CN101848683A - 用于插入到骨组织的钛基金属植入物的表面的制备方法 - Google Patents
用于插入到骨组织的钛基金属植入物的表面的制备方法 Download PDFInfo
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C8/00—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- C—CHEMISTRY; METALLURGY
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- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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- A61C8/0012—Means to be fixed to the jaw-bone for consolidating natural teeth or for fixing dental prostheses thereon; Dental implants; Implanting tools characterised by the material or composition, e.g. ceramics, surface layer, metal alloy
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Abstract
本发明涉及制备用于插入骨组织的钛基金属植入物的表面的方法,包含(a)在所述植入物的外部区域在一定压力下喷射氧化铝颗粒;(b)用含有硫酸和氢氟酸的酸混合物对喷砂后的植入物外部区域进行化学处理;(c)对喷砂和化学处理后的植入物外部区域在200-450℃的温度下加热15-120分钟进行热处理。同时,本发明提供了一个具有上述表面的金属植入物。所制备的表面具有良好的微米级的表面粗糙度以及合适的形态,以及几乎没有杂质的组成,并且表面的厚度约为传统表面厚度的3倍,这些特征使所述的表面具有良好的骨整合性。
Description
发明领域
本发明涉及用于插入到骨组织的金属植入物领域。特别是,本发明涉及制备金属植入物表面的方法,该表面具有良好的粗糙度并具有优化的化学组成和厚度,从而具有良好的细胞反应,并因此使植入物与骨接合的更好。本发明还涉及具有上述性质的金属植入物。
背景技术
众所周知,在本领域的现有技术中使用某些金属或金属合金如钛、锆、铪、钽、铌或这些金属合金与骨组织形成相对牢固的连接。特别是,大约从1950年以来,人们就已经知道钛及其合金的金属植入物与骨组织具有良好的接合性能。这种接合被Branemark等人称为骨整合(Branemark et al.,“Osseointegrated implants in the treatment ofthe edentulous jaw.EXperience from a 10-year period”,Scand.J.Plast.Reconstr.Surg.,II,suppl 16(1977))。
虽然这种金属与骨组织之间的接合是相对牢固的,但人们仍希望改进这种接合。本领域现有技术中已经开发了许多方法来处理这类金属植入物以在其上获得合适的表面从而改进它们的骨整合。所述术语“表面”应当理解为指的是植入物的表层或其最外侧区域,它主要由相应的金属氧化物组成,其物理性质与制成所述植入物的主体材料明显不同。
这些方法中的一些方法目标在于改变所述表层的形态,增加其粗糙度以提供更大的接触面积,并因此使所述植入物和所述骨组织之间的结合面积增大,从而具有更高的机械保持力和强度,也就是说使植入物的骨整合更好。
