CN105121385A - 可烧结和/或可熔融的陶瓷物料及其制备和用途 - Google Patents

可烧结和/或可熔融的陶瓷物料及其制备和用途 Download PDF

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CN105121385A
CN105121385A CN201480017213.3A CN201480017213A CN105121385A CN 105121385 A CN105121385 A CN 105121385A CN 201480017213 A CN201480017213 A CN 201480017213A CN 105121385 A CN105121385 A CN 105121385A
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ceramic material
sintering
quality
preparation
mixture
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CN105121385B (zh
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G.贝格尔
A.施皮策尔
D.尼科拉德斯
J.京斯特
H.马克斯
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Bundesministerium fuer Wirtschaft und Technologie
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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
    • A61F2/02—Prostheses implantable into the body
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    • A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
    • A61F2/30771—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth applied in original prostheses, e.g. holes or grooves
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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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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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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Abstract

本发明涉及可烧结和/或可熔融的陶瓷物料及其制备方法，该陶瓷物料包含长期稳定的由磷灰石、硅灰石、钛铁矿和任选的方英石的晶体相构成的复合材料，该复合材料通过玻璃相稳定化。该陶瓷物料可以通过烧结一种混合物获得，该混合物单独地或者与至少一种碱金属氧化物组合地至少包含成分SiO2、CaO、P2O5、MgO、CaF2和TiO2，其中所述碱金属氧化物选自Na2O和K2O。本发明还涉及成型体形式的烧结材料用于使医学植入物的表面固化、清洁、粗糙或抛光或者作为内假体的用途。

Description

可烧结和/或可熔融的陶瓷物料及其制备和用途
本发明涉及可烧结和/或可熔融的陶瓷物料（下文称为陶瓷物料）以及包含该陶瓷物料的成型体，特别涉及生物活性或生物反应性（即引起直接的不含结缔组织的骨接触）的陶瓷物料、长期稳定的骨替代物以及其制备方法和结构化方法。
