉冷至200~300°C,再以16°C /min升温至1700°C、保温220min,以5°C /min升温至2000~2200°C、保温320min ;烧结完毕,真空度为KT4Pa~ KT3Pa,以11°C /min的速率冷却至1520°C,保温60min ;以13°C /min的速率冷却至1200°C, 保温90min ;以13°C /min的速率冷却至800°C,然后随炉冷却; 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升温至1250°C进行去应力退火处理,在升温之前退火炉内的真空度达到l〇_4Pa,以15°C /min的速率从室温升至1030°C,保温480min ;再以5°C /min的速率冷却至1000°C,保温180min ;以11°C /min的速率冷却至800°C,保温IOSmin ;以21°C /min的速率冷却至室 The amount of gas fed lL / min; then turn off the power, the samples were degreased furnace cooling, the amount of argon passed into lL / min, until the close of argon while cooling to room temperature; for samples degreased with tungsten placed high high-temperature vacuum sintering furnace l〇_3Pa degree of vacuum to 11 ° C / min temperature increase to 1580 ° C, 200min incubation, the furnace was cooled to 200 ~ 300 ° C, and then at 16 ° C / min temperature increase to 1700 ° C , incubated 220 min, at 5 ° C / min was heated to 2000 ~ 2200 ° C, holding 320min; sintering is completed, the vacuum degree of KT4Pa ~ KT3Pa, at a rate of 11 ° C / min, cooled to 1520 ° C, incubated 60min; to 13 rate ° C / min, cooled to 1200 ° C, incubated 90min; at a rate of 13 ° C / min, cooled to 800 ° C, then cooling with the furnace; for cooling the sample after the vacuum sintering with alumina in a vacuum annealing furnace vessel warmed to 1250 ° C for stress relief annealing, heating before the degree of vacuum in the annealing furnace reaches l〇_4Pa to 15 ° C / min to a rate of 1030 ° C from room temperature, incubated 480 min; then to 5 ° rate of C / min, cooled to 1000 ° C, incubated 180min; at a rate of 11 ° C / min, cooled to 800 ° C, incubated iosmin; at a rate of 21 ° C / min cooling to room 温;最后进行常规后处理制得多孔钽。 Temperature; and finally subjected to conventional obtain a porous tantalum.
CN201410110916.2A 2011-09-29 2011-09-29 A suitable alternative to tantalum porous bone tissue of human teeth CN103846443B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201110295867.02011.09.29 2011-09-29
CN 201110295867 CN102796893B (en) 2011-09-29 2011-09-29 Preparation method of porous tantalum applicable to replacing human dentale tissue

Publications (2)

Publication Number Publication Date
CN103846443A CN103846443A (en) 2014-06-11
CN103846443B true CN103846443B (en) 2015-10-07

Family

ID=47196185

Family Applications (3)

Application Number Title Priority Date Filing Date
CN 201110295867 CN102796893B (en) 2011-09-29 2011-09-29 Preparation method of porous tantalum applicable to replacing human dentale tissue
CN201410110916.2A CN103846443B (en) 2011-09-29 2011-09-29 A suitable alternative to tantalum porous bone tissue of human teeth
CN201410110740.0A CN103849792B (en) 2011-09-29 2011-09-29 A suitable alternative to tantalum porous bone tissue of human teeth

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN 201110295867 CN102796893B (en) 2011-09-29 2011-09-29 Preparation method of porous tantalum applicable to replacing human dentale tissue

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN201410110740.0A CN103849792B (en) 2011-09-29 2011-09-29 A suitable alternative to tantalum porous bone tissue of human teeth

Country Status (2)

Country Link
CN (3) CN102796893B (en)
WO (1) WO2013044857A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103768655B (en) * 2014-02-17 2015-12-09 苏州大学 Method for preparing porous tantalum skeleton
CN106474554A (en) * 2015-08-31 2017-03-08 重庆润泽医药有限公司 Porous metal material and preparation method thereof
CN105855553B (en) * 2016-03-30 2018-01-23 山东省立医院 A process for producing a porous tantalum implant materials for oral
CN106267331A (en) * 2016-09-28 2017-01-04 广州凯耀资产管理有限公司 Oral cavity implant and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0560279B1 (en) * 1992-03-11 2000-06-14 Ultramet Open cell tantalum structures for cancellous bone implants and cell and tissue receptors
CN1485453A (en) * 2003-07-30 2004-03-31 强 张 Method for manufacturing preformed component of metal matrix composite reinforcing phase
CN1936045A (en) * 2005-09-22 2007-03-28 中南大学 Three-dimensional through-hole or part-hole interconnecting porous metal foam and its preparing method
CN101121982A (en) * 2007-09-30 2008-02-13 北京师范大学 Porous foam tungsten and preparation method thereof
CN101193664A (en) * 2005-05-04 2008-06-04 维塔尔植入物公司 Dental implant comprising a porous trabecular structure
CN101405039A (en) * 2006-02-17 2009-04-08 拜欧麦特制造公司 Method and apparatus for forming porous metal implants

