CN115190806A - 一种用于可以集成到硬组织和软组织中的植入物、螺钉和板的白色、抗菌、生物相容的、粘附牢固的涂层及其制备方法 - Google Patents
一种用于可以集成到硬组织和软组织中的植入物、螺钉和板的白色、抗菌、生物相容的、粘附牢固的涂层及其制备方法 Download PDFInfo
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Abstract
提出了一种用于可以集成到硬组织和软组织中的元件的白色、抗菌、生物相容的、粘附牢固的涂层，所述元件特别是植入物、螺钉或板，所述涂层具有氧含量变化的含金属的梯度层的构造，其中最外梯度层的带隙大于3.1eV，其中最外梯度层是结晶的并且其中所述梯度层具有钽和/或铌和/或锆和/或钛。
Description
技术领域
本发明涉及一种用于可以集成到硬组织和软组织中的植入物、螺钉和板的白色、抗菌、生物相容的、粘附牢固的涂层，相关的制备方法以及具有这种涂层的植入物。
在抗菌性、生物相容性条件和化学抗性方面满足特殊要求的涂层已被多次描述。可以引用以下出版物作为示例：R.Thull,Elektrochemische Prüfung von(Ti,Nb)ONbeschichteten Legierungen((Ti,Nb)ON涂层合金的电化学测试),BiomedizinischeTechnik,Vol.36(9),pages 214 and following,1991；W.W.Plitz,Reib-und Verschleiβuntersuchungen von(Ti,Nb)ON Schichten((Ti,Nb)ON层的摩擦磨损检查),LaborBiomechanik,Munich,1994；R.Thull,K.Taubner,E.J.Kahle,biologische undtierexperimentelle Untersuchungen(Ti,Zr)O2und(Ti,Nb)ON(生物和动物实验检查(Ti,Zr)O2和(Ti,Nb)ON),Biomedizinische Technik,Vol.37,7-8,1992；R.Thull,K.Taubner,E.J.Kahle,Modell zur immunologischen Prüfung von Biomaterialien(生物材料免疫学测试模型),Biomedizinische Technik,Vol.37,162-169,1992；D.Repenning,Materialempfindlichkeit bei Titanimplantaten(钛植入物的材料敏感性)–第1部分,Zahnheilkunde Management ZMK,2010；M.Stelzel et al.,Verhalten verschiedenerTitanoberfl
chen bei oraler Exposition–eine In-vivo-Studie(口腔暴露时不同钛表面的行为-体内研究),Philips University,Marburg,Dept.Parodontology 2003；D.Repenning,Oberfl
chenbeschichtung auf Implantaten,oss
re Integration(植入物表面涂层，骨整合)53-61,Springer Verlag；Betz,Reuther,5-j
hrige klinischeStudie enossaler Implantate unter besonderer Berücksichtigung des periimplant
ren Gewebes(在特别考虑植入体周围组织下的内骨质植入体的5年临床研究),DeutscheZeitschrift für Mund-und Kieferchirurgie,1995。
所有这些层的缺点是它们不满足白色表面的审美标准。在本说明书上下文中，“白色”在此应理解在浅灰色到浅粉色直至纯白色之间着色的色域，其在相应的有机环境中被感知为白色。
特别是对于由钛制成的经涂层的牙科植入体，存在提供美观的白色表面的愿望。这同样适用于植入体的内骨质部分和基台。同时，表面符合上述生物相容性要求(ELISA，Thull)，以及有效防腐蚀保护以防止基材材料中的离子逸出和抗菌性，特别是对致病性、厌氧性细菌。最后但并非最不重要的一点是，经形貌优化调整的表面必须确保可靠的骨整合。