在本文中，陶瓷物料是指无机非金属材料，其呈现为烧结和烧制的形式或者待烧结或烧制的材料的形式。陶瓷成型体通常在室温下由例如浆料或糊料的原材料形成并且通过在高温下的烧结过程而固化。用于烧结的材料的制备也可以包括烧结材料的第一烧结和后续的磨碎，例如通过使该磨碎的材料然后再次用于制备浆料或糊料，由此形成生坯。例如，该生坯可以生成烧结玻璃陶瓷。该制备也可以同样包括磨碎预先熔融的玻璃。此外，可以使熔融的玻璃经历温度处理，从而相应于传统的玻璃陶瓷方法在玻璃基质内进行结晶。
所述陶瓷物料可以作为粒料存在，其在合适的预处理之后直接用作天然的骨材料或者用于填补在活体中的骨。但同样可以将陶瓷物料加工成成型体，其在合适的预处理之后完全替代在活体中的骨。可使用的加工方法还包括递增制造方法（additive Fertigungsverfahren），例如所谓的3D-打印和其它的快速原型法和任选随后的特定烧结步骤或者用活细胞浸渍或定植由此获得的结构。
已知的长期稳定和生物活性/生物反应性的玻璃陶瓷或陶瓷物料主要由磷灰石和硅灰石组成。其可以作为烧结玻璃陶瓷 (Kokubo [1])或者根据传统的玻璃陶瓷法 (Berger等 [2]) 制备。纯的羟基磷灰石-材料（先验地认为生物活性和长期稳定的）通常不能制备成任意的特定打印的成型体，并且通常在用作骨替代材料时具有不足够的强度值。在本文中，与可再吸收的材料或可再吸收的复合材料不同，长期稳定的骨替代物或者长期稳定的复合材料是指这样的材料，该材料在应用时间段（例如对应于各种生物体（脊椎动物、人）的通常寿命）中不再吸收并且不会被天然的骨代替，而是基本上保持不变。因此，其在活体中或者在细胞和/或组织培养的生理条件下的溶解度非常低。这表明，跨整个应用时间段，该材料的界面保持不变，在该界面处在生物体中的继续重塑过程中可以积聚天然骨物质或者该界面在技术应用中起到研磨的作用。
特别地，基于仅仅具有主要晶体相磷灰石和硅灰石的玻璃陶瓷的已知产物的溶解度仍然太大。如果该溶解度通过添加Al2O3、ZrO2或者TiO2而降低，则根据添加物的量提高了该材料在生理条件下或在生理溶液中的耐受性，但是降低了不含结缔组织的直接骨接触率，因为这些物质 (Al2O3、ZrO2、TiO2) 位于在前和形成自身的层 [3]。
基于这样的背景，本发明提供了根据权利要求1的陶瓷物料、根据权利要求5的陶瓷物料的制备方法、根据权利要求17-25的陶瓷物料以及由其获得的成型体的用途和根据权利要求26的成型体。
借助下面的说明书和所附的权利要求书可以得到更多的实施方案、变型方案和改进方案。
根据一个实施方案，提供了陶瓷物料，其包含长期稳定的由磷灰石、硅灰石和钛铁矿的晶体相构成的复合材料，该复合材料通过玻璃相稳定化。该陶瓷物料的特征特别在于可烧结和/或可熔融的。
该实施方案的优点在于，将所述的晶体相稳定地嵌入共同的玻璃相中，该玻璃相在生理介质中至少部分地可溶并且因此提供了对于生长细胞的有利的锚固可能性和天然骨物质的积聚，而不会使该陶瓷物料例如在体内溶解或者再吸收。由此有利地产生出色的骨整合以及高的骨接触率。
根据一个实施方案，提供了陶瓷物料，其除了所述的主要晶体相磷灰石、硅灰石和钛铁矿之外还含有方英石。
该实施方案的优点在于，将全部所述的晶体相稳定地嵌入共同的玻璃相中、使该陶瓷物料在生理介质中非常稳定以及出色的骨整合和高的骨接触率。
根据一个实施方案，提供了陶瓷物料，其特征在于该陶瓷物料单独地或者与至少一种选自Na2O和K2O的碱金属氧化物组合地包含SiO2、CaO、P2O5、MgO、CaF2和TiO2。
该实施方案的优点在于，玻璃相的溶解度通过所述物质的化学计量比调节，并且因此达到有利高的骨接触率。
在本文中，化学计量的成分是指上述物质的物质量比或者质量比，其中所述氧化物或者氟化钙的化学计量比可以通过称重不同的起始物质获得。例如，为了导入所希望的物质量的钙、钾或钠，也可以称重草酸的相应盐。
根据另一个实施方案，提供了陶瓷物料，其中在烧结之后陶瓷物料中的玻璃相的含量为小于25质量%，优选小于10质量%。
所述少量的玻璃相的主要优点在于所述烧结的陶瓷物料在生理介质中提高的稳定性，特别当存在血清和当定植活细胞的时候，尤其在骨整合时。
根据另一个实施方案，提供可烧结和/或可熔融的陶瓷物料的制备方法，其包括下列步骤：