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD118501A3 (en) * 1974-04-11 1976-03-12
CN1560300A (en) * 2004-03-09 2005-01-05 株洲硬质合金集团有限公司 Preparation method of Taw Yalloy bar
US6902809B1 (en) * 2004-06-29 2005-06-07 Honeywell International, Inc. Rhenium tantalum metal alloy
EP2149414A1 (en) * 2008-07-30 2010-02-03 Nederlandse Centrale Organisatie Voor Toegepast Natuurwetenschappelijk Onderzoek TNO Method of manufacturing a porous magnesium, or magnesium alloy, biomedical implant or medical appliance.
CN101518467A (en) * 2009-03-06 2009-09-02 中南大学 Medicinal porous titanium implant and method for preparing same
CN101549175B (en) * 2009-05-15 2012-07-04 中南大学 Method for preparation of pore heterogeneous distribution bionic bone material
CN101660076A (en) * 2009-10-14 2010-03-03 北京师范大学 Macro mesh structural porous tantalum prepared by dipping and sintering organic foams
CN101709419B (en) * 2009-12-18 2011-09-28 北京有色金属研究总院 Tantalum foam and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0560279B1 (en) * 1992-03-11 2000-06-14 Ultramet Open cell tantalum structures for cancellous bone implants and cell and tissue receptors
CN1485453A (en) * 2003-07-30 2004-03-31 强 张 Method for manufacturing preformed component of metal matrix composite reinforcing phase
CN101193664A (en) * 2005-05-04 2008-06-04 维塔尔植入物公司 Dental implant comprising a porous trabecular structure
CN1936045A (en) * 2005-09-22 2007-03-28 中南大学 Three-dimensional through-hole or part-hole interconnecting porous metal foam and its preparing method
CN101405039A (en) * 2006-02-17 2009-04-08 拜欧麦特制造公司 Method and apparatus for forming porous metal implants
CN101121982A (en) * 2007-09-30 2008-02-13 北京师范大学 Porous foam tungsten and preparation method thereof

Also Published As

Publication number Publication date
CN102796893B (en) 2014-03-05
CN103849792A (en) 2014-06-11
CN103849792B (en) 2015-11-25
CN103846443A (en) 2014-06-11
CN102796893A (en) 2012-11-28
WO2013044857A1 (en) 2013-04-04

Similar Documents

Publication Publication Date Title
Bansiddhi et al. Porous NiTi for bone implants: a review
Li et al. A novel porous Ti6Al4V: characterization and cell attachment
US10052405B2 (en) Biodegradable implant and method for manufacturing same
Singh et al. Titanium foams for biomedical applications: a review
CN1568167A (en) Surgical implants
Köhl et al. Powder metallurgical near‐net‐shape fabrication of porous NiTi shape memory alloys for use as long‐term implants by the combination of the metal injection molding process with the space‐Holder technique
CN101032632A (en) Material for bone tissue engineering scaffold and making method thereof
CN101518467A (en) Medicinal porous titanium implant and method for preparing same
JP2013502945A (en) Method for producing a tooth portion made of dental metal powder
Seyedraoufi et al. Synthesis, microstructure and mechanical properties of porous Mg Zn scaffolds
CN102747245A (en) Preparation method of medical porous titanium and titanium alloy
US20130011691A1 (en) Porous tantalum used for medical implantation and method for preparing the same
CN101418392B (en) Bio-medical porous titanium products and preparation method thereof
Wu et al. Nickel release behavior, cytocompatibility, and superelasticity of oxidized porous single‐phase NiTi
Li et al. The influence of addition of TiH2 in elemental powder sintering porous Ni–Ti alloys
CN102388157A (en) Process for manufacturing magnesium alloy based products
Maya et al. Zr–Ti–Nb porous alloys for biomedical application
Rao et al. Phase composition, microstructure, and mechanical properties of porous Ti–Nb–Zr alloys prepared by a two-step foaming powder metallurgy method
Wang et al. Mechanical properties of porous titanium with different distributions of pore size
CN100451144C (en) Method for preparing shape memory nickel titanium alloy with gradient porosity
Schwarz et al. Hierarchically structured polyglycolide–a biomaterial mimicking natural bone
CN100536938C (en) Process for preparing porous biological ceramics supporting frame
WO2016134626A1 (en) Method for preparing three-dimensional interconnected porous magnesium-based material and use thereof
CN101608271B (en) Method for preparing through-hole foam copper
CN104131195A (en) Preparation method of biomedical porous titanium

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model