迄今为止可用的涂层具有从金色(氮化物)到深蓝色(陶瓷钛锆氧化物层)到黑色(DLC＝类金刚石碳)的颜色外观。已知的白灰色涂层以羟基磷灰石涂层(HA涂层)为代表，其用于更好的骨整合。然而，这些HA涂层在组织中会随时间吸收。此外，它们仅适用于植入物的内骨质部分，而不适用于植入物的经龈部分。
白色或通过电解方法产生的类白色的二氧化钛涂层也已为人所知。但是，二氧化钛不符合上述对抗菌的要求(参见M.Stelzel et al.,Verhalten verschiedenerTitanoberfl
chen bei oraler Exposition–eine In-vivo-Studie(口腔暴露时不同钛表面的行为-体内研究),Philips Universit
t,Marburg,dept.Parodontologie 2003)，并且仅在较低程度上具有生物相容性(参见R.Thull,K.Taubner,E.J.Kahle,biologische undtierexperimentelle Untersuchungen(Ti,Zr)O2 und(Ti,Nb)ON(生物和动物实验检查(Ti,Zr)O2和(Ti,Nb)ON),Biomedizinische Technik,Vol.37,7-8,1992)。其他已知的涂覆植入体的方法是基于溶胶-凝胶工艺和喷涂工艺。等离子喷涂(APS)、冷喷涂(CGS)、高速火焰喷涂(HVOF)、电弧喷涂(AS)、粉末火焰喷涂(PFS)以及最后但并非最不重要的线火焰喷涂属于喷涂工艺。所有这些层的缺点是它们不能以足够粘附牢固地施加于医疗应用或/和不能以足够的精度施加到细分区的植入体上。
目前，白色牙科植入体由二氧化锆全陶瓷制成。为了防止断裂，陶瓷掺杂有氧化钇。陶瓷植入物有一个特殊的缺点，即它们的表面不能进行最佳的形貌调整以实现可靠的骨整合，并且由于断裂的风险，它们对操作和长期稳定性(或第一年的过早损失)构成了特别和增加的挑战。此外，由于材料技术系统的原因，陶瓷的组成不能自由变化，因此不能使材料充分适应生物环境。
在上述陈述的背景下，本发明的目的是克服现有技术的缺点，并提供一种用于植入物的涂层，该涂层不仅在表面颜色方面符合美学标准，而且具有良好的生物相容性，长期稳定性和抗菌性。
该任务通过具有权利要求1的特征的涂层解决。该任务进一步通过生产具有权利要求12的特征的涂层的方法和具有权利要求21的特征的植入物来解决。
从属权利要求将提供有利的进一步发展。
本发明的一个基本思路在于以梯度层构建多层的涂层，梯度层中的氧含量是变化的。施加在元件上的最低梯度层优选设计为金属性粘附促进层。在本发明的上下文中，金属性粘附促进层被理解为是指由金属构成并且基本上不含氧的梯度层。经此实现对元件的最佳附着力。在金属性粘附促进层上形成的梯度层优选具有从最下面的在元件上施加的梯度层到最外面的梯度层增长至全化学计量的氧含量，使得最外梯度层是具有全化学计量的金属氧化物层。
通过梯度层逐渐增加氧含量，提高梯度层之间的粘合力。金属性粘附促进层和氧含量低于最外层金属氧化物梯度层的全化学计量的梯度层都具有由具有氧含量的梯度层内的晶体结构中的缺陷引起的色泽，其中出现电子中间态，导致特征性吸收并由此产生材料的色泽。具有完全化学计量的最外梯度层是结晶的并且在结构中基本上没有影响着色的缺陷。因此，一方面所产生的涂层由于从金属性粘附促进层到最外层金属氧化物梯度层的逐渐变化的氧含量表现出优异的粘附性能，同时通过最外金属氧化物梯度层的存在具有白色。
最外金属氧化物梯度层的带隙大于3.1eV，使得最外层不吸收可见光范围内的电磁波，因此呈现白色。
此外，带隙大于3.1eV的材料，特别是陶瓷系统，具有高电阻(R>>1000Ωcm-2)，并有助于避免生物组织与由该材料形成的植入物之间通过电子交换的反应。
根据本发明用涂层实现的抗菌性、生物相容性和粘附强度对于与植入物相关使用的所有元件都是有利的。因此，根据本发明的涂层可用于整个植入物组件。在这一点上应再次明确指出，根据本发明的涂层适用于可以集成到硬组织和软组织中或可以与之相连的整个元件及其表面，例如植入物、基台和连接元件(例如螺钉)的所有表面，包括它们的整个外表面以及包括螺纹部分的内表面。
优选地，具有氧含量的梯度层中的至少一个，特别是至少最外面的金属氧化物梯度层具有5nm或更大的晶粒尺寸。晶粒尺寸在亚微米范围内的纳米晶体结构有助于提高层的断裂韧性。晶粒尺寸的确定是通过X射线衍射法进行的。