提供一种混合物，该混合物单独地或者与至少一种选自Na2O和K2O的碱金属氧化物组合地至少包含成分SiO2、CaO、P2O5、MgO、CaF2和TiO2；
研磨该混合物；
在第一温度处理步骤中将研磨的混合物烧结或煅烧成第一物料，其中所述烧结或煅烧的温度为650℃至800℃，特别是720℃，烧结时间为至少1小时，优选烧结时间为8至24小时；
磨碎该第一物料；
悬浮该磨碎的第一物料而生成浆料；
由该浆料形成生坯；
在第二温度处理步骤中烧结该生坯，其中生坯的烧结温度为850℃至1200℃，特别是920℃至1150℃, 烧结时间为至少18小时至24小时。
该制备方法的优点在于，可以提供可烧结和/或可熔融的陶瓷物料，其适用于制备骨替代材料和人造骨。该制备方法的特别优点在于，提供了可流动性的粉末和粒料，其特别适用于递增制造方法。
根据另一个实施方案，在第一温度处理步骤的烧结或煅烧之前在低于1650℃，特别是低于1620℃的熔融温度下将研磨的混合物熔融。根据一个示例性的实施方案，该熔融例如可以在由例如铂/铑构成的坩埚中进行。
这提供了特别优点以获得嵌入玻璃基质中的具有细晶体结构的磷灰石、硅灰石、钛铁矿和方英石，或者获得包含具有细晶体结构的磷灰石、硅灰石、钛铁矿和方英石的玻璃陶瓷。
根据制备方法的另一个实施方案，提供的混合物包含35-45质量% SiO2；25-35质量% CaO；10-15质量% P2O5；2-4质量% MgO；4-6质量% CaF2和4-10质量% TiO2，并且可以含有0.001-5质量% Na2O和/或0.001-0.2质量% K2O。
该实施方案的优点在于，在本文中描述的组成下同步进行晶体相磷灰石、硅灰石、钛铁矿和任选的方英石的沉积，而不会在烧结过程结束之后出现在前的富氧化钛层，该富氧化钛层例如会阻碍在接受者内部的直接骨接触。
根据制备方法的另一个实施方案，为了获得陶瓷物料而混合的成分的颗粒的平均直径为0.5–3000 µm，优选0.5–3 µm；特别是2–10 µm；10–100 µm；50–1000 µm或者300–3000 µm。
该实施方案的优点在于，均匀地出现或者均匀地分布沉积的晶体相磷灰石、硅灰石、钛铁矿和通常还有方英石。不依赖于主要的应力方向，微晶的均匀分布会使所获得的成型体具有好的强度。
根据另一个实施方案，所提供的制备方法包括填充烧结模具。该烧结模具匹配于最终所需的成型体的大小和形状，因此在烧结之后不需要进一步的加工。这特别可以如下实现：使用所提供的起始物料组成，不必需要除掉在前的层，例如富氧化钛层，因为这样的层不会出现。因此，烧结的成型体可以直接使用，例如用作骨替代物。
根据所提供的可烧结和/或可熔融的陶瓷物料的制备方法的另一个实施方案，在两个步骤中的烧结在无压力下进行。
该实施方案的优点在于极大地简化了方法实施。例如，烧结步骤可以以粉末-喷射-烧结的形式包括粉末的烧结。
根据另一个实施方案，在第一步骤中的无压力烧结的温度为650至800℃，特别是720℃，时间长度为1至48小时，时间长度特别为24小时；而在第二步骤中的无压力烧结的温度为850至1200℃，特别是920至1150℃，时间长度为1至48小时，时间长度特别为24小时。
该实施方案的优点在于，考虑到所获得的材料的优选骨接触率和优选机械负荷能力，在相当低的技术消耗下实现了有利的相组成。
根据后两个实施方案的一个变型方案，在第二烧结步骤之前研磨在第一烧结步骤之后获得的陶瓷物料。
优点特别在于考虑到孔分布的均匀结构和不同晶体相的均匀分布，以及所获得的成型体由此达到的各向同性的强度。这提供了特别优点以使所获得的成型体适用于其各自的可能用途。
根据另一个实施方案，将起始物质SiO2、CaO、P2O5、MgO和CaF2之和的质量与所使用的TiO2的质量的比例调节为8:1至20:1。有利的实施例详见表5。
根据另一个实施方案，提供一种制备方法用于可烧结和/或可熔融的陶瓷物料，其包含通过玻璃相稳定化的长期稳定的由磷灰石、硅灰石、钛铁矿和任选的方英石的晶体相构成的复合材料。该制备方法的特征在于，陶瓷物料的起始物质的混合物中的SiO2、CaO和P2O5之和与这些起始物质的混合物中所含的TiO2的质量比为7:1至20:1。有利地，在该质量比的情况下可以避免形成在前的富氧化钛层。
根据该制备方法的另一个实施方案，逐层地或者使用递增法通过使用浆料而形成生坯，该浆料为研磨的起始物质的浆料或者由在第一烧结步骤之后获得的研磨的陶瓷物料形成的浆料。