过去几年中,人们研究了提高表面粗糙度的方法背后的原因,证明了通过微米级表面粗糙度可以提高植入物在中短期的骨整合(Buser et al.,“Influence of surfacecharacteristics on bone integration of titanium implants.A histomorphometric study inminiature pigs”,J Biom Mater Res,(1991),25:889-902;Wennerberg et al.,“Torque andhistomorphometric evaluation of c.p.titanium screws blasted with 25-and 75-um-sizedparticles of Al2O3”,J Biom Mater Res,(1996);30:251-260;Buser et al.,“Removal torquevalue of titanium implants in the maXilla of miniature pigs”,J Oral MaXillofac Implants(1998)13:611-619;and Lazzara et al.,“Bone response to dual acid-etched and machinedtitanium implant surfaces”,Bone Engineering,chap.34(2000)J.E.Davies eds.)。
另外,其他一些研究证明植入物表层具有微米级的粗糙度能够提高造骨细胞的细胞表达,从而使细胞分化更好和使造骨细胞表达的更好。其结果就是提高了骨整合和更好的骨结构(Buser et al.1991,supra;Cochran et al.,“Attachment and growth of periodontalcells on smooth and rough titanium”,Int.J Oral MaXillofac Implants(1994)9:289-297;Martin et al.,“Effect of titanium surface roughness on proliferation,differentiation,andprotein synthesis of human osteoblast-like cells(MG63)”,J Biom Mat Res(1995)29:389-401;Lazzara et al.2000,supra;and Orsini et al.,“Surface analysis of machined vs sandblasted andacid-etched titanium implants”,J.Oral MaXillofac Implants(2000)15:779-784)。
还有,一些基于研究的制造商,如诺贝尔生物护理公司(Nobel Biocare),开发了表面处理方法以提高钛氧化层的厚度和结晶度,因为一些研究显示,结晶度和植入物的良好骨整合之间存在一定的关系(Sul et al.,“OXidized implants and their influence on thebone response”,J Mater Sci:Mater in Medicine(2002);12:1025-1031)。
在本领域的现有技术中用于提高植入物表面粗糙度的方法有很多。其中,包被整个表面,用粒子冲击表面和用化学侵蚀表面的方法比较突出。
包被金属植入物表面的常用方法包括采用各种已知的技术如等离子喷涂或等离子喷雾的方法包被金属,通常为钛或陶瓷层以及羟磷灰石(Palka,V.et al.,“The effect ofbiological environment on the surface of titanium and plasma-sprayed layer ofhydroXylapatite”.Journal of Materials Science:Materials in Medicine(1998)9,369-373)。
冲击表面的方案中,采用各种材料和大小的颗粒,将它们喷射到植入物的表面以改变植入物表面的形态。通常采用金刚砂(矾土)颗粒(Buseret al.1991,supra;Wennerberget al.1996;supra)或钛氧化物颗粒(Gotfredsen,K.et al.,“Anchorage of TiO2-blasted,HA-coated,and machined implants:an eXperimental study with rabbits”.,J Biomed MaterRes(1995)29,1223-1231)。
