CN1826088A - 骨诱导钛酸镁植入物及其制造方法 - Google Patents
骨诱导钛酸镁植入物及其制造方法 Download PDFInfo
- Publication number
- CN1826088A CN1826088A CNA2004800209670A CN200480020967A CN1826088A CN 1826088 A CN1826088 A CN 1826088A CN A2004800209670 A CNA2004800209670 A CN A2004800209670A CN 200480020967 A CN200480020967 A CN 200480020967A CN 1826088 A CN1826088 A CN 1826088A
- Authority
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- China
- Prior art keywords
- magnesium
- implant
- magnesium titanate
- film
- oxide
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
- 239000007943 implant Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 151
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 141
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 141
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 133
- 239000010936 titanium Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 27
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 18
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 15
- 239000012153 distilled water Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 19
- 230000015556 catabolic process Effects 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 2
- 238000001356 surgical procedure Methods 0.000 abstract description 6
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- 238000002316 cosmetic surgery Methods 0.000 abstract description 3
- 238000010883 osseointegration Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 2
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- 229940021013 electrolyte solution Drugs 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
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- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 4
- 108060003393 Granulin Proteins 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
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- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
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- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 3
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- 229910000157 magnesium phosphate Inorganic materials 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
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- 238000004381 surface treatment Methods 0.000 description 3
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Images
Classifications
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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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- 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
- A61C8/0013—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 with a surface layer, coating
- A61C8/0015—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 with a surface layer, coating being a conversion layer, e.g. oxide layer
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- 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
- C23C8/40—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 liquids, e.g. salt baths, liquid suspensions
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- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
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Abstract
本发明涉及可以植入活体植入物,用于牙科、矫形外科、上颌面外科和整形外科之类的医学领域的钛酸镁氧化膜,还涉及制造该植入物的方法。根据本发明,钛酸镁氧化膜植入物通过在钛或钛合金的表面形成结合有镁的氧化钛膜(钛酸镁氧化膜)而制得。用来制造本发明钛酸镁氧化膜植入物的方法包括在蒸馏水中用紫外光对由钛或钛合金制成的移植体辐照2小时以上;将用紫外光辐照过的移植体浸入含镁的电解质溶液中;在60至500伏的电压下通过阳极氧化在浸入的移植体上镀敷钛酸镁氧化膜。因此,本发明可以提供一种植入物,该植入物具有通过阳极氧化形成的具有更高生物相容性和生物活性的氧化钛膜,并为钛酸镁(TixMgyOz)植入物的成功骨整合提供最佳的钛酸镁氧化物(TixMgyOz)厚度。
Description
技术领域
本发明涉及可以植入活体,用于牙科、矫形外科、上颌面外科和整形外科之类的医学领域的钛酸镁氧化膜植入物,还涉及制造该植入物的方法。
背景技术
通常在对钛(或钛合金)植入物进行车床加工和铣削之后,还要对其进行各种表面处理,以改进其生物相容性。这些表面处理方法的例子是在酸性/碱性溶液中蚀刻,颗粒吹净,等离子喷射,热氧化,使用羟磷灰石、生物玻璃和生物陶瓷之类的生物活性材料的溶胶-凝胶引起的镀敷,物理/化学气相沉积,离子植入或等离子源离子植入,电化学阳极氧化和使用它们的任意组合的应用技术。
在这些方法中,作为使用电化学阳极氧化的表面处理方法的例子,已知有一种使用硫酸和盐酸的混合溶液、或硫酸和磷酸的混合溶液、或磷酸和草酸的混合溶液制造氧化膜的方法(德国专利第2,216,432号,日本专利公报延迟公开平02-194,195号,瑞典专利第1999-01973号);一种用来制造包含钙和磷的氧化膜的方法(美国专利第5,478,237号);一种涉及先形成阳极化膜、然后进行热处理的方法(美国专利第5,354,390号);一种涉及先用阳极氧化法形成钙的磷酸盐,然后进行水合加热处理,从而制得羟磷灰石的方法(美国专利第5,354,390);一种通过阳极氧化法制造无水磷酸二钙(DCPA,CaHPO)、磷酸三钙(α-TCP)、无定形磷酸钙(ACP)和二水合磷酸二钙(DCPD)的方法(美国专利第5,997,62?),以及通过阳极氧化法制造氧化钛膜的方法(欧洲专利公报第0676179号)。
