CN101415655B - 制造三维陶瓷成型体的方法和设备 - Google Patents

制造三维陶瓷成型体的方法和设备 Download PDF

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CN101415655B
CN101415655B CN2007800124483A CN200780012448A CN101415655B CN 101415655 B CN101415655 B CN 101415655B CN 2007800124483 A CN2007800124483 A CN 2007800124483A CN 200780012448 A CN200780012448 A CN 200780012448A CN 101415655 B CN101415655 B CN 101415655B
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weight
layer
print head
suspension
nozzle
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CN101415655A (zh
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克里希纳·乌伊贝尔
赖纳·特勒
奥尔斯特·费希尔
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Emre Ozkol
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Emre Ozkol
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Abstract

本发明描述一种制造三维陶瓷成型体的方法，所述方法通过利用喷墨式印刷机将包含陶瓷成型体成型所需组分的悬浮液以期望的二维形状来分层印刷到基材上，干燥和硬化所形成的复合层，所述方法的特征在于：使用在包含水性勃姆石溶胶、至少一种低分子量醇、至少一种干燥抑制剂和至少一种有机流化剂的分散介质中包含50～80重量％陶瓷颗粒的悬浮液来实施印刷，本发明还涉及实施所述方法的一种设备。

Description

制造三维陶瓷成型体的方法和设备
本发明涉及通过利用喷墨式印刷机将包含陶瓷成型体成型所需组分的悬浮液以期望的二维形状来分层印刷到基材上，干燥和硬化所形成的复合层从而制造三维陶瓷成型体的方法以及用于进行该方法的设备。
制造三维陶瓷成型体的常规方法通常包括使用与待制造的成型体匹配的工具，例如压模或浇铸模具。虽然该方法适于制造大量相同的三维成型体，但是当只要制造少量的具有不同三维形状的成型体时，所述方法是不利的。这使得难以基于这样的三维陶瓷成型体来制造用于人体的假体，因为这些假体必须要单独地匹配。
然而，另一方面这样的成型方法也是已知的，它包括由几何上的小单元通过有控制的材料沉积来直接构造复杂的成型体，这个过程由计算机控制的三维计算机模型作为起点。与常规模塑成型方法相比重要的优势是自由模塑成型，如果需要的话也能够使用另外的支撑结构。这类计算机控制的制造方法也称为实体自由成型制造或快速原型化。后者包括微型挤出、立体光刻、激光制造等，而喷墨印刷和选择性激光烧结也已知用于制造自由成型的实体(SFF)。
EP 0 847 314 B1描述了在基底上制造烧结结构的方法，其中利用喷墨式印刷机在基底上施加负载有颗粒的液体，之后蒸发所述液体并且烧结保留的颗粒。在该方法中，利用激光分层地进行颗粒的烧结。该方法目前为止是不令人满意的，因为利用激光的颗粒的分层烧结必须要使用昂贵的设备。