另一方面,可以用不同的无机酸如氢氟酸、盐酸、硫酸等对所述表面进行化学侵蚀。例如,植入物创新公司(Implant Innovations Inc)的美国系列专利(US 5,603,338;US5,876,453;US 5,863,201and US 6,652,765)介绍了两步法酸处理,使用该方法获得了商业表面。第一步,使用氢氟酸水溶液去除金属表面上的自然氧化物层,第二步,用盐酸和硫酸的混合物获得具有微米级粗糙度的表面。在仍然来自植入物创新公司的欧洲专利申请EP 1477 141中,介绍了这种方法的变种,其中,氢氟酸和盐酸的混合物用于第二步处理基于钛和Ti6Al4V合金的植入物表面。
冲击植入物表面后再用化学侵蚀的两个技术的组合应用也被描述了。在这些方法中,例如Buser(Buser et al.1991,Buser at al.1998,supra)报道了用矾土中等颗粒冲击,再用氢氟酸和硝酸蚀刻,以及用粗糙矾土冲击,再用盐酸和硫酸的混合物进行化学侵蚀。相似的,Cochran(Cochran et al.1994,supra)用精细或粗金刚砂颗粒冲击后,用盐酸和硫酸进行化学侵蚀来处理钛表面。类似的,Choi Seok等(KR 2003007840)报道了用磷酸钙颗粒冲击,然后用盐酸和硫酸的混合物进行处理的方法。同样的,Astra Tech的国际专利WO 2004/008983,报道了一种处理植入物表面的方法,即用精细和粗钛氧化物颗粒联合冲击再用氢氟酸处理。还有,Franchi(Franchi等,(2004)“Early detachment oftitanium particles from various different surfaces of endosseous dental implants”,Biomaterials 25,2239-2246)和Guizzardi(Guizzardi et al.,(2004)“Different titanium surfacetreatment influences human mandibular osteoblast response”,J Periodontol 75,273-282)报道了用精细和粗氧化锆颗粒冲击,再用未指明的酸处理的方法。
至于热处理,Browne(Browne等,(1996),“Characterization of titanium alloy implantsurfaces with improved dissolution resistance”,Journal of Materials Science:Materials inMedicine 7,323-329)和Lee(Lee等,(1998),“Surface characteristics of Ti6Al4V alloy:effectof materials,passivation and autoclaving”,Journal of Materials Science:Materials inMedicine 9,439-448)报道了用400℃热空气对先前未经过处理的钛合金处理45min获得对溶解有更好抵抗力和具有更厚的氧化层的表面,尽管该表层厚度只有4nm。
因此通过这些方法,获得了具有微米级粗糙度的表面,但表面的钛氧化层厚度大大降低,其缺点是没有非常稳定钛氧化层和不能降低释放到介质中的金属离子。
因此,本领域的现有技术仍需要处理金属植入物表层的替代方法,以提供具有微米级粗糙度的表面,并具有改进的化学组成和厚度,以优化骨整合过程。
本作者的西班牙专利申请200701518报道了一种获得钛基金属植入物表面的方法,该植入物实质上不含杂质,具有与传统表面相比大约3倍的厚度,且具有微米级的粗糙度和形态(图1a和2a),优化了骨整合和骨锚定过程。
所述方法包括在压力作用下,将锆氧化物颗粒喷砂到植入物的外部区域,然后用特定组合的酸进行化学处理,以及最后的热处理。所使用的硫酸和氢氟酸的混合物,以及这三种处理的组合,和最后热处理的条件至今未见报道。
本发明人发现在上述方法的喷砂过程中,颗粒类型的替换结合颗粒大小的改变以及喷射时所用的压力,使其获得了具有微米级形态的另一种金属植入物表面,该形态不同于以往,但适于优化骨整合和骨锚定过程。
因此,本发明的方法使得获得了另一种钛基金属植入物的表面,该表面具有更优的性质如化学组成,厚度和微米级粗糙度及形态,这它们都能获得更好的骨整合和细胞反应性质。
发明内容
发明目的