然而,对钛或钛合金上镀敷有上述钙的磷酸盐或羟磷灰石的植入物来说,由于植入的机体与镀敷材料之间的界面上或镀敷材料内部发生生物作用,植入物发生镀敷材料剥离的问题,或发生生物降解和再吸收的问题,导致植入物附近的骨组织发生慢性炎症,因此长期使用这种植入物会造成成功率持续下降。另外,氧化膜越厚,其机械强度越低,氧化膜会从植入物和骨组织之间的界面剥离,进入骨组织。
说明书
技术问题
因此,针对上述问题,本发明的一个目标是提供一种钛酸镁氧化膜植入物,该植入物通过阳极氧化形成具有更高生物相容性和生物活性的氧化钛膜;以及提供制造该植入物的方法。
本发明的另一个目标是通过在钛和钛合金植入物的表面上形成具有骨诱导(osseoinductive)性质和极好机械强度的氧化膜,提供一种钛酸镁氧化膜植入物。该植入物用于牙科、矫形外科、耳鼻喉科、上颌面外科和整形外科,引发快速而牢固的骨结合,从而成功地实现骨整合(osseointegration);以及制造该植入物的方法。
技术解决方案
根据本发明一个方面,通过提供一种钛酸镁氧化膜植入物可完成上述目标和其他目标,所述植入物包括:包含钛或钛合金的移植体;和形成于该移植体表面的钛酸镁氧化膜。
在本发明中,通过低电压电介质击穿阳极氧化形成钛酸镁氧化膜。较佳的是,钛酸镁氧化膜的主要成分包括6至26%的钛,51至71%的氧和1.8至32%的镁;其次要成分为6至15%的碳,0.3至6%的磷,0.3至2.1%的钠和1至2%的氮;还包含作为添加剂的含量小于1%的硫、钙和钾。
根据本发明另一方面,提供了一种用来制造钛酸镁氧化膜植入物的方法,该方法包括:
在蒸馏水中用紫外光对钛或钛合金制成的移植体辐照2小时以上;将用紫外光辐照过的移植体浸入含镁的电解质溶液中;在60至500伏的电压下通过阳极氧化在浸入的移植体上镀敷钛酸镁氧化膜。
现在将参照附图详细描述本发明的钛酸镁氧化膜植入物及其制造方法。
本发明的钛酸镁氧化膜植入物由移植体和形成于移植体表面的钛酸镁氧化膜组成。本发明所用的移植体由钛或钛合金制成。钛酸镁氧化膜是这样形成的,即在低压下通过电介质击穿阳极氧化法向植入物的氧化膜内引入镁。较佳的是,以原子比计,钛酸镁氧化膜的主要成分包括1.8至50%的镁、6至26%钛和51至71%的氧,钛酸镁氧化膜还任选包含6至15%的碳、0.3至6%的磷、0.3至2.1%的钠、1至2%的氮和痕量的硫、钙和钾。另外,所述钛酸镁氧化膜具有双层结构,该双层结构包括上部的多孔层和下部的隔离氧化层。钛酸镁氧化膜的厚度优选为300纳米至30微米,更优选为500纳米至10微米。
具有这种结构的钛酸镁氧化膜植入物的生物化学作用机理如下。所述钛酸镁氧化膜植入物在氧化钛膜的化学组成中还包含镁,从而引起植入物与骨组织之间迅速地发生牢固的生物化学结合作用。Mg2+离子迁移到植入物的最外层或迁移入体液内,从而引起与体液中的Ca2+离子的离子交换反应,造成离子迁移。结果,植入物表面通过静电作用与具有多阴离子性质的骨基质蛋白质结合,所述骨基质蛋白质如I型骨胶原、凝血栓蛋白、纤连蛋白、玻璃粘连蛋白、微纤维蛋白、osteoadherin、骨桥蛋白、骨涎蛋白质、骨钙素、骨连接素和BAG-75。植入物和骨基质蛋白质之间的这种静电结合连续地促进了植入物周围的生物矿化。另外,本发明的植入物具有多孔的钛酸镁表面,它反过来诱导骨组织向表面的孔内生长,从而在植入物和骨组织之间引发了牢固的机械结合。也即是说,所述多孔钛酸镁氧化膜具有骨诱导表面性质,因此在植入物和骨组织之间产生的生物化学结合和机械结合的协同作用造成了快速而牢固的骨整合。
接下来将描述用来制造本发明钛酸镁氧化膜植入物的方法。
用来制造本发明的钛酸镁氧化膜植入物的方法包括以下步骤:在蒸馏水中用紫外光辐照移植体2小时以上;将紫外光辐照过的移植体浸入含镁的电解质溶液;以及通过阳极氧化在浸入的移植体上镀敷钛酸镁氧化膜。
下面详细描述上述方法的各个步骤。首先用诸如醇之类的合适试剂对移植体进行清洗和淋洗,从而使其脱脂,然后在蒸馏水中用紫外光辐照移植体2小时以上。在蒸馏水中用紫外光辐照移植体2小时以上的技术,会影响本发明阳极氧化过程中离子植入的效果。
然后将经过这种辐照的移植体浸入含镁溶液。本发明的溶液能够在任意含镁的单独或混合溶液,例如乙酸镁、磷酸镁、硫酸镁、碘酸镁、葡糖酸镁、硝酸镁、氢氧化镁和氯化镁中,通过本发明的低电压电介质击穿阳极氧化形成含镁氧化钛膜(钛酸镁氧化膜,TixMgyOz)。另外,本发明的钛酸镁氧化膜优选将镁含量保持在1至35%。出于该目的,溶液中的上述化合物的组成比可以改变。另外,为了调节任意单独或混合的含镁溶液的pH,可向其中加入以下化合物:硫酸、磷酸、各种有机酸(例如乙酸、草酸、苹果酸、琥珀酸、丙二酸)和硼酸、作为缓冲剂的氢氧化钠或氢氧化钾。
然后将所述植入物作为正极、铂作为负极,通过在大约60-500V的低压下在正极表面上引发短时间微弧(microarc),在植入物表面上形成钛酸镁氧化膜。尽管钛酸镁氧化膜的形成机理尚未得到充分了解,但是人们相信镁离子或镁络合离子化合物在电场驱动力的作用下发生胶体沉淀。