在J.Am.Ceram.Soc.，85(2002)，2113-2115中，X.Zhao等人描述了通过利用喷墨式印刷机分层印刷包含陶瓷颗粒的印刷液体来制造垂直陶瓷壁。此处使用的印刷液体包括二氧化锆颗粒、分散剂、异丙醇、辛烷和蜡。利用喷墨式印刷机在印刷台每次在z方向上降低以单层的形式印刷该印刷液体之后，将印刷的三维样品进行干燥并随后在高温下热解以除去有机组分。随后烧结所述Zr2陶瓷颗粒。
然而，已经发现该方法看起来不适合于批量制造三维陶瓷成型体，由于使用的所述印刷液体不具有必需的稳定性，使得悬浮的陶瓷颗粒沉降、喷墨式印刷机的印刷头的喷嘴阻塞，最终不能将陶瓷材料以期望的层的形式均匀沉积和因此不能均匀沉积三维成型体。结果，热解和烧结之后的成型体不具有期望的尺寸精度和均匀的密度和因此不具有期望的强度。
本发明的一个目的是提供一种方法和设备，利用所述方法和设备可以克服这些缺点，并且能够以简单的方式制造具有高尺寸精度和恒定机械性能的各种形状的三维陶瓷成型体，并且同时解决用于喷墨式印刷机的包含悬浮陶瓷颗粒的印刷液体的稳定性和分散状态以及适合性的问题。
现在意外地发现，该目的可以由此实现，即利用喷墨式印刷机印刷所用的悬浮液包含分散介质和其中悬浮的陶瓷颗粒，所述分散介质包含水性勃姆石溶胶(Boehmitsol)作为重要组分。
本发明因此提供根据权利要求1的方法和根据权利要求39的设备。
所述从属权利要求涉及本发明的这些主题的优选实施方案。
本发明因此涉及尤其是一种制造三维陶瓷成型体的方法，所述方法通过利用喷墨式印刷机将包含陶瓷成型体成型所需组分的悬浮液以期望的形状分层印刷到基材上，干燥和硬化所形成的复合层，所述方法的特征在于：使用在包含水性勃姆石溶胶、至少一种低分子量醇、至少一种干燥抑制剂和至少一种有机流化剂(Verfluessiger)的分散介质中包含50～80重量％陶瓷颗粒的悬浮液来实施印刷。
意外地发现在本发明的方法中用作印刷液体的悬浮液显示很好的稳定性，并且即使在高固体含量下所述陶瓷颗粒也几乎没有沉降的趋势，如果需要的话，所述陶瓷颗粒可以通过简单的振动来再分散。此外，根据本发明使用的悬浮液即使在高固体含量即50～80重量％的陶瓷颗粒含量下也具有适用于印刷过程的粘度以及良好的润湿性能和干燥性能。与所述的现有技术的教导相反，利用所述悬浮液和根据本发明的方法可以制造高尺寸精度的任意三维陶瓷成型体，所述陶瓷成型体具有均匀的机械性能且在经过烧结的陶瓷成型体中没有气孔形成。
在一个优选实施方案中，根据本发明的印刷悬浮液的分散介质中包含的勃姆石溶胶的固体含量为0.001～2重量％，更优选为0.001～1重量％，并且还更优选为0.01～0.5重量％。此处，勃姆石溶胶包含纳米晶体勃姆石颗粒和溶解的氢氧化铝(Aluminiumhydrat)。
纳米晶体勃姆石颗粒(AlO(OH))优选具有3～20nm的颗粒尺寸，更优选为4～5nm，并且特别有利地具有长度对宽度的比例(长宽比)为1.4:1～2.2:1，由此陶瓷颗粒可以以特别稳定的方式保持在悬浮液中。
作为溶解的氢氧化铝，根据本发明的分散介质中包含的勃姆石溶胶含有具有以下式的中性或离子化合物：[Al(H2O)6]3+、[Al(H2O)5OH]2+、[Al(H2O)4(OH)2]+、Al(OH)3(aq)、[Al(OH)4]-。
根据本发明特别有利的是，所述勃姆石溶胶的pH值为1.7～11，优选为4～10，并且还更优选为5～8。在该范围内的勃姆石溶胶的pH值下，陶瓷颗粒的非常良好的胶态悬浮液可以以稳定的方式保持，同时实现了悬浮液的良好的泵送能力和可印刷性。
在本发明的另一个优选实施方案中，所述分散介质包含48～88重量％的勃姆石溶胶，50～20重量％的低分子量醇，5～20重量％的干燥抑制剂和2～12重量％的有机流化剂或有机分散剂。