因此,本发明的目的是提供一种制备用于插入骨组织的钛基金属植入物表面的方法。
本发明另一个目的是提供一种用所述方法制备的表面。
最后,本发明的另一个目的是提供一种具有上述表面的金属植入物。
附图说明
图1a表示用本发明人前述方法获得的表面的显微图(150X)。
图1b表示用本发明的方法获得的表面的显微图(150X)。
图2a显示了由本发明人前述方法获得的表面用共聚焦显微镜获得的三维粗糙度。
图2b显示了由本发明的方法获得的表面用共聚焦显微镜获得的三维粗糙度。
图3显示了由本发明方法获得的植入物表面的外线区域部分的重构和所述表面的相应粗糙度的检测。
图4显示了由本发明方法获得的表面的能量色散X射线光谱(EDS)。
图5显示了相对于其它的传统表面来说,由本发明方法获得的表面在12,24,72小时的细胞活性,用作指示细胞毒性。
图6显示了相对于其他的传统表面来说,将成骨细胞接种到由本发明方法获得的表面(03/136/14)上培养6天后碱性磷酸酶的活性,用作指示成骨细胞产生的骨基质。
发明详述
本发明提供了一种制备用于插入骨组织的钛基金属植入物表面的方法,下称为“本发明的方法”,所述方法包括如下步骤:
1)在一定的压力下,将氧化铝颗粒喷射在植入物的外部区域上;
2)用含有硫酸和氢氟酸的酸混合物对喷砂过的植入物外部区域进行化学处理;和
3)对喷砂过的和化学处理过的植入物外部区域在200-450℃加热15-120分钟进行热处理。
如上所述,钛基植入物的表面是主要由氧化钛组成的表层或最外部区域。
根据本发明方法获得的表面,具有8-50nm的厚度,优选10-30nm厚,更优选的是15nm厚。正如前面所指出的,所述厚度几乎是传统表面厚度的3倍,极大提高了植入物的骨整合,并明显地减少了杂质。
同样,由本发明方法获得的表面含有大约98%重量百分比的几乎理想配比的氧化钛组成(通过XPS或光电子发射光谱测量的百分比,1分钟的溅蚀后或用加速的离子轰击,以去除所获得的表面的最外侧区域中存在的污染物,这是所述的分析方法所固有的,并获得其真实的组分)。
本发明方法获得的表面还具有优良的微米级的表面粗糙度,因此具有很好的骨整合和细胞反应性质。实际上,表面处理后的形态与骨小梁的表面形态非常相似,适于骨修复的起始。同样,其多孔性和粗糙度特征可以使残余应力均匀化,有助于起始蛋白的粘附和固定,还有助于细胞粘附,增殖和成熟,以及细胞外部基质的稳定。
待被处理的金属植入物是钛或钛合金植入物。钛可以为商用纯钛;同样,钛合金可以是任何适宜的钛合金,例如:钛、铝和钒的合金Ti6Al4V。所述钛基金属植入物是适于插入骨组织的,因此该植入物可以是牙科植入物,矫形植入物等,取决于该植入物要植入的骨组织。
在本发明的所述方法的一个具体实施例中,在植入物外表面喷射氧化铝颗粒的步骤a是在1-6个大气压下进行的。在一个优选实施例中,氧化铝颗粒的喷射是在3个大气压下进行的。
在本发明方法的另一个具体实施例中,步骤(a)中所用的氧化铝颗粒大小为10-100μm。在另一个优选的实施例中,所述氧化铝颗粒的具体大小为25μm。
由于氧化铝颗粒是非常好的生物相容性材料,因此在用氧化铝颗粒进行喷砂时,在所述步骤结束时会留下这类氧化铝颗粒,由此所出现的生物适应性的问题就可以避免。而且,具有所述大小的这类材料的颗粒具有很多的尖锐凸起和边,这样在喷砂压力的共同作用下,导致冲击点具有明显的凹形,这样适于良好的细胞反应。
任何适宜的装置,如仁福牌(Renfert)初级卡特罗(Basic Quattro)型喷砂设备,可以用于进行喷砂或使机械应力均匀化。将所述装置与压缩空气回路连接,就可以将装填到机器内的氧化铝砂进行喷射。喷砂一结束,可以用任何本领域适宜的方法清洗表面,如用压缩空气和超声清洗处理。
在本发明方法的一个具体实施例中,步骤(b)所用的酸混合物包含15-50%(v/v)的硫酸和0.01-1%(v/v)的氢氟酸。在另一个优选实施例中,所用的酸混合物包含28.8%(v/v)的硫酸和0.024%的氢氟酸(v/v)。
这种特定酸的组合产生了特定的粗糙度和形态,这与几乎没有杂质的表面化学组合物结合产生了最佳的细胞反应。
在本发明方法的另一具体实施例中,步骤(b)的化学处理是在50-110℃的温度下处理4-60分钟。在一个优选实施例中,所述化学处理是在75℃的温度下处理12分钟