本发明的钛酸镁氧化膜提供了与常规的氧化膜植入物不同的全新化学结构。图1和图2分别是根据本发明进行阳极氧化之后的骨诱导钛酸镁氧化膜植入物的电子显微照片。图1是骨诱导钛酸镁氧化膜的表面的电子显微照片,图2是骨诱导钛酸镁氧化膜植入物表面的纵向截面图。如图1所示,由于钛酸镁氧化膜的表面具有多孔钛酸镁表面,它可以使骨组织向这些孔内生长,从而使植入物和骨组织之间产生牢固的机械结合。如图2所示,本发明的骨诱导钛酸镁氧化膜植入物由钛或钛合金制成的移植体1以及钛酸镁氧化膜2和3组成,钛酸镁氧化膜进一步分为表面多孔氧化层3以及形成于表面和移植体之间的隔离氧化层2。
另外,为了确保植入物在体内成功地长期发挥功能,氧化膜应当具有极好的机械性质(例如抗压强度和抗张强度)。为了在结构上加强含镁氧化钛膜的机械强度,在进行阳极氧化时,本发明将电流密度提高到4,000毫安/厘米2。提高电流密度会增加隔离氧化层在植入物表面的生长速率,与表面多孔氧化层3的厚度相比,下部隔离氧化层2的厚度变得更厚。结果,与整个氧化膜被孔或通道填充的常规氧化膜植入物相比,本发明的钛酸镁氧化膜的结构特性是对外力具有更高的抵抗作用。
另外,提高含镁氧化钛膜的生长速率的另一种方法是将溶液的温度尽可能保持在30℃。
同时,氧化膜越厚,其机械强度(例如抗张强度和抗压强度)越低。这样,所述钛酸盐氧化膜会从植入物和骨组织之间的界面剥离进入骨组织。本发明提供了最佳的钛酸镁氧化物(TixMgyOx)厚度,从而使钛酸镁氧化膜植入物能够成功地进行骨整合。为了完成这一点,本发明同时提供能够形成相应的最佳厚度氧化膜的电压(60至500伏)。
另外,在低电压电介质击穿阳极氧化过程中,为了防止植入物的正极表面上产生的气体(大部分是O2,H2)残留在钛酸镁氧化膜中,使它产生化学缺陷和结构缺陷,进而削弱其机械强度,需要将搅拌器的转速保持在500rpm以上,以最大程度减少植入物的正极表面吸附的气体。
骨诱导表面性质,例如钛酸镁氧化膜中的镁含量和表面加工性、表面形状和氧化膜的厚度,可根据各种因素,如溶液的组成比、施加的电压、电流密度、溶液温度、转速和pH改变。除了这些性质以外,本发明的钛酸镁氧化膜可通过任何常规的阳极氧化方法和设备形成。
有利的效果
本发明提供了能够使钛酸镁(TixMgyOz)植入物实现最成功的骨整合的最佳钛酸镁氧化膜(TixMgyOz)厚度。本发明的多孔钛酸镁氧化膜(TixMgyOz)具有不同于常规氧化膜植入物的全新骨诱导表面性质。具体地说,在植入物氧化膜的化学组成内加入镁,可以借助生物化学结合作用引发与骨组织的快速骨整合(生物化学骨整合)。同样,氧化膜的多孔表面结构引发了骨基质蛋白质的固着,使骨组织向孔内生长,从而提供了加强与植入物的机械骨整合(机械骨整合)的机会。结果,由于植入物与骨组织之间的生物化学结合和机械结合的协同效应,多孔钛酸镁氧化膜植入物引发了迅速而牢固的骨整合,从而持久地改善了钛和钛合金植入物的功能,提高了它们应用在诸如牙科、矫形外科、耳鼻喉科学、上颌面外科和整形外科领域的成功率。这样迅速产生的牢固的骨结合,必定导致成功的骨整合。
附图描述
通过以下结合附图的详细描述,可以更清楚地理解本发明的上述目标和其它目标、特征和其它优点,其中:
图1是本发明的骨诱导钛酸镁氧化膜植入物表面的电子显微照片;
图2是本发明的骨诱导钛酸镁氧化膜植入物表面的纵向截面图;
图3显示的是使用XPS分析法对本发明的钛酸镁氧化膜进行定性分析的结果;
图4显示使用XPS分析法对本发明钛酸镁氧化膜组分中的Mg进行定性分析的结果;
图5显示使用XPS分析法对本发明钛酸镁氧化膜组分中的Ti进行定性分析的结果;
图6显示使用XPS分析法对本发明钛酸镁氧化膜组分中的O进行定性分析的结果;
图7和图8分别是本发明的钛酸镁氧化膜表面的电子显微照片;
图9显示本发明钛酸镁氧化膜的增加速率与时间/电压之间关系;
图10显示本发明钛酸镁氧化膜的厚度与电压的关系。
最佳方式
现在将对本发明钛酸镁氧化膜植入物及其制造方法的优选实施方式进行详细描述。
本发明使用X-射线光电子分光仪(XPS)、俄歇电子分光仪(AES)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和X射线衍射(XRD)之类的高分辨率表面分析仪器,对上述钛/钛合金植入物的钛酸镁骨诱导表面性质,例如钛酸镁(TixMgyOz)的化学组成、钛酸镁的厚度、其孔的结构、钛酸镁表面和纵向截面的形状和结构以及其结晶度进行定性或定量表征。具体的试验条件列于以下实施例中。这些实施例仅是用于说明本发明,不应对本发明的范围和精神构成限制。
发明方式
实施例
