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CN110732044A - 玻璃-金属馈通件 - Google Patents

玻璃-金属馈通件 Download PDF

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CN110732044A
CN110732044A CN201910663264.8A CN201910663264A CN110732044A CN 110732044 A CN110732044 A CN 110732044A CN 201910663264 A CN201910663264 A CN 201910663264A CN 110732044 A CN110732044 A CN 110732044A
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glass
expansion
coefficient
metal
conductor
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CN110732044B (zh
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R·海特乐
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Schott AG
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Abstract

本发明涉及一种玻璃‑金属馈通件，其由外导体、玻璃材料和内导体构成，其中内导体具有膨胀系数α内，玻璃具有膨胀系数α玻璃并且外导体具有膨胀系数α外，其特征在于，内导体的膨胀系数α内大于玻璃的膨胀系数α玻璃，并且在20℃直至玻璃转变温度的温度范围中外导体的膨胀系数α外比玻璃的膨胀系数α玻璃高至少2ppm/K、优选至少4ppm/K。

Description

玻璃-金属馈通件
技术领域
本发明涉及一种玻璃-金属馈通件，其由外导体、玻璃材料和内导体构成，并且涉及其在医疗设备、尤其植入式医疗设备和装置中的应用，还涉及具有这种玻璃-金属馈通件的设备。
背景技术
玻璃-金属馈通件应用在电子技术的不同应用领域中。例如，其应用于电子技术和传感技术中的结构元件的壳体中的电导体的馈通件。在此，这种构件具有玻璃与各种金属材料的熔融连接。通过将金属构成的内导体熔化到通过由金属构成的外导体包围的玻璃或玻璃陶瓷材料中可在壳体中提供导体的严密密封的馈通件。非常特殊的玻璃-金属馈通件是这种馈通件，在其中馈通件本身或馈通件的一部分与人体接触。在这种馈通件中需要确保使用的所有部件具有高的抗腐蚀性以及良好的耐久性。尤其这种馈通件仅释放有限量的Ni，从而防止形成过敏性反应。这在用于所谓的镍释放的极限值的标准中限定。对此参考DIN EN 1811和DIN EN 12472。
在玻璃-金属馈通件中作为用于馈通件的导体的材料主要使用Fe-Ni、Fe-Ni-Co、Fe-Ni-Cr合金。这些材料的优点是其热膨胀极优异地匹配熔融玻璃。但是所有这些材料在基础材料中都具有显著的Ni含量。此外，其具有镍涂层，从而保护材料以防腐蚀，这又释放了不期望量的镍。
为了防止释放Ni，在现有技术中规定，馈通件导体或内导体设有足够厚的金涂层，以便降低镍渗透。但是这具有的缺点是，其仅仅能不充分地防止Ni渗出，或为了实现该效果需要设置非常厚的、厚度大于2.5μm的金涂层。
代替对涂层导体的解决方案，DE 198 42 943 A1作为最接近的现有技术提出，使用钽作为内导体或替代地使用无镍的、无锈的铁素体优质钢，例如根据US标准AISI 446的钢，其为不锈的、耐热的、具有铝添加物的铁素体铬钢。铁素体优质钢AISI 446的膨胀系数仅稍微高于常见的玻璃。因此存在的风险是，内导体在冷却时比玻璃收缩更强烈，并且与玻璃的接口裂开。DE 198 42 943 A1的另一缺点是，对无Ni材料的选择是有限的，因为仅在内导体的膨胀系数α内小于玻璃的膨胀系数α玻璃时提供馈通件的足够密封性。
由US 3,770,568 A已知一种玻璃组合物，其可用于严密密封的钽电解电容器，并且在玻璃组合物中包括有效的铬含量。
发明内容
因此，本发明的目的是提供一种玻璃-金属馈通件，其允许更宽泛地选择内导体的材料，并且提供密封的馈通件。