用标准实验室设备在通风橱(Cruma牌9001-GH通风橱)中进行蚀刻,以阻止酸蒸汽。化学处理后,将植入物从酸浴中取出,洗去残留的酸,然后用超声清洗,并干燥。至于干燥,可以用适宜的传统干燥装置,如Renfert牌干燥炉。
在本发明方法的另一具体实施例中,热处理步骤(c)是在285℃的温度下处理60min。
在指定的温度下进行一定时间的热处理,使得表面的氧化钛层进行了重构,增加了晶体度,并减少了杂质,从而提高了细胞反应性。而且,所述热处理增加了表面氧化钛层的厚度。在正常条件之下,曝露在空气中的钛发生了氧化并形成了大约5纳米厚的氧化钛层。这个氧化层保护剩余的钛不被氧化。因此,它对于获得具有更大厚度的氧化钛层是有用的,但是该厚度并不会太厚,以使得当所述植入物在插入过程中与骨头摩擦时,所述层的易碎性会产生微颗粒。从这个意义上讲,由本发明的方法获得的8-50nm的厚度范围是可接受的。
因此,为获得上述提到的厚度,必须在足够的温度进行热处理,以加速空气中的氧在植入物材料中的扩散,但又不能太高,引起钛的氧化,这会引起视觉可见的颜色变化。因此,选择的工作温度是200-450℃之间。
最后,需要控制的第二个参数是处理时间。太短的时间不能让氧有效扩散;太长的时间会引起表层厚度过量的增加,不能工业化。根据处理的温度,在这两个极端之间的合理的范围是15分钟到24小时。因此,所选的工作时间在15分钟到120分钟之间变化。
可以用传统的装置进行热处理,例如用低温Memmert UM-100型炉。
本发明的另一个方面,提供了一种用前述方法获得的表面。如前所述,所述表面包括实质上纯的氧化钛层,并具有8-50nm的厚度,优选10-30nm厚,最好是15nm厚。
本发明的另一个方面,提供一种用于插入骨组织的钛基金属植入物,该金属植入物具有上述方法制备的表面。在一个具体的实施例中,所述的金属植入物是钛或钛合金植入物。在一个具体的实施例中,所述的金属植入物是牙科植入物。
通过下述实施例进一步阐明本发明,但不能认为是限制本发明。
实施例1
制备具有由本发明方法所获得的表面的钛牙科植入物
以2cm到3cm之间的间距垂直于正被处理的表面上布置排气孔,用25μm氧化铝颗粒在3个大气压下对用商业纯钛制造的具有螺纹的圆锥-圆柱形Defcon TSA骨内植入物进行喷砂。喷砂后,用压缩空气进行清洗,然后浸在在纯水中超声清洗10min。然后再用压缩空气干燥。
然后,按下述组成配制水溶液:28.8%体积百分比的硫酸和0.024%体积百分比的氢氟酸。将装有所述试剂的烧杯放在温度为75°+/-2℃的热浴中。一旦所述试剂达到设定的温度,通过将先前喷砂过的植入物浸入到所述试剂溶液中12分钟(+/-15秒)进行化学处理。一旦所述的处理结束后,从酸浴中移出所述植入物,随后在两个连续的纯水池中震荡清洗15秒。然后,将其浸没在纯水中超声清洗10分钟并随后在炉中干燥。
然后,上述处理的植入物在低温Memmert UM-100炉中在285℃(+/-20℃)热处理60分钟。
实施例2
实施例1中所获的表面的性质
形态
通过表面显微图,以及用共聚焦显微镜测定粗糙度,研究了实施例1中所获的表面的形态。
表面显微图
用JEOL JSM 840扫描电镜获得的表面显微图,扫描束电压为15KV。
图1b示出了该表面的显微图(150x),其中可以看到所述表面显示了十分特有的表面粗糙度,其粗糙度值Ra(平均粗糙度)大约1μm,其特征是由于酸对所述表面的侵蚀作用使圆的形态具有尖锐的外边并出现了分布均匀的深孔。
这种粗糙度水平符合不同科技文献对植入物表面粗糙度和细胞良好锚定关系的要求(Buser et al.1991,Cochran et al.1994,Martin et al.1995,Wennerberg et al.1996,Wennerberg et al.1997,Buser et al.1998,Lazzara et al.2000,Orsini et al.2000,supra)。
共聚焦显微镜测定粗糙度
用共聚焦显微镜连同Escuela Técnica大学光学系(Escuela Técnica Universitaria deTerrassa(Universitat Politècnica de Catalunya))开发的软件PLμ一起进行三维粗糙度的测定。根据DIN 4768标准,用具有800μm的高斯截止滤波器进行测定。
图2b显示了由本发明的技术获得的表面的三维粗糙度。同样,图3示出了根据所述表面的横断面,在所述植入物外线区域的重建和相应的粗糙度的测量值。