递增法通常需要与各个方法匹配的在所使用的粉末、粒料或浆料中存在的平均粒度的分布。由于通过研磨步骤基本上不能调节的大小分布和平均粒度或者由于借助匹配的喷射烧结而可调节的平均粒度，因此可以使各个粒度匹配优选的递增法。因此可以利用递增法的已知优点。例如，可以借助合适的压力方法加工浆料。这例如可以使用所述的陶瓷物料用于制造三维的逐层构造的成型体。
根据另一个实施方案，磨碎第一烧结物料不加入添加物质。优点在于减少的时间消耗和降低的成本。
根据另一个实施方案，将所述可烧结和/或可熔融的陶瓷物料作为用于医学植入物的喷射剂（Strahlmittel），其中该喷射剂的平均粒径为50–5000 µm，优选50-1000 µm。
由有利的生理相容性和高的骨接触率可以避免目前的喷射剂，例如刚玉的缺点。喷射的表面不必经受复杂的清洁，任选在表面背切中保留的喷射物甚至可以改善处理表面的生长。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料在浆料浇注方法中以可浇注物料的形式使用，其中在可浇注物料中分散的颗粒的平均粒径为0.5-7 µm，优选0.5-3 µm。
优点在于所述陶瓷物料适用于递增制造方法中。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料可以用于使医学植入物的表面固化、清洁、粗糙或抛光，其中所述陶瓷物料构成为成型体并且该成型体在一个空间方向上的平均大小为0.25 µm至1 cm，特别是0.5 µm至500 µm。
优点在于所述陶瓷材料的普遍可用性，例如作为用于金属或聚合物表面或者用于包含复合材料的成型体的表面的磨具、细喷射剂或者抛光剂。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料和由此获得的成型体可以作为用于医学植入物或内假体的磨具使用。
由有利的生理相容性和高的骨接触率可以避免目前的磨具，例如刚玉的缺点。用磨具处理的表面不必经受复杂的清洁，任选在表面背切中保留的材料甚至可以改善处理表面的生长。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料可以用于处理金属表面。
优点在于该陶瓷成型体的强度以及该陶瓷物料以及由其制成的成型体的出色生物相容性。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料可以在可浇注的物料中用于浆料浇注，其中所述陶瓷物料的离散颗粒的单个颗粒的平均直径为0.5 µm至 7 µm，优选0.5至3 µm。
优点在于，基于浆料浇注的方法允许磨具形状和生坯大小的相当大的自由度。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料可以用于制备压制粒料，其中所述压制粒料的平均粒料颗粒大小为0.5 µm至500 µm。
有利地，所述陶瓷物料适用于制备大小范围在很宽的范围内可以调节的粒料颗粒。因此，可以提供特定应用的粒料，该粒料具有本文所述的烧结陶瓷物料的有利特性。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料可以用于制备递增制造方法用的可流动性粉末，其中所述可流动性粉末的平均粉末颗粒大小为10 µm至125 µm。
可流动性的粉末由于有效的材料使用率和工艺经济性可以用于湿床以及干床（Tockenbett）工艺。该可流动性粉末的可以自由调节的平均颗粒大小允许应用相关的工艺优化。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料可以以植入物粒料的形式提供并且用于替代或者用于填补天然骨材料，其中所述植入物粒料的平均颗粒大小为300 µm至3000 µm。
优点在于这类植入物粒料特别适用于例如空腔外科和整形外科。
根据另一个实施方案，前面描述的可烧结和/或可熔融的陶瓷物料可以作为喷射物用于表面处理，其中所述陶瓷物料的平均颗粒大小为50 µm至5000 µm，例如50 µm至2500 µm。