尤其如此内导体是可能的，该内导体一方面在其与人体接触时没有释放镍，另一方面也具有足够的可焊接性。
该目的通过具有权利要求1的整体特征的玻璃-金属馈通件来实现。本发明的有利设计方案是从属权利要求的主题。
根据本发明的玻璃-金属馈通件的特征是，内导体的膨胀系数α内大于玻璃的膨胀系数α玻璃，并且在20℃直至玻璃转变温度的温度范围中外导体的膨胀系数α外和玻璃的膨胀系数α玻璃之间的差至少为2ppm/K、优选至少4ppm/K，并且外导体的膨胀系数α外大于玻璃的膨胀系数α玻璃。
通过将外导体以压力预紧到玻璃上实现了，玻璃也将正压力(接合压力)施加到玻璃与内导体的界面上。从中得出以下优点，该压力可靠密封地保持连接。此外，实现了玻璃-金属馈通件的小的结构高度，并且这可用于不同的应用领域、例如可用于监控病人的设备或休闲领域的手环。
对作为内导体的销相对于玻璃的较大膨胀的限制以及外导体相对于玻璃的膨胀大至少2ppm/K，这尤其在销的材料膨胀很大、具有的膨胀高于10ppm/K的情况下有很大效果。在该范围中几乎没有好的熔融玻璃。
令人惊奇的是，本发明已经发现，例如可使用具有10.5％和20％之间的高的铬含量的铁素体优质钢、优选铬含量从15至17％的优质钢，例如铁素体优质钢AISI 430。代替铁素体优质钢也可使用其他材料，例如钼、钨或铂。这些其他材料同样具有低的过敏可能性。对于这些材料必须满足根据本发明的膨胀系数的条件α内＞α玻璃，其中α内是内导体的膨胀系数并且α玻璃是玻璃的膨胀系数。
但是使用这些钢的问题是，其11.6至11.5·10-6/K的热膨胀系数α内明显高于在10.6至6.1·10-6/K范围中的玻璃的膨胀系数α玻璃。本发明人惊奇地发现，尽管导体的α内较大，其高于α玻璃，其与现有技术规定的在玻璃-金属馈通件中内导体的热膨胀不允许高于使用的玻璃的热膨胀以便提供足够的密封性相反，但是在α内大于α玻璃的情况下，在提供正的高的接合压力时此时提供了密封的嵌入，该接合压力从外导体施加到玻璃上。如进一步的研究显示，在接合压力仅为正的时，对于密封性是不够的，而是接合压力必须大于30Mpa、优选大于50Mpa、尤其大于100Mpa，从而实现可靠的嵌入。
在α内小于α玻璃的情况下，在由外导体将足够的压力预紧施加到玻璃上时，此时提供了高的接合压力。在熔化之后对馈通件进行冷却时调节此时获得的在玻璃和内导体之间的接合压力。如果接合压力明显为正的、即大于30Mpa或大于50Mpa、尤其大于100Mpa，则在玻璃和金属之间的过渡部、即从玻璃至内导体的过渡部保持闭合，并且虽然α内小于α玻璃，由此是密封的。接合压力直接取决于膨胀差。此外，也还可想到的是本发明的几何结构。接合压力是面压力。接合压力是指以每个面积单位上的多大的力将第一主体压到第二主体上。
为了施加所需的接合压力，外导体的膨胀系数α外和玻璃的膨胀系数之间的差至少为2ppm/K、优选至少4ppm/K，其中该膨胀系数大于玻璃的膨胀系数α玻璃。在特别优选的实施方式中，内导体的α内选择为使得内导体的膨胀系数α内比玻璃的膨胀系数α玻璃大1.1倍。在特别优选的实施方式中，α内处于1.1·α玻璃至2·α玻璃的范围中。为了将外导体的所需压力施加到玻璃材料上并且确保密封性而规定了，外导体由无镍的、不锈的、耐化学性的钢(优质钢)构成。外导体的膨胀系数大于玻璃的膨胀系数，从而提供所需的接合压力。
特别优选的是，外导体是奥氏体优质钢、优选优质钢316L，其特征在于良好的可焊接性和高的膨胀系数。
除了无镍的铁素体优质钢、尤其不可硬化的具有高铬含量的铁素体优质钢，其膨胀系数α内大于玻璃材料的膨胀系数，也可想到，对于内导体使用钼或钨或铂。优选地，如此选择膨胀系数，使得内导体上的接合压力为至少30Mpa、优选至少50Mpa、尤其至少100Mpa。
除了馈通件，本发明也提供了根据本发明的玻璃-金属馈通件在植入式医疗设备或装置中的应用，以及包括在人体或动物体或含细胞培养物的活生物细胞可引入的或可附接的具有根据本发明的玻璃-金属馈通件的元件，其中，外导体和内导体至少在其表面区域中由具有降低的过敏可能性的金属构成，该表面区域在运行状态下与人体或动物体接触。优选地，外导体和内导体也都由这些金属构成。
外导体的和内导体的金属可与人体或动物体或细胞培养物接触，并且其特征在于没有镍和/或铬沉积。
优选地，外导体的金属和内导体的金属至少在其表面区域由无镍的钢和/或无铬的钢构成，所述表面区域在运行状态下与人体或动物体或细胞培养物的生物细胞接触。