所获得的粗糙度值得出了平均值Ra(平均粗糙度)为1.0μm,两个峰之间的距离Sm为12μm。这些值接近前面段落中提及的参考书目中所述的理想值。
表面化学组成
用两种不同的技术:能量色散X射线光谱(EDS)分析和X射线光电子能谱(XPS)分析对所述表面的化学组成进行分析。
能量色散X射线光谱(EDS)分析
该技术能够确定厚度大约1μm具有较高的空间分辨率的表面的定量组成。能量 色散X射线光谱(EDS)可以检测原子量在硼和铀之间的原子的存在,并对所研究表面的含量进行定量测定。
EDS测定在巴塞罗那大学科技服务部完成。采用具有EDS Link Inca装置的莱卡Electroscan 360扫描电镜可以检测原子量等于或大于硼的原子。图4显示了所获得的能 量色散X射线光谱。
用EDS方法进行的分析,只显示了在处理钛样品表面中钛和氧的存在,以及痕量的铝。铝的存在是由于前述为使应力均一进行处理的结果,它可以使一些氧化铝颗粒黏附在表面上。不同的分析显示这种现象存在于经处理的植入物的整个表面。
X射线光电子光谱法(XPS)分析
X射线光电子光谱法分析由巴塞罗那大学科技服务ESCA和TEM分析部进行。结果(按原子百分比)如表1所示,并与前文所提到的文献中的几种牙科植入物的X射线光电子光谱法分析进行比较(Wieland et al.,“Measurement and evaluation of the chemicalcomposition and topography of titanium implant surfaces”,Bone Engineering,chap.14(2000)J.E.Davies eds;Massaro et al.,“Comparative investigation of the surface properties ofcommercial titanium dental implants.Part I:chemical composition”.J Mat Sci:Mat inMedicine(2002)13:536-548)。
表1.样品与其它商业植入物的表面进行XPS分析的结果比较
1-所分析的本发明的表面没经过溅射(包括检测所获表面外部区域的杂质,这是分析方法本身固有的)。
2-本发明的表面经过1分钟溅射后。
4-ITI SLA:喷砂+酸处理(Straumann)。
5-3i Osseotite:酸处理(Biomet 3i)。
N.a.:未检测
结果比较显示所分析的本发明样品的表面化学组成与市场上的其它植入物完全相等,甚至具有更低的碳或硅杂质(Wennerberg et al.1996,supra;Wieland et al.2000,supra;and Sittig et al.,“Surface characterization of implant materials c.p.Ti,Ti6Al7Nb andTi6Al4V with different pretreatments”,J Mater Sci:Mater in Medicine(1999),10:35-46)。
表面上的一些元素如氮的存在,是由于热处理过程引入的。在其它方法中常见的其它杂质如硅或钠未检测到。残留百分比接近100%是由于被检测的氩(未指出),它是XPS测量过程中残留的下来的。
实施例3
与实施例1所述相似方法获得的钛样品的细胞反应
用与实施例1所述相似方法处理的钛样品(直径5mm的商业纯钛片)进行生物评估研究由063-13研究组(西班牙Santiago de Compostela大学药物与牙科学院药物学系)进行。
将人成骨细胞接种于改良Dulbecco培养基中的测定样品上(8×103细胞/片,三个平行),该培养基含有10%胎牛血清和1%的抗生素。由本发明方法获得的表面(编号为03/136-14)的细胞生物活性(表面的细胞毒性指标)和碱性磷酸酶产量(由成骨细胞产生的细胞骨基质的指标)与以下几种进行比较:机械加工相同钛片未处理表面(编号为03/136-07),喷砂加工相同钛片的未处理表面(金刚砂抛光5微米纸抛光)(编号为03/136-18),与ITI SLA表面相似喷砂且酸处理后的未处理表面(编号为03/136-09)。
图5显示了12,24,72小时在所述样品中的细胞活性检测结果。图6依次显示了培养所述样品6天后碱性磷酸酶活性检测结果。