所述分散介质可以优选包含甲醇、乙醇、丙醇、异丙醇或其混合物作为低分子量醇，多元醇、长链烃或其混合物例如甘油和/或乙二醇作为干燥抑制剂。所述分散介质优选包含合成的有机聚电解质和/或羧酸制剂作为有机流化剂或有机分散剂。作为合成的有机聚电解质，优选具有4000～6000重均分子量的聚丙烯酸和/或聚甲基丙烯酸，这些酸优选以碱金属盐或铵盐的形式存在。这些优选的合成有机聚电解质产生不起泡沫的悬浮液，并且由于这些有机流化剂的存在，可以利用常规的喷墨式印刷机非常好地分层印刷到基底材料。尤其优选可以从Zschimmer&Schwarz公司获得的商品名为Dolapix CE64、Dolapix PC75和Dolapix ET85的以铵盐形式存在的聚丙烯酸。
在另一个优选实施方案中，所述分散介质包含62～91重量％的勃姆石溶胶，5～15重量％的乙醇，2～15重量％的甘油和/或乙二醇以及2～8重量％的铵盐形式的聚丙烯酸和/或聚甲基丙烯酸。
在本发明的一个有利的实施方案中，用作印刷液体的悬浮液包含陶瓷颗粒，所述陶瓷颗粒由下列物质组成：纯的Al2O3、纯的ZrO2、纯的Al2O3-ZrO2、纯的Si3N4、用勃姆石稳定化了的Al2O3、用Y2O3、HfO2、CeO2、MgO和/或CaO稳定化了的ZrO2、用Y2O3、HfO2、CeO2、MgO和/或CaO稳定化了的Al2O3-ZrO2、用Al2O3、Y2O3、Fe2O3和/或另外的稀土氧化物稳定化了的Si3N4或其混合物。
如果需要的话用Y2O3、HfO2、CeO2、MgO和/或CaO稳定化了的Al2O3-ZrO2混合陶瓷优选包含30～70重量％的Al2O3和相应的70～30重量％的ZrO2。特别优选用Y2O3稳定化了的ZrO2，它可以以TZ-3YS-E的的商品名从Tosoh公司，Tokyo获得。
根据本发明，尤其优选所述悬浮液包含量为60～70重量％的陶瓷颗粒。此处，陶瓷颗粒的颗粒尺寸必须小于使用的喷墨式印刷机的印刷头喷嘴的开口和进料管线的开口，并且优选d90值为0.01～3μm，更优选为0.5～1.5μm。
有利的是，在根据本发明的分散介质中的陶瓷颗粒悬浮液的pH值为4～11，优选为7～9，并且在25℃和γ>400的剪切速率下测量的粘度为5～25mPas，在γ<50的低剪切速率下测量的粘度为100～500mPas，这是由于悬浮液在该粘度下可容易地利用常规喷墨式印刷机的泵被输送通过这些常规喷墨式印刷机的印刷头和印刷喷嘴并且印刷。
在本发明的方法中，将形成期望的三维陶瓷成型体的层印刷到平面基材上，所述基材例如是具有开口孔隙率为0～10％的石墨薄片、铂片、陶瓷或玻璃陶瓷。
在本发明的另一个实施方案中，可以将形成三维陶瓷成型体的层印刷到基材上，在所述基材上事先使用悬浮液印刷一个或更多个在所述复合层硬化时可以除去的具有规定尺寸的层，所用悬浮液在前述的分散介质中包含在所述复合层硬化期间挥发的材料。以这种方式可以形成具有针对性的凹陷、开口等的三维陶瓷成型体，利用所述凹陷和开口可精确地将所述成型体连接至相应的对应件(Gegenstueck)例如金属部件或者植入牙齿的陶瓷部件，在其中根据本发明制造的三维成型体用作齿冠。
在本发明的一个优选实施方案中，除利用第一印刷头印刷的层之外或在利用第一印刷头印刷的层之间，利用第二印刷头使用悬浮液印刷一个或更多个在所述复合层硬化时可以除去的具有规定尺寸的层，所用悬浮液在前述的分散介质中包含在所述复合层硬化期间挥发的材料。以这种方式可以在单个印刷步骤中制造在期望位置具有凹陷、咬边等的三维陶瓷成型体，使得可以借助于这些来将所述陶瓷成型体按形状匹配于待相连的对应件。
作为在本发明的该实施方案中的挥发性材料，优选使用在高于200℃的温度蒸发或在氧的存在下在高于400℃的温度热解的材料。
尽管用于本发明的方法的悬浮液或印刷液体显示了陶瓷颗粒沉降或粘附至喷墨式印刷机的印刷头喷嘴的极低趋势，根据本发明的一个优选实施方案，所述印刷头的喷嘴在印刷一个或更多个层之后利用包含水、低分子量醇和多元醇的清洗液进行清洗。所述清洗液优选包含水:乙醇:多元醇重量比为6～10:1～4:1～3的，优选为8:1:1的水、乙醇和至少一种多元醇的混合物。