特别适合作为内导体的至少在表面区域中的金属的是选自以下组中的金属：铁素体优质钢、如铂、铂/铱、铌、钛、钼、钨及其组合，所述表面区域在运行状态下与人体或动物体或细胞培养物的生物细胞接触。铁素体优质钢包括AISI4xx族，例如AISI 430。
外导体的金属至少在表面区域中优选选自如下组：
AISI 316L
AISI 430
AISI 630及其组合，所述表面区域在运行状态下与人体或动物体或细胞培养物的生物细胞接触。外导体的其他材料可选自如下组：奥氏体优质钢AISI 3xx或铁素体优质钢AISI 4xx。
附图说明
下面参考附图再一次详细描述本发明。其中：
图1示出了本发明的实施方式的示意图；
图2a-2b示出了导体和玻璃的接合压力的分布图。
具体实施方式
图1示例性地在示意图中示出了本发明的实施方式的剖面。在图1示出的穿过壳体1的玻璃-金属馈通件中，馈通件3被装入壳体1的开口5中，壳体优选可由铝制成。馈通件3包括馈通件导体或装入外导体9中的内导体7。外导体9也可称为基体，并且优选由热膨胀系数高的奥氏体优质钢构成。外导体也可称为基体，并且与壳体优选通过焊接连接。内导体或馈通件导体7居中地嵌入外导体中。这通过以下方式实现，内导体7在绝缘的玻璃体11中完全充满外导体9之内的空间。使内导体熔化在其中的玻璃优选是生物可容的玻璃。
在图1中同样示出了馈通件导体7的直径d以及开口5的所谓孔直径。
根据本发明规定了，玻璃具有膨胀系数α玻璃，内导体具有膨胀系数α内内，并且外导体具有膨胀系数α外。如此选择材料，使得内导体的膨胀系数α内大于玻璃的膨胀系数α玻璃。外导体的膨胀系数和玻璃的膨胀系数之间的差至少为2ppm/K、优选至少4ppm/K。在20℃直至玻璃转变温度的温度范围中外导体的膨胀系数α外大于玻璃的膨胀系数α玻璃。由此在内导体处提供的接合压力至少为30Mpa、优选至少50Mpa、尤其至少100Mpa。
在如本发明所要求的，内导体的膨胀系数α内大于玻璃的膨胀系数α玻璃时，则产生提供馈通件的足够密封性的问题。在这种情况下，仅在外导体可将足够高的接合压力构建到玻璃上时才确保足够的密封性。在图2a中示出了根据现有技术取决于d/D的接合压力，其中，作为馈通件导体的材料使用科伐铁镍钴合金，其具有的α值为7.3至6.6·10-61/K，稍微高于膨胀系数α玻璃的值，并且不包括在本发明中。在此d表示导体的直径并且D表示开口5的直径。d/D给出导体直径d和孔直径D之间的比例。通常适用的是，小的d/D值表征导体和开口之间的大的间隙，并且大的d/D值表征导体和开口之间的小的间隙。
虽然根据图2a的馈通件是严密密封的，但是具有的缺点是，科伐铁镍钴合金具有高的镍含量，从而可从馈通件导体中释放镍。
因此根据本发明规定了，科伐铁镍钴合金馈通件导体由不释放镍的材料代替。令人惊奇地发现，对此合适的材料是铁素体的无Ni优质钢、尤其AISI 430。但是无Ni的铁素体优质钢、例如AISI 430的缺点是α内为11.5·10-6K-1并且由此明显高于玻璃材料的膨胀系数α玻璃。加入的玻璃的膨胀系数α玻璃在6.1·10-6K-1至10.6·10-6K-1的范围中。
为了在这种情况下实现压力密封的嵌入，必须构建足够高的接合压力，该接合压力通过外导体施加。
在图2b中示出了用于这种馈通件的与d/D相关的接合压力。
如从图2b中看出，对于使用AISI 430作为馈通件构件的材料来说，尤其在外导体由具有的α外为18.3·10-6/K的奥氏体优质钢构成时，实现了足够高的接合压力。这种构造具有足够高的接合压力，从而确保密封性。这种材料组合的接合压力用附图标记100和200表示。接合压力随着更大的d/D以及小的间隙提高到高于150Mpa的值。
曲线300和400描述了AISI 430馈通件导体的接合压力，其中外导体是AISI430或AISI 630，并且玻璃具有10.6·10-6/K的膨胀系数，并且因此在外导体以及馈通件导体的膨胀系数的范围中。由此不可构建所需的接合压力。通常这种材料组合表现出低的接合压力。曲线300和400平缓地伸延，并且受直径比例的影响很小。
在根据图2b“关于d/D的接合压力”的图表中不同曲线的材料由下列表格中得出：
表格
在此，曲线100、200的材料组合具有特别高的接合压力，从而为馈通件提供了严密密封性。
所述玻璃-金属馈通件可应用在植入式医疗设备或装置中。所述玻璃-金属馈通件可成本有利地制成并且其特征在于有非常低的Ni渗出。此外，所述玻璃-金属馈通件由于高的接合压力而具有严密密封性，即氦泄漏低于1·10-8mbar/sec。