根据本发明的实施方式,将0.01M至1.0M的乙酸镁、磷酸镁、硫酸镁、碘酸镁、葡糖酸镁、硝酸镁、氢氧化镁、氯化镁或乙二胺四乙酸以单一溶液或其任意混合溶液的形式用作形成钛酸镁氧化膜的电解质溶液。另外,为了将单一或混合溶液的pH调节到3.0至12.5,又向其中加入以下的酸:硫酸、磷酸或各种有机酸(例如乙酸、草酸、苹果酸、琥珀酸、丙二酸)或硼酸。另外,向其中加入氢氧化钠或氢氧化钾作为缓冲剂。当加入这些缓冲剂时,电解质溶液的总浓度最高增加至20M。
根据本发明的实施方式,将含镁电解质溶液的电流密度设定在10至4000毫安。另外,根据本发明的实施例,阳极氧化的电压可在直流23至500伏的范围内有不同的设定值。另外,为了防止本发明实施方式的钛酸镁氧化膜的机械强度发生化学削弱和/或结构削弱,将转速保持在500rpm以上,将溶液温度保持在30℃以下。上述实施例的试验条件简要地列于下表1。
表1
编号 | 电解质溶液的组成 | 电解质溶液的浓度(摩尔/升) | 电流密度(毫安/平方厘米) | 电压(伏,直流) | pH |
1 | 乙酸镁+缓冲剂 | 0.01-1.0 | 30-4000 | 50-500 | 低于7.0 |
2 | 磷酸酶+缓冲剂 | 0.01-1.0 | 30-4000 | 50-500 | 低于7.0 |
3 | 硫酸镁+缓冲剂 | 0.01-1.0 | 30-4000 | 50-500 | 低于7.0 |
4 | 碘酸镁+缓冲剂 | 0.01-1.0 | 120-1000 | 50-500 | 低于7.0 |
5 | 葡糖酸镁+缓冲剂 | 0.01-1.0 | 60-4000 | 50-500 | 低于7.0 |
6 | 硝酸镁+缓冲剂 | 0.01-1.0 | 10-300 | 23-500 | 低于7.0 |
7 | 氢氧化镁+缓冲剂 | 0.01-1.0 | 30-4000 | 50-500 | 低于7.0 |
8 | 氯化镁+缓冲剂 | 0.01-1.0 | 30-4000 | 50-500 | 低于7.0 |
9 | 硝酸镁+乙酸+缓冲剂 | 0.01-1.0 | 30-2000 | 23-500 | 3.5-12.5 |
10 | 磷酸镁+苹果酸+缓冲剂 | 0.01-1.0 | 20-4000 | 50-500 | 3.5-12.5 |
11 | 乙酸镁+草酸+缓冲剂 | 0.01-1.0 | 10-1000 | 50-500 | 3.5-12.5 |
12 | 硫酸镁+乙二胺四乙酸+缓冲剂 | 0.01-1.0 | 30-4000 | 50-500 | 3.5-12.5 |
13 | 葡糖酸镁+氢氧化钠+缓冲剂 | 0.01-1.0 | 30-4000 | 50-500 | 3.5-12.5 |
14 | 氢氧化镁+磷酸+缓冲剂 | 0.01-1.0 | 30-4000 | 50-500 | 3.5-12.5 |
15 | 碘酸镁+乙酸+缓冲剂 | 0.01-1.0 | 120-2000 | 50-500 | 3.5-12.5 |
16 | 氯化镁+草酸+缓冲剂 | 0.01-1.0 | 50-1000 | 50-500 | 3.5-12.5 |
表2显示根据本发明实施方式,通过在含镁溶液中进行低电压电介质击穿阳极氧化在植入物表面形成的钛酸镁氧化膜原子组成的XPS定量分析结果。
表2
元素 | 样品1 | 样品2 | 样品3 | 样品4 | 样品5 | 样品6 |
Ti | 18.78 | 26.29 | 5.72 | 6.4 | 6.51 | 7.32 |
O | 55.72 | 56.22 | 69.23 | 67.35 | 56.32 | 50.07 |
Mg | 1.84 | 2.25 | 13.6 | 15.23 | 25.58 | 32.31 |
C | 15.24 | 9.57 | 9.44 | 7.02 | 7.32 | 6.38 |
P | 5.86 | 3.1 | 0 | 1.4 | 0 | 2.4 |
N | 1.4 | 2.02 | 0 | 0 | 0.6 | 1.2 |
S | 0.3 | 0 | 0.5 | 0.5 | 0 | 0 |
Na | 0.5 | 0.5 | 0 | 0 | 2.13 | 0.3 |
K | 0 | 0 | 0 | 0.6 | 0 | 0 |
Ca | 0 | 0 | 0 | 0 | 0.8 | 0 |
从上表2可以看到,本发明的钛酸镁的主要成分包含6-26%的钛、51-71%的氧和1.8-32%的镁,次要成分包含6-15%的碳、0.3-6%的磷、0.3-2.1%的钠和1-2%的氮,还包含少于1%的硫、钙和钾。
图3至图6显示通过XPS分析法对本发明钛酸镁氧化膜进行定性分析的结果。从图4可以看到,镁在Mg 1s的结合能显示从1303.96eV至1302.88eV的化学位移。这意味着钛酸镁氧化膜表面的化学结合态随元素镁的含量而变化。这些结果说明钛酸镁氧化膜中的自然数x、y和z可在恒定的范围内变化。