印刷头的喷嘴的清洗有利地以此方式进行，使得清洗液进入喷嘴和喷嘴的前室。清洗液进入喷嘴和喷嘴前室可以在包含悬浮液的印刷墨盒(Druckpatrone)中的减压或升高的外压力作用下产生。这可以例如通过设定印刷墨盒的气相的内压力为低于大气压2～100mbar(对应于200～10000Pa)，优选为低于大气压2～25mbar(对应于200～2500Pa)来实现，并且在一个特别优选的方案中，根据悬浮液在印刷墨盒中填充水平来控制，使得在印刷墨盒内部的压差根据悬浮液在印刷墨盒中的填充水平保持恒定。
在本发明的另一个优选实施方案中，在用所述清洗液浸渍的物体的作用下进行所述印刷头的喷嘴的清洗，所述物体在0.01～1N/mm2，优选为0.02～0.05N/mm2的压力下在所述印刷头上的喷嘴区域周期性地传送。该物体优选为开孔的泡沫或微纤维织物或其组合，也就是例如用微纤维织物绷紧的开孔泡沫。该物体例如是圆柱状并且围绕其纵向轴旋转以给定的压力来挤压印刷头的喷嘴并且经过所述喷嘴。在一个优选的实施方案中，所述印刷头在传送到达其末端位置或任意位置时经过该清洗设备。
此外，还可以在超声的作用下实施印刷头的喷嘴的清洗，并且该手段也可以与使用清洗液浸渍的物体的机械清洗相组合。优选印刷头的喷嘴的清洗在印刷墨盒中或印刷头处的压力循环之间在超声的作用下周期性地进行。
印刷之后，在65～105℃的温度下干燥所印刷的层，优选在施加之后干燥每个单个的层。优选通过将在喷墨式印刷机的印刷区域的每个单个的印刷的层加热至65～105℃的温度，优选68～85℃来干燥，如果需要的话，使用鼓风机、施加真空或采用对流来排出液体的蒸气。这些层的干燥也可以通过利用卤素灯、红外线灯辐射，通过离子辐射、激光辐射或使用布置在印刷区域中的加热元件来实施。
进行悬浮液的印刷使得干燥后的由陶瓷材料构成的单个层具有1μm～30μm，优选0.05μm～10μm的厚度，并且如果需要的话，由在复合层硬化期间挥发的材料构成的单个的印刷的层具有0.05μm～5μm的厚度。
最后一层干燥之后，以此方式获得的干燥的复合层通过烧结陶瓷材料进行硬化，在此优选的是，如果需要的话在升高的温度下例如在约80℃的温度下在干燥箱中保存印刷过程之后获得的复合层。优选在800～1500℃的温度下通过烧结来实施所形成的陶瓷材料复合层的硬化以形成三维陶瓷成型体。在此优选进行烧结直至烧结密度为理论密度的100％，优选直至所述理论密度的98％。
已经发现使用本发明的方法能够制造具有高尺寸精度的三维陶瓷成型体，所述陶瓷成型体没有干裂，各个层没有显示出分离并且优异地适合于制造医学陶瓷假体。
本发明的方法因此尤其针对医学陶瓷假体的制造，尤其是躯体、四肢和头、面部、口腔范围内的假体、牙齿植入物、牙齿嵌体、齿冠和齿桥的制造。
本发明还提供实施所述方法的设备，其特征在于：所述设备是常规的、计算机控制的喷墨式印刷机，所述喷墨式印刷机具有可以在z方向垂直移动、在计算机控制之下每次可降低一层的高度、可以在y方向移动并且如果需要的话，可以在x方向(印刷头的运动方向)移动的用于基材的支撑物，在印刷区域中的干燥装置和用于印刷头的喷嘴的清洗系统。
所述喷墨式印刷机优选是市售的按需滴液式印刷机(Drop-on-Demand-Drucker)，例如可以从Hewlet Packard Company获得的印刷机，已经通过在印刷区域中安装干燥设备和安装用于印刷头的喷嘴的清洗系统对其进行改装。这种设备的清洗系统优选包含可以用清洁液浸渍的物体，所述物体可以在清洗步骤中在压力下与印刷头的喷嘴接触。所述可以用清洗液浸渍的物体优选为圆柱状的开孔泡沫，在清洗步骤中印刷头的印刷喷嘴在压力下于清洗接触下经过其上。所述泡沫圆柱体优选可以绕其纵轴旋转并且其背离印刷头的一侧浸入到清洗液中。此处使得泡沫圆柱体的所述轴平行于喷墨式印刷机的印刷方向即印刷头的移动方向(x方向)或垂直于所述印刷方向(y方向)是有利的。
在本发明的设备的一个优选实施方案中，在泡沫圆柱体离开清洗液的位置和其接触喷墨式印刷机的印刷头的位置之间具有用于除去过量清洗液的擦版辊(Abstreifrolle)。