优选地，梯度层具有钽和/或铌和/或锆和/或钛。这些金属的特点是生化稳定性高。
根据本发明的方法，涂层的施加优选地通过PVD(物理气相沉积)工艺进行。PVD工艺通常用于医用植入物和器械的涂层。其优点是调整化合物的高度可变性，无论是纯金属、氧化物、氮化物、碳化物或更复杂的组分。
根据本发明，氧化的至少纳米晶体层作为梯度层借助PVD工艺制备，其中至少最外梯度层的带隙Eg大于3.1eV。借助梯度层实现层的粘附，首先将金属性粘附促进层施加到元件上，然后将层的氧含量调节至全化学计量，优选小于500nm之内。重要的是梯度层没有缺陷，以至于没有建立导致带隙减小或用作长波光的吸收中心的电子状态。
PVD工艺的一个特别的缺点，即在热力学平衡之外的沉积条件被消除了，因为涂层是在高于T＝300℃的升高温度下制成的和/或这些层随后在氧气气氛下完善。关于抗菌性的额外特定要求优选通过层的多阶段调整来实现。多相层在表面上的pzzp(point of zerozeta potential)变化具有细菌排斥作用。
在下文中，还将依据实施例就进一步的特征和优点来描述本发明，这些实施例基于附图被更详细地解释。
在此图1显示了具有根据本发明的涂层的元件的示意图。
图1示出了由诸如螺钉或板可以集成到硬组织和软组织中的植入物形成的元件20。在元件20上施加了由多个梯度层11、12、13构成根据本发明的涂层。形成在元件20上的最下层梯度层11是金属性粘附促进层。最外梯度层13是包含具有完全化学计量的金属氧化物的白色层。在梯度层11和13之间，形成一个或多个梯度层12，其氧含量从元件20上形成的最下梯度层11增长到具有全化学计量的最外梯度层13。
在最简单的情况下，将白色层调整为二氧化锆层。二氧化锆作为全陶瓷材料用于种植学。然而，到目前为止，还没有成功地将二氧化锆作为牢固粘附的白色层施加到钛植入体上。在根据本发明的实施中，在其表面优选地被粗糙化并且在优选的实施形式中由钛形成的元件20上首先沉积厚度为20nm的金属层作为由锆制成的最下梯度层11。在下文中，借助典型的PVD反应过程连续供应氧气，使所述层经由梯度层12最终形成达到存在于最外梯度层13中的全化学计量。所述涂层的整个层厚优选调整到5微米。可以进行工艺控制，使得沉积在升高的温度下发生，从而不产生另外的PVD典型(X射线非晶)层，而是产生至少纳米晶层。
在第二实施例中，针对最外梯度层13调整具有20Mol％Nb2O5和80Mol％Ta2O5的混合相，并且从最下面的金属梯度层11开始经由中间梯度层12构建全化学计量。这些层表现处特别高的生化稳定性和负表面电位。负表面电位导致钙离子的稳定吸附和与之相关的可靠的骨整合。
在另一个实施例中，最外梯度层13采用具有ZrTi2O6化学计量的层。(Ti,Zr)O2-x层是高度生物相容性的并由于其高缺陷的结构、其X射线无定形的形态和不精确的组成调节而具有蓝黑色。根据本发明的涂层具有带隙Eg为3.1eV或更大的外梯度层13，并且在化学计量方面被精确调整。这种梯度层13是纳米晶体。由于其高负值的自由生成焓，最外梯度层13另外具有显著改善的生化稳定性。其零电位点为pH 6-7。
Claims (21)
1.一种用于可以集成到硬组织和软组织中的元件(20)的白色、抗菌、生物相容的、粘附牢固的涂层，所述元件特别是植入物、螺钉或板，所述涂层具有由金属梯度层(11、12、13)构成的结构，所述含金属的梯度层具有变化的氧含量，其中最外梯度层(13)的带隙(Eg)大于3.1eV，其中所述最外梯度层是结晶的，并且其中所述梯度层(11、12、13)具有钽和/或铌和/或锆和/或钛。
2.根据权利要求1所述的涂层，其中施加到所述元件(20)上的最下面的梯度层(11)是金属性粘附促进层，最外面的梯度层(13)是具有全化学计量的金属氧化物层，并且其中中间梯度层(12)具有从施加到元件上的最下梯度层(11)增长到最外梯度层(13)的全化学计量的氧含量。
3.根据权利要求1或2所述的涂层，其中具有氧含量的梯度层(12、13)中的至少一个，优选地至少最外梯度层(13)具有5nm或更大的晶粒尺寸。
4.根据前述权利要求中任一项所述的涂层，其中所述梯度层(11、12、13)还具有铝和/或锡。
5.根据前述权利要求中任一项所述的涂层，其中所述梯度层(12、13)中的金属浓度用至少二元的氧化物调节，使得具有至少二元氧化物的梯度层(12、13)具有大于3.1eV的带隙(Eg)。