如所述的，平均颗粒大小能够自由调节。因此，本文描述的可烧结和/或可熔融的陶瓷物料可以用不同的技术加工或者将由其制成的成型体用于不同的领域中，例如用作骨替代材料、用于骨构造、用于实现框架和支撑结构、用作生物相容的填充材料和用作人造骨。
根据另一个实施方案，提供包含本文所述的可烧结和/或可熔融的陶瓷物料的成型体，其中所述成型体选自：微粒、球体、粒料、多面体、片体、盘体、椭圆体、棒、管、圆柱体、圆锥体、骨形结构或者上述成型体的至少一种的部分或者片段。
可获得的形状的所述多样性覆盖了尽可能宽范围的优选应用。特别优选需要好的生物相容性、好的骨接触率、快速骨整合和/或好的细胞和组织相容性（特别是对于哺乳动物细胞和哺乳动物组织）的应用。
可行的应用领域包括所述材料和成型体在兽医、人类医学、医学研究和与之相关的表面处理方面的应用。
上述的实施方案可以任意地相互组合。
附图示意了实施方案并且与说明书一起用于阐述本发明的原理。
图1显示了温度处理的材料借助扫描电子显微镜获得的图像。
图2以方块图的形式显示了晶体相和玻璃含量随表4中的温度处理的变化。
图3以方块图的形式显示了表5的AWT变化方案的化学计量组成。
特别地，图1显示了嵌入玻璃基质中的晶体的通过提供的温度处理获得的构造的细晶体结构(参照在图像边缘处的测量条"300 nm")。该玻璃陶瓷由可熔融的陶瓷物料AWT7-o.K-Si获得(参照表5，最后几行)。
基于产生具有主要晶体相磷灰石和硅灰石 (AW)的陶瓷物料，尤其是玻璃陶瓷的组合物，通过添加目前不常见高的TiO2-组分完全令人惊讶地生成了由硅酸钛或由钛铁矿组成的第三主要晶体相。通常，当在烧结和凝固所述陶瓷物料之后接着进行另一烧结步骤时，由所提供的组合物可以沉积出第四主要晶体相，即方英石。两个附加的主要晶体相的沉积，即所述第三(钛铁矿)和第四主要晶体相(方英石)的出现导致陶瓷物料的玻璃相含量减少。相比于基于磷灰石和硅灰石的玻璃陶瓷，在所提供的陶瓷物料中的玻璃相的含量减少到仅仅约10质量%。这同样有助于提高化学耐受性以及有助于所提供的陶瓷物料在生理溶液或活体中的长期稳定性。
在此，陶瓷物料通常理解为起始物质的组合物，例如粉末混合物。该组合物或该粉末混合物在充分混合之后（也可以例如通过研磨和/或均质化实现）加工成生坯，其在烧结过程之后形成具有所有本文描述的性能的固体或固体陶瓷物料。烧结的陶瓷物料至少包含四种所述主要晶体相和玻璃相。
尽管如所述地实现了玻璃相含量在该陶瓷物料中的减少，该玻璃相含量在所提供的陶瓷物料中却仍然足够地高，从而可以由粒化的、熔融的玻璃陶瓷物料打印出在在无压力烧结之后具有足够机械稳定性的3D-成型体 (参照表1)，以便可以例如用作骨替代物。
粒度 [µm] 强度 [MPa]
25-45 4.1
45-100 2.6
表1. AWT7-o.K-Si 3D-打印-成型体的强度。
在此可以理解，由所述陶瓷物料或玻璃陶瓷物料制成的成型体在传统的陶瓷加工之后（在成型体制造时使用压力）相比于上述的无压力制造的成型体具有较高的机械强度。例如作为实施例以片状形式压制的成型体证明了这一点 (参照表2)。
粒度 [µm] 强度 [MPa]
0.5-3.0 38.4
1.5-35.0 120.7
表2. AWT7-o.K-Si压制成型体的强度。
本领域技术人员已知，在向陶瓷烧结物料中添加高含量的氧化钛时在获得的磷灰石-和硅灰石-玻璃陶瓷上会出现富氧化钛层，其严重限制了所获得的玻璃陶瓷作为骨替代材料的适用性。在本文中，4-5质量%的TiO2–含量已经评价为高，7质量%的TiO2–含量已经评价为非常高。因此，通常避免高于4-5质量%，此外7质量%和更高的TiO2–含量，从而避免富氧化钛层在烧结的成型体的表面上的沉积。
然而已证实，根据所提供的方法，在向该体系中添加5质量%或更高的TiO2从而获得磷灰石-和硅灰石-玻璃陶瓷时，可以避免出现在前富氧化钛层的目前缺点。令人惊奇地也证实，当向该陶瓷物料添加例如7质量%或更高，通常最多10质量%的TiO2时，没有出现在前富氧化钛层，但除了磷灰石和硅灰石之外在烧结的陶瓷物料中还存在钛铁矿和方英石。因此，这样获得的成型体的骨接触率相对于具有在前的富氧化钛层的情况得到提高并且材料的长期稳定性也同时增加。