此外，本发明的设备的清洗系统可包括装有清洗液的超声波浴，具有印刷喷嘴的印刷头可以沉入其中。该实施方案的超声波浴优选布置在印刷头的停放位置的区域中。
实际实施本发明的方法时，首先在计算机上形成待制造的三维陶瓷成型体的精确形状，例如可以通过扫描模型来进行。例如，待形成的成型体所需的数据可以利用软件程序诸如Microsoft WORD在市售的计算机上建立。后来的三维成型体的x和y尺寸由在该WORD文档中以待印刷的各个层的形式建立的对象的二维描述给出。成型体的三维度(Dreidimensionalitaet)通过重复印刷具有合适尺寸的各个层来制造。
随后用待印刷的悬浮液填充所述印刷墨盒，之后印刷头对应于控制程序在基材上传送并且将悬浮液以层的形式以期望的形状印刷到基材上。随后在施加下一层之前干燥该层。继续这些步骤同时每次将基材的支撑物降低一层的高度，直至制造完成三维陶瓷成型体的生坯。随后，如果需要的话在干燥箱中在80℃下储存该成型体之后，在彻底烧结所述陶瓷材料需要的温度下烧结该成型体，并且得到具有高表面精度和表面品质的期望的三维陶瓷成型体。
根据本发明的该运行方式使得可以毫无问题地印刷大于10000个印刷循环，即印刷大于10000个具有期望的二维形状的层，而不阻塞印刷机的喷嘴。
以下实施例用于进一步说明本发明。
实施例
为制造用于本发明的分散介质的勃姆石溶胶，通过添加65％的硝酸将700ml水的pH值调节为2。将混合物加热到80℃并且加入2.1g勃姆石(Dispersal P2，来自Sasol公司，Hamburg)，搅拌所述混合物10分钟。将混合物冷却至室温，添加25％的氨至pH值为8.5并且将获得的水性勃姆石溶胶保存在聚乙烯瓶中。
为制造适当的印刷分散液，将150g如上所述制造的勃姆石溶胶与30g的85％的甘油混合，加入4.5g聚丙烯酸铵(Dolapix CE64，来自Zschimmer&Schwarz公司，Lahnstein)和11g聚丙烯酸铵(Dolapix75，来自Zschimmer&Schwarz公司，Lahnstein)，并且搅拌所述混合物30秒钟。随后加入450g用氧化钇稳定化了的二氧化锆(TZ-3YS-E，来自Tosoh公司，Tokyo)并且在具有合适分散头(S25N-10G，IKA-Werke，Staufen)的分散设备(Ultra-Turrax T25Basic，IKA-Werke，Staufen)中在6500～13500min-1下混合所述混合物一分钟，在混合期间加入25g的乙醇。随后在24000min-1下分散所述混合物另外2分钟并且将获得的悬浮液注入空的印刷墨盒中。
为制造用于印刷在复合层的硬化期间除去的层的悬浮液，将85g蒸馏水装入250ml聚乙烯瓶中，并且加入8.5g甘油和2.5g聚丙烯酸铵(DolapixET85，Zschimmer&Schwarz公司，Lahnstein)。然后混入1.5g聚乙二醇400、34g乙醇和38.5炭黑(Arosperse15，Degussa，Frankfurt)。加入200-250g直径为5mm的Al2O3研磨介质并且将所述材料在辊工作台(Rollenbank)上匀浆化40～45小时。然后除去研磨介质并且将获得的悬浮液注入空的印刷墨盒中。
使用上述第二悬浮液首先在石墨薄板基材上印刷三维陶瓷成型体，其在最终待制造的三维成型体中形成尺寸精确的凹陷。为此使用按需滴液式技术的喷墨式印刷机，所述喷墨式印刷机已经经过改装，使得其可以计算机控制印刷台在z方向上的降低，从而可以以这种方式制造三维成型体的分层构造。将所述印刷悬浮液引入印刷墨盒并且以通常的方式操作喷墨式印刷机，在此印刷头在计算机控制之下以通常的方式在x方向上在通过印刷机控制在y方向上移动的基材上传送。在该操作模式下的定位精度是20μm。