长久以来碱性磷酸酶活性一直被认为与生物钙化有关。因此这些酶表达的提高被认为是骨基质矿化必须的,可以为羟基磷灰石结晶的成核和增殖提供丰富的无机磷酸,它是骨组织的主要成份。
从图5和6可以看到,结果显示本发明方法获得的表面(编号为03/136/14)比机械加工的表面(编号为03/136/07),喷砂加工的(金刚砂抛光5微米纸抛光)对照(编号为03/136/18)具有较好的细胞反应。另一方面,本发明的表面与喷砂且酸处理的对照表面(编号为03/136/09)的细胞反应实验结果相同。
Claims (14)
1.一种制备钛基金属植入物的表面的方法,所述的钛基金属植入物用于插入到骨组织中,其特征在于,所述的方法包含下述步骤:
(a)在一定压力下,将氧化铝颗粒喷射到所述植入物的外部区域;
(b)用含有硫酸和氢氟酸的酸混合物对喷砂过的所述植入物的外部区域进行化学处理;
(c)在200-450℃的温度下,对喷砂过的和化学处理过的植入物的外部区域加热15-120分钟进行热处理。
2.根据权利要求1所述的方法,其特征在于,步骤(a)中所述的将氧化铝颗粒喷射到所述植入物的外部区域是在1-6个大气压下进行的。
3.根据权利要求2所述的方法,其特征在于,步骤(a)中所述的将氧化铝颗粒喷射到所述植入物的外部区域是在3个大气压下进行。
4.根据权利要求1所述的方法,其特征在于,步骤(a)中所用的氧化铝颗粒大小为10-100μm。
5.根据权利要求4所述的方法,其特征在于,步骤(a)中所用的氧化铝颗粒大小为25μm。
6.根据权利要求1所述的方法,其特征在于,步骤(b)中所用的酸混合物含有15-50%(v/v)的硫酸和0.01-1%(v/v)的氢氟酸。
7.根据权利要求6所述的方法,其特征在于,步骤(b)中所用的酸混合物含有28.8%(v/v)的硫酸和0.024%(v/v)的氢氟酸。
8.根据权利要求1所述的方法,其特征在于,步骤(b)中所述的化学处理是在50-110℃的温度下进行4-60分钟。
9.根据权利要求8所述的方法,其特征在于,步骤(b)中所述的化学处理是在75℃的温度下进行12分钟。
10.根据权利要求1所述的方法,其特征在于,步骤(c)中所述的热处理是在285℃的温度下进行60分钟。
11.根据权利要求1-10中任一项权利要求所述的方法制备的表面。
12.用于插入到骨组织中的钛基金属植入物,其特征在于,所述的金属植入物具有权利要求11所述的表面。
13.根据权利要求12所述的金属植入物,其特征在于,所述的金属植入物为钛或钛合金植入物。
14.根据权利要求13所述的金属植入物,其特征在于,所述的金属植入物是牙科植入物。
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CN112656549A (zh) * | 2020-05-22 | 2021-04-16 | 北京科仪邦恩医疗器械科技有限公司 | 髋臼假体的表面处理方法及髋臼假体 |
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EP2215991A1 (en) | 2010-08-11 |
EP2215991A4 (en) | 2012-10-17 |
JP2010538719A (ja) | 2010-12-16 |
ES2315194A1 (es) | 2009-03-16 |
US8277577B2 (en) | 2012-10-02 |
ES2315194B1 (es) | 2010-02-26 |
AR068377A1 (es) | 2009-11-11 |
US20100218854A1 (en) | 2010-09-02 |
WO2009034197A1 (es) | 2009-03-19 |
CA2699036A1 (en) | 2009-03-19 |
BRPI0722131A2 (pt) | 2014-04-08 |
US20130022787A1 (en) | 2013-01-24 |
RU2448739C2 (ru) | 2012-04-27 |
US9057124B2 (en) | 2015-06-16 |
RU2010114171A (ru) | 2011-10-20 |
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