在所提供的条件下，这四个晶体相磷灰石、硅灰石、钛铁矿和方英石同步沉积，其中有利地没有出现在前的富TiO2层。所获得的陶瓷材料的特点在于高的生物活性。在本文中，生物活性是指相关陶瓷的不含结缔组织的骨固定。特别地，其是指骨在烧结陶瓷物料或包含所提供的陶瓷物料的骨替代材料或具有该陶瓷物料的植入物或成型体或用其处理的内假体表面（即生物体内不含结缔组织的骨整合）的表面中或表面上的嵌入生长或附着生长。
本领域技术人员已知，通过不同的方法技术，特别是通过选择成型体或其单个颗粒成分的起始大小可以在很大程度上改变相组成，无论其涉及相同的化学计量组成还是甚至相同的起始批量。这在表3中在下面的实施例中得到阐述。起始物质是组合物AWT7-o.K-Si。
表3
该变化方案的合理原因在于，所选择的方法条件持续地影响表面结晶的体积。
当本身以研磨的形式使用各个微晶(主要晶体相)、多个或所有四个主要晶体相作为起始形态的成分时，这四个主要晶体相在烧结过程中的沉积也是可行的。磷灰石在此是指通式Ca5[(F, Cl, OH)|(PO4)3)的晶体化合物；方英石是指通式SiO2的晶体化合物；钛铁矿是指式CaTi[O|SiO4]的晶体化合物；和硅灰石是指式CaSiO3或Ca3[Si3O9]的晶体化合物。可以理解，这些晶体化合物可以具有嵌入的痕量其它元素，其在由起始物质形成晶体时作为伴随的痕量元素存在。在所使用的研磨物中含有的起始物质具有“p.a.”的纯度，并且因此基本上不含杂质。
本领域技术人员也已知，通过烧结时的不同温度性能可以在很大程度上改变相组成，无论其涉及相同的化学计量组成还是甚至相同的起始批量。在表4中列出的实验数据提供了相应的证据。
表4 以大约质量%表示的晶体相和玻璃含量
AWT7-o.K-Si-样品烧结变化方案 磷灰石 硅灰石 钛铁矿 方英石 玻璃相
玻璃 100
950℃/1h 12 12 20 14 42
1000℃/1h 15 15 27 13 31
1050℃/1h 16 16 31 15 22
1100℃/1h 12 13 17 16 42
1150℃/1h 12 16 23 24 24
1200℃/1h 16 10 20 14 40
在表4中给出的值的图形描述显示在图2中。
因此，提供给使用者长期稳定的玻璃陶瓷材料，其可以直接以粒料的形式作为骨替代物使用或者在使用各种工艺技术的情况下加工成成型体，该成型体同样具有对于骨替代物重要的性能。同样地，所述陶瓷材料可以用于各类内假体或植入物的表面处理，特别是金属成型体的表面处理。
这样的表面处理的实例是根据喷砂类型用于使内假体表面粗糙的喷射，其中在此使用的喷射物包含所提供的陶瓷材料。借助在此描述的玻璃陶瓷物料的表面处理的另一实例是喷丸。在这类应用的情况中，用于喷丸的喷射剂包含烧结陶瓷材料的紧实成型体，优选球形的。借助在此描述的玻璃陶瓷物料或用其成型体的表面处理的另一实例是抛光。在此，将该玻璃陶瓷物料或者由其组成的磨具用作抛光剂。用于抛光的磨具可以有利地具有多面体形状，例如棱柱、长方体或球形的形状或者椭圆体的形状。该待使用的抛光剂例如可以包含各种形状和大小的颗粒，其中各种颗粒或磨具的形状、大小和混合比例由待抛光的物体的各自性质所决定。优选地，所述磨具用于磨光和/或抛光内假体的金属部分。
所有提供类型的内假体表面处理（通过与包含所提供组合物的陶瓷物料的成型体接触，其中该组合物经历至少两个烧结步骤）的共同优点在于，在内假体的表面上保留的陶瓷物料残余物促进了内假体的骨整合；相反地，通常用作喷射剂的刚玉阻碍处理的表面或用喷射剂喷射的表面的生物相容性。
所提供的陶瓷物料是一种新型的材料组合，其特征在于晶体相磷灰石、硅灰石、钛铁矿和方英石在玻璃相中的均匀分布。
除了开启了新的科学观点之外，这种材料因此适用作骨替代物和成型体，并且适用作稳定和改善的用于处理植入物表面的喷射物。根据现有技术使用的烧结刚玉的缺点在于，在喷射的金属粒子中，例如锚固在髋关节内假体柄中的刚玉颗粒阻碍了直接的不含结缔组织的骨接触。
本发明制备和研究了具有不同组成和性能的玻璃陶瓷形式的陶瓷物料，其中为了获得玻璃陶瓷而混合的起始混合物列在下面的表5中。
表5. AWT-变化方案的化学计量组成 (以质量%计)
样品 SiO2 CaO P2O5 K2O Na2O MgO CaF2 TiO2
AW [2] 44.30 31.89 11.21 0.20 4.60 2.80 5.00 -
AWT5 42.19 30.37 10.68 0.19 4.38 2.67 4.76 4.76