Claims (13)

1.一种玻璃-金属馈通件，其由外导体、玻璃材料和内导体构成，其中所述内导体具有膨胀系数α内、所述玻璃具有膨胀系数α玻璃并且所述外导体具有膨胀系数α外，其特征在于，
所述内导体的膨胀系数α内大于所述玻璃的膨胀系数α玻璃，并且在20℃直至玻璃转变温度的温度范围中所述外导体的膨胀系数α外与所述玻璃的膨胀系数α玻璃的差至少为2ppm/K、优选至少为4ppm/K，并且所述外导体的膨胀系数α外大于所述玻璃的膨胀系数α玻璃。
2.根据权利要求1所述的玻璃-金属馈通件，其特征在于，所述内导体的膨胀系数α内比所述玻璃的膨胀系数α玻璃大1.1倍，优选为其两倍，尤其在4·α玻璃至1.5·α玻璃的范围中。
3.根据权利要求1至2的任一项所述的玻璃-金属馈通件，其特征在于，所述外导体由优选无镍的、无锈的、耐化学的钢(优质钢)制成。
4.根据权利要求3所述的玻璃-金属馈通件，其特征在于，所述外导体由无锈的耐化学的钢、尤其奥氏体优质钢、尤其AISI 316L制成。
5.根据权利要求1至4的任一项所述的玻璃-金属馈通件，其特征在于，
外导体由无镍的、无锈的、耐化学的钢、尤其铁素体优质钢、尤其AISI430制成。
6.根据权利要求1至5的任一项所述的玻璃-金属馈通件，其特征在于，
内导体由以下材料之一构成：
-无镍的铁素体优质钢、尤其不可硬化的铁素体优质钢、优选具有高的铬含量的、尤其铬含量在10.5和20％之间、优选在15和17％之间、优选AISI 430，
-钼
-钨
-铂
-铌
-钛
-铂/铱。
7.根据权利要求1至6的任一项所述的玻璃-金属馈通件，其特征在于，
如此选择内导体的膨胀系数和外导体的膨胀系数，使得在内导体上构造的接合压力至少为30Mpa、优选至少50Mpa、尤其至少100Mpa。
8.根据权利要求1至7的任一项所述的玻璃-金属馈通件在可植入式医疗设备或装置中的应用。
9.一种元件，所述元件可被引入人体或动物体或包含细胞培养物的活体生物细胞或可被附接到人体或动物体或包含细胞培养物的活体生物细胞上，所述元件具有根据权利要求1至7的任一项所述的玻璃-金属馈通件，其中，至少在运行状态中与人体或动物体接触的表面区域中所述外导体和所述内导体由具有降低的过敏可能性的金属构成。
10.根据权利要求9所述的元件，其特征在于，与人体或动物体或细胞培养物接触的所述外导体的金属和所述内导体的金属没有镍和/或铬沉积。
11.根据权利要求9至10的至少一项所述的元件，其特征在于，至少在运行状态中与人体或动物体或细胞培养物的生物细胞接触的表面区域中所述外导体的金属和所述内导体的金属由无镍的钢和/或无铬的钢构成。
12.根据权利要求9至11的至少一项所述的元件，其特征在于，至少在运行状态中与人体或动物体或细胞培养物的生物细胞接触的表面区域中所述内导体的金属选自以下组：
铁素体优质钢(AISI 4xx)
-铂
-铂/铱
-铌
-钛
-钼
-钨
及其组合物。
13.根据权利要求12所述的元件，其特征在于，至少在运行状态中与人体或动物体或细胞培养物的生物细胞接触的表面区域中所述外导体的金属选自以下组：
-奥氏体优质钢AISI 3xxx，尤其
-AISI 316 L
-铁素体优质钢AISI 4xxx，尤其
-AISI 430
-AISI 630
及其组合物。
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