接下来,电解质溶液浓度的变化给钛酸镁氧化膜带来了以下影响。在显示电压-时间特征的曲线中,通常较高的含镁电解质溶液浓度会使钛酸镁氧化膜的形成速率降低,并降低电介质击穿电压。因此,含镁电解质溶液的浓度越高,吸附进氧化钛膜的镁的量越高,直至镁含量达到32%。图7是使用较低浓度电解质溶液的钛酸镁氧化膜表面的电子显微照片,图8是使用较高浓度电解质溶液的钛酸镁氧化膜的电子显微照片。从图7和图8可以看到,与在较低浓度混合溶液中形成的钛酸镁氧化膜相比,在较高浓度混合溶液中形成的钛酸镁氧化膜具有更大的表面孔隙率。
根据本发明的实施方式,钛酸镁氧化膜中的镁含量也随电流密度的改变而变化。一般来说,当电流密度增加至高达4000毫安/平方厘米时,阳极化膜的形成速率急剧增加,结果膜的厚度也会增大。另外,将电流密度增加至高达4000毫安/平方厘米会使钛酸镁氧化膜表面的孔径变大,表面孔隙率的增大会引起蛋白质的结合以及骨组织向孔内的生长,从而加强了它们与植入物的机械结合。
接下来,在钛酸镁氧化膜上发生阳极氧化时的电压的变化引起了以下结果。钛酸镁氧化膜的厚度与特定的电压和时间成正比,可以增加至高达几十微米。例如,在表1所列的任意溶液中,在500伏的直流电压下含镁氧化膜的厚度可生长至高达30微米。用来使镁离子胶体沉积在氧化膜中,并同时在钛酸镁氧化膜表面上形成孔的电压是直流60伏。另外,由于较厚的氧化膜会降低其机械强度(例如抗张强度、抗压强度),氧化膜从植入物和骨组织之间的界面剥落入骨组织的风险很大。因此,用来达到使钛酸镁氧化膜植入物成功骨整合的最佳钛酸镁氧化膜厚度——300纳米至20微米——所需的电介质击穿电压是60至450伏。这是优选的电压范围,所得到的钛酸镁表面的孔径和孔隙率能够在发挥骨诱导性质的同时满足钛酸镁氧化膜中镁含量高于5%的要求。
尽管本发明出于说明的目的已经描述了优选实施方式,但是本领域技术人员能够理解,可以在不背离附加权利要求书所揭示的本发明范围和精神的基础上,对本发明进行各种改变和替换。
权利要求书
(按照条约第19条的修改)
1.一种钛酸镁植入物,包括:
包含钛或钛合金的移植体;和
通过低电压电介质击穿阳极氧化在单一或混合的含镁溶液中形成在所述移植体表面上的钛酸镁氧化膜。
3.如权利要求1所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜的主要成分包括6至26%的钛、51至71%的氧和1.8至32%的镁。
4.如权利要求1所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜具有双层结构,该双层结构包括上部的多孔层和下部的隔离层。
5.如权利要求1所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜的厚度为300纳米至30微米。
6.如权利要求5所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜的厚度为500纳米至10微米。
7.一种制造钛酸镁氧化膜植入物的方法,包括:
在蒸馏水中用紫外光对钛或钛合金制成的移植体辐照2小时以上;
将用紫外光辐照过的移植体浸入含镁的电解质溶液中;
在60至500伏的电压下通过阳极氧化在浸入的移植体上镀敷钛酸镁氧化膜。
8.如权利要求7所述的方法,其特征在于,所述电解质溶液是单一或混合的含镁溶液。
9.如权利要求7或8所述的方法,其特征在于,所述电解质溶液的浓度为0.01M至1.0M。
10.如权利要求7或8所述的方法,其特征在于,所述电解质溶液的pH为3.0至12.5。
11.如权利要求7或8所述的方法,其特征在于,用来进行阳极氧化的电流密度为30-4000毫安/平方厘米。
Claims (11)
1.一种钛酸镁植入物,包括:
包含钛或钛合金的移植体;和
形成在所述移植体表面上的钛酸镁氧化膜。
2.如权利要求1所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜是通过低电压电介质击穿阳极氧化在单一或混合的含镁溶液中制造的。
3.如权利要求1或2所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜的主要成分包括6至26%的钛、51至71%的氧和1.8至32%的镁。
4.如权利要求1或2所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜具有双层结构,该双层结构包括上部的多孔层和下部的隔离层。
5.如权利要求1或2所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜的厚度为300纳米至30微米。
6.如权利要求5所述的钛酸镁植入物,其特征在于,所述钛酸镁氧化膜的厚度为500纳米至10微米。
7.一种制造钛酸镁氧化膜植入物的方法,包括:
在蒸馏水中用紫外光对钛或钛合金制成的移植体辐照2小时以上;