AWT7 41.40 29.80 10.48 0.19 4.30 2.62 4.67 6.54
AWT9 40.64 29.26 10.28 0.18 4.22 2.57 4.59 8.26
AWT11 39.91 28.73 10.10 0.18 4.14 2.52 4.51 9.91
AWT7-o.KNa 43.17 31.07 10.94 - - 3.41 4.87 6.54
AWT7-o.K 42.29 30.44 10.70 - 1.91 3.34 4.78 6.54
AWT7-o.K-Si 39.60 32.04 11.26 - 2.01 3.52 5.03 6.54
作为起始物质称重SiO2、CaCO3、Ca3(PO4)2、MgO、CaF2、TiO2、Na2CO3、K2CO3，在辊式混合器中均质化一个小时，然后在1550至1600℃下熔融三个小时。根据再加工，将稀液状的熔体浇注或熔结在钢板上。
在表格中使用的缩写AW表示根据现有技术已知的磷灰石/硅灰石 [2]，而AWT表示根据在本文的说明书和示例性表述的权利要求在烧结时形成的磷灰石-硅灰石-钛铁矿。缩写AWT之后的数值表示其它添加组分的质量含量。缩写“AWT-o.K”或“AWT-o.KNa”在此表示不含钾或不含钾和钠的混合物。表5中的数值在图3中以方块图的形式再次给出。这样形象地描述了组合物的变化方案。
所提供的组合物因此是无机晶体材料的组合，其以合适的方式满足了长期稳定的骨替代物的要求。最佳的特征组合特别是低的溶解度、该材料在生理条件下各自的高的化学耐受性、形成成型体的出色可加工性和该成型体的高强度以及直接的不含结缔组织的生长行为（即所提供的陶瓷物料的生物活性），这些特征组合有利于该陶瓷物料用于骨替代材料的各个方面。相应地，可以将该陶瓷材料用作骨缺陷填充材料和用于骨增长（增殖）、用作骨替代物或成型体、用作使内假体粗糙和/或喷丸和/或抛光的喷射剂和成型体。具体的实施例涉及处理颌植入物、膝植入物和髋关节植入物的表面，特别是使髋关节内假体柄粗糙。
总之，本发明因此涉及可烧结和/或可熔融的陶瓷物料及其制备方法，该陶瓷物料包含长期稳定的由磷灰石、硅灰石、钛铁矿和任选的方英石的晶体相构成的复合材料，该复合材料通过玻璃相稳定化。该陶瓷物料可以通过烧结一种混合物获得，该混合物单独地或者与至少一种碱金属氧化物组合地至少包含成分SiO2、CaO、P2O5、MgO、CaF2和TiO2，其中所述碱金属氧化物选自Na2O和K2O。不言而喻地，在提供玻璃相或者在提供本领域技术人员已知的起始物质用于形成玻璃相的情况下也可以使用包含研磨的晶体相磷灰石、硅灰石、钛铁矿和方英石的起始材料用于制备所述陶瓷物料。其它实施方案涉及成型体形式的烧结材料用于使医学植入物的表面固化、清洁、粗糙或抛光或者作为内假体的用途。
在本发明中，尽管描述和说明了特定的实施方案，但是可以适当地修改所示的实施方案，而不使其偏离本发明的保护范围。下文的权利要求首要地、但非强制性地尝试一般性限定本发明。
参考文献：
[1] Kokubo, T. (1991): Bioactive Glass-Ceramics；Properties and Applications；Biomaterials, 12: 155-163.
[2] Berger, G.；Sauer, R.；Steinborn, G.；Wihsmann, F.G.；Thieme, V.；Köhler, St.；Dressel, H. (1989): Clinical application of surface reactive apatite/wollastonite containing glass-ceramics. in: XV. Int. Congress on Glass, Leningrad, USSR, 3.-7.7.1989, Volume 3a: 120-126.
[3] Berger, G.；Atzrodt, V. (1984): In vitro characterization of bioactivity of glass-crystalline implant materials using AUGER electron spectroscopy；physica status solidi (a), 85(1): 9-13.