6.根据前述权利要求中任一项所述的涂层，其中一个或多个梯度层(11、12、13)包含碳和/或氮和/或硼和/或氟。
7.根据前述权利要求中任一项所述的涂层，其中施加到所述元件上的最下梯度层(11)具有50nm或更小的厚度。
8.根据前述权利要求中任一项所述的涂层，其中具有降低的氧化学计量的梯度层(12)的总厚度为500nm或更小，优选200nm或更小，进一步优选100nm或更小，进一步优选60nm或更小。
9.根据前述权利要求中任一项所述的涂层，其中所述最外梯度层(13)的厚度为10μm或更小。
10.根据前述权利要求中任一项所述的涂层，其中所述涂层的总厚度介于3μm与7μm之间，优选介于4μm与6μm之间，进一步优选介于4.5μm与5.5μm之间。
11.一种用于生产用于可以集成到硬组织和软组织中的元件(20)的白色、抗菌、生物相容的粘附牢固的涂层的方法，所述元件特别是植入物、螺钉或板，特别是根据前述权利要求中任一项的涂层，其具有以下步骤：
-借助PVD(物理气相沉积)将金属性粘附促进层作为第一梯度层(11)施加到元件(20)的表面上上，
-将具有钽和/或铌和/或锆和/或钛以及氧的梯度层(12、13)以增加的氧含量施加到金属性粘附促进层(11)上，所述增加的氧含量通过在施加梯度层(12、13)的过程中氧含量的增加直至达到最外梯度层(13)中的完全化学计量，
其中最外梯度层(13)的带隙(Eg)大于3.1eV。
12.根据权利要求11所述的方法，其中所述梯度层(11、12、13)的施加是在300℃或更高的温度下进行的。
13.根据权利要求11或12所述的方法，其中所述梯度层(11、12、13)在氧气气氛下被固化。
14.根据权利要求11至13中任一项所述的方法，其中所述梯度层(11、12、13)形成具有5nm或更大的晶粒尺寸。
15.根据权利要求11至14中任一项所述的方法，其中所述梯度层(11、12、13)具有钽和/或铌和/或锆和/或钛以及氧。
16.根据权利要求11至15中任一项所述的方法，其中所述梯度层(11、12、13)还具有铝和/或锡。
17.根据权利要求11至16中任一项所述的方法，其中进行所述梯度层(11、12、13)的施加使得施加到所述元件(20)上的最下梯度层(11)是金属性粘附促进层，最外梯度层(13)是具有完全化学计量的金属氧化物层，并且其中中间梯度层(12)具有的氧含量从施加到元件上的最下梯度层(11)增长到最外梯度层(13)的全化学计量。
18.根据权利要求11至17中任一项所述的方法，其中所述梯度层(12、13)中的金属浓度用至少二元的氧化物调节，使得具有至少二元氧化物的所述梯度层(12、13)具有大于3.1eV的带隙(Eg)。
19.根据权利要求11至18中任一项所述的方法，其中一个或多个梯度层(11、12、13)包含碳和/或氮和/或硼和/或氟。
20.一种具有根据权利要求1至10中任一项所述的涂层的植入物，优选按照根据权利要求11至19中任一项所述的方法制备。
21.根据权利要求20所述的植入物，其中所述植入物由具有内骨质部分和基台的牙科植入体形成，其中所述涂层被施加到所述牙科植入体的内骨质部分和基台上。
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| CN101636186A (zh) * | 2006-11-10 | 2010-01-27 | 山特维克知识产权股份有限公司 | 外科植入物复合材料和试剂盒以及制造方法 |
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| Publication number | Publication date |
|---|---|
| WO2021151832A1 (de) | 2021-08-05 |
| JP2023512010A (ja) | 2023-03-23 |
| US20230091812A1 (en) | 2023-03-23 |
| KR20220133945A (ko) | 2022-10-05 |
| DE102020101882A1 (de) | 2021-07-29 |
| EP4096731A1 (de) | 2022-12-07 |
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