将用紫外光辐照过的移植体浸入含镁的电解质溶液中;
在60至500伏的电压下通过阳极氧化在浸入的移植体上镀敷钛酸镁氧化膜。
8.如权利要求7所述的方法,其特征在于,所述电解质溶液是单一或混合的含镁溶液。
9.如权利要求7或8所述的方法,其特征在于,所述电解质溶液的浓度为0.01M至1.0M。
10.如权利要求7或8所述的方法,其特征在于,所述电解质溶液的pH为3.0至12.5。
11.如权利要求7或8所述的方法,其特征在于,用来进行阳极氧化的电流密度为30-4000毫安/平方厘米。
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2004
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- 2004-03-04 US US10/562,925 patent/US7452566B2/en not_active Expired - Fee Related
- 2004-03-04 CN CN200480020967A patent/CN100584289C/zh not_active Expired - Fee Related
- 2004-03-04 AT AT04717311T patent/ATE482667T1/de not_active IP Right Cessation
- 2004-03-04 WO PCT/KR2004/000460 patent/WO2005084577A1/en not_active Application Discontinuation
- 2004-03-04 EP EP20040717311 patent/EP1659978B1/en not_active Expired - Lifetime
- 2004-03-04 DE DE200460029377 patent/DE602004029377D1/de not_active Expired - Lifetime
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102525673A (zh) * | 2010-10-07 | 2012-07-04 | 长庚医学科技股份有限公司 | 一种牙植体表面处理的方法 |
CN104853694A (zh) * | 2013-06-07 | 2015-08-19 | 韩国牙材股份有限公司 | 骨移植材牙齿加工自动化机械 |
CN104853694B (zh) * | 2013-06-07 | 2016-08-24 | 韩国牙材股份有限公司 | 骨移植材牙齿加工自动化机械 |
CN103536371A (zh) * | 2013-10-21 | 2014-01-29 | 中国科学院上海硅酸盐研究所 | 一种牙科种植体及其制备方法 |
CN103536371B (zh) * | 2013-10-21 | 2016-03-23 | 中国科学院上海硅酸盐研究所 | 一种牙科种植体及其制备方法 |
CN104928678A (zh) * | 2015-05-15 | 2015-09-23 | 佳木斯大学 | 一种含钛试件表面制备微纳结构钛酸镁活性功能涂层的方法及应用 |
CN104928678B (zh) * | 2015-05-15 | 2019-06-14 | 佳木斯大学 | 一种含钛试件表面制备微纳结构钛酸镁活性功能涂层的方法 |
CN112545713A (zh) * | 2020-11-23 | 2021-03-26 | 天衍医疗器材有限公司 | 一种骨填充假体及其制备工艺 |
CN115969551A (zh) * | 2023-02-20 | 2023-04-18 | 北京华益圣亚医疗器械有限公司 | 口腔种植体及该种植体的制作方法 |
Also Published As
Publication number | Publication date |
---|---|
ATE482667T1 (de) | 2010-10-15 |
EP1659978A4 (en) | 2009-02-25 |
CN100584289C (zh) | 2010-01-27 |
WO2005084577A1 (en) | 2005-09-15 |
DE602004029377D1 (de) | 2010-11-11 |
BRPI0411404A (pt) | 2006-07-25 |
EP1659978A1 (en) | 2006-05-31 |
EP1659978B1 (en) | 2010-09-29 |
US7452566B2 (en) | 2008-11-18 |
US20060161263A1 (en) | 2006-07-20 |
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