Claims (26)

1.陶瓷物料，其包含长期稳定的由磷灰石、硅灰石和钛铁矿的晶体相构成的复合材料，该复合材料通过玻璃相稳定化。
2.权利要求1的陶瓷物料，其中所述复合材料还包含方英石。
3.权利要求1或2的陶瓷物料，所述陶瓷物料单独地或者与至少一种选自Na2O和K2O的碱金属氧化物组合地包含SiO2、CaO、P2O5、MgO、CaF2和TiO2。
4.权利要求1至3任一项的陶瓷物料，其中烧结之后在所述陶瓷物料中的玻璃相的含量小于25质量%，优选小于10质量%。
5.陶瓷物料的制备方法，其包括：
提供一种混合物，该混合物单独地或者与至少一种选自K2O和Na2O的碱金属氧化物组合地至少包含成分SiO2、CaO、P2O5、MgO、CaF2和TiO2；
研磨该混合物；
烧结该研磨的混合物，其中烧结温度为650℃至800℃，特别是720℃，烧结时间为至少1小时，优选8至24小时；
磨碎该烧结的混合物；
悬浮该磨碎的混合物而生成浆料；
由该浆料形成生坯；
在第二烧结步骤中烧结该生坯，其中生坯的烧结温度为850至1200℃，特别是920至1150℃，烧结时间为至少18至24小时。
6.权利要求5的制备方法，其中在烧结研磨的混合物之前在低于1620℃的熔融温度下将该研磨的混合物熔融。
7.权利要求5或6的制备方法，其中该混合物包含：
35-45质量% SiO2；25-35质量% CaO；10-15质量% P2O5；2-4质量% MgO；4-6质量% CaF2和4-10质量% TiO2；以及任选0.001-0.2质量% K2O和/或0.001-5质量% Na2O。
8.权利要求5至7任一项的制备方法，其中为了获得陶瓷物料，所述成分的颗粒的平均直径为0.5–3000 µm，优选0.5–3 µm；2–10 µm；10–100 µm；50–1000 µm或者300–3000 µm。
9.权利要求5至8任一项的制备方法，还包括：
用所述研磨的混合物填充烧结模具。
10.权利要求5至9任一项的制备方法，其中在两个步骤中的烧结在无压力下进行。
11.权利要求5至10任一项的制备方法，其中在第一步骤中的烧结的温度为650至800℃，特别是720℃，时间长度为1至48小时，时间长度特别为24小时；而在第二步骤中的烧结的温度为850至1200℃，特别是920至1150℃，时间长度为1至48小时，时间长度特别为24小时，均在无压力下进行。
12.权利要求10或11的制备方法，在第二烧结步骤之前研磨在第一烧结步骤中获得的陶瓷物料。
13.权利要求5至12任一项的制备方法，其中在混合物中的成分SiO2、CaO、P2O5、MgO和CaF2之和的质量与在混合物中获得的TiO2的质量的比例为8:1至20:1。
14.权利要求5至12任一项的制备方法，其中在混合物中的成分SiO2、CaO和P2O5之和的质量与在混合物中获得的TiO2的质量的比例为7:1至20:1。
15.权利要求5至14任一项的制备方法，其中生坯的形成逐层地或者通过使用递增法进行。
16.权利要求5至15至少一项的制备方法，其中磨碎第一烧结物料是不加入添加物质的。
17.根据权利要求1至4至少一项的陶瓷物料作为用于医学植入物的喷射剂的用途，其中细喷射剂的平均粒径为50 - 1000 µm。
18.根据权利要求1至4至少一项的陶瓷物料作为浆料浇注方法中的可浇注物料的用途，其中在可浇注物料中分散的颗粒的平均粒径为0.5–7 µm。
19.根据权利要求1至4至少一项的陶瓷物料用于使医学植入物的表面固化、清洁、粗糙或抛光的用途，其中所述陶瓷物料构成为成型体，并且该成型体在一个空间方向上的平均大小为50 µm至1 cm，特别是100 µm至2 mm。
20.根据权利要求1至4至少一项的陶瓷物料作为用于医学植入物、内假体或者用于处理金属表面的磨具的用途。
21.根据权利要求1至4至少一项的陶瓷物料在可浇注的物料中用于浆料浇注的用途，其中所述陶瓷物料具有离散的颗粒并且颗粒的平均直径为0.5 µm至7 µm，优选0.5至3 µm。
22.根据权利要求1至4至少一项的陶瓷物料用于制备压制粒料的用途，其中所述压制粒料的平均粒料颗粒大小为0.5 µm至500 µm。
23.根据权利要求1至4至少一项的陶瓷物料用于制备递增制造方法用的可流动性粉末的用途，其中所述可流动性粉末的平均粉末颗粒大小为10 µm至125 µm。
24.根据权利要求1至4至少一项的陶瓷物料作为植入物粒料用于替代或者用于填补天然骨材料的用途，其中所述植入物粒料的平均颗粒大小为300 µm至3000 µm。
25.根据权利要求1至4至少一项的陶瓷物料作为喷射物用于表面处理的用途，其中所述陶瓷物料的平均颗粒大小为50 µm至5000 µm。
26.包含权利要求1至4至少一项的陶瓷物料的成型体，其中所述成型体选自：微粒、球体、粒料、多面体、片体、盘体、椭圆体、棒、管、圆柱体、圆锥体、骨形结构或者上述成型体的至少一种的部分或者片段。
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