随后利用卤素灯来干燥每个施加的层，所述卤素灯的光利用光学凸透镜聚焦在印刷区域。同时，基底上的排风扇产生对流并且因此加速干燥。在该工序期间，基材和所施加的层的温度保持低于130℃，优选为约80℃。构建在复合层的硬化期间挥发的材料的三维成型体之后，将印刷墨盒用包含第一所述悬浮液的印刷墨盒替代，第一所述悬浮液包含用氧化钇稳定化了的二氧化锆构成的陶瓷颗粒，并且将基于陶瓷颗粒的第二三维成型体以期望的形状以相同的方式分层印刷到第一三维成型体上，在此以上述方式分别将所述层干燥。
完成三维成型体的制造之后，将其在约80℃的温度下在干燥箱中短时间干燥并然后在氧的存在下加热到约400℃的温度，以蒸发或热解仍存在的有机组分。然后在1400℃的温度下烧结所得三维成型体以形成期望的具有高尺寸精度和表面品质的三维陶瓷成型体，所述所得三维成型体具有对应于基于在复合层硬化期间挥发的材料的第一三维成型体的凹陷。
该陶瓷成型体具有理论烧结密度的约98％的密度，没有显示裂缝，具有高弯曲断裂强度并且因此高度适合作为医学陶瓷假体，例如作为牙齿植入物的冠。

Claims (55)

1.一种制造三维陶瓷成型体的方法，所述方法通过利用喷墨式印刷机将包含陶瓷成型体成型所需组分的悬浮液以期望的二维形状来分层印刷到基材上，干燥和硬化所形成的复合层，所述方法的特征在于：使用在包含水性勃姆石溶胶、至少一种低分子量醇、至少一种干燥抑制剂和至少一种有机流化剂的分散介质中包含50～80重量％陶瓷颗粒的悬浮液来实施印刷，并且所述低分子量醇包括甲醇、乙醇、丙醇、异丙醇或其混合物。
2.根据权利要求1的方法，其特征在于：所述勃姆石溶胶的固体含量为0.0001～2重量％。
3.根据权利要求2的方法，其特征在于：所述勃姆石溶胶的固体含量为0.001～1重量％。
4.根据权利要求2的方法，其特征在于：所述勃姆石溶胶的固体含量为0.01～0.5重量％。
5.根据权利要求1～4中任一项的方法，其特征在于：所述勃姆石溶胶包含纳米晶体勃姆石颗粒和溶解的氢氧化铝。
6.根据权利要求5的方法，其特征在于：所述纳米晶体勃姆石颗粒的颗粒尺寸为3～20nm。
7.根据权利要求6的方法，其特征在于：所述纳米晶体勃姆石颗粒的颗粒尺寸为4～5nm。
8.根据权利要求5的方法，其特征在于：所述纳米晶体勃姆石颗粒的长度对宽度的比例为1.4∶1～2.2∶1。
9.根据权利要求1～4中任一项的方法，其特征在于：所述勃姆石溶胶包含[Al(H2O)6]3+、[Al(H2O)5OH]2+、[Al(H2O)4(OH)2]+、Al(OH)3水溶液、[Al(OH)4]-和/或Al13离子作为溶解的氢氧化铝。
10.根据权利要求1～4中任一项的方法，其特征在于：所述勃姆石溶胶的pH为1.7～11。
11.根据权利要求1～4中任一项的方法，其特征在于：所述分散介质包含48～88重量％的勃姆石溶胶、5～20重量％的低分子量醇、5～20重量％的干燥抑制剂和2～12重量％的有机流化剂。
12.根据权利要求11的方法，其特征在于：所述分散介质包含多元醇、长链烃或其混合物作为干燥抑制剂，和合成的有机聚电解质和/或羧酸制剂作为有机流化剂。
13.根据权利要求12的方法，其特征在于：所述分散介质包含甘油和/或乙二醇作为多元醇。
14.根据权利要求12的方法，其特征在于：所述分散介质包含重均分子量为4000～6000的聚丙烯酸和/或聚甲基丙烯酸作为合成的有机聚电解质。
15.根据权利要求12的方法，其特征在于：所述分散介质包含重均分子量为4000～6000的聚丙烯酸和/或聚甲基丙烯酸的碱金属盐或铵盐作为合成的有机聚电解质。
16.根据权利要求1～4中任一项的方法，其特征在于：所述分散介质包含62～91重量％勃姆石溶胶、5～15重量％乙醇、2～15重量％甘油和/或乙二醇以及2～8重量％有机流化剂。
17.根据权利要求1～4中任一项的方法，其特征在于：所述陶瓷颗粒由下列物质组成：纯的Al2O3、纯的ZrO2、纯的Al2O3-ZrO2、纯的Si3N4、用勃姆石稳定化了的Al2O3、用Y2O3、HfO2、CeO2、MgO和/或CaO稳定化了的ZrO2、用Y2O3、HfO2、CeO2、MgO和/或CaO稳定化了的Al2O3-ZrO2、用Al2O3、Y2O3、Fe2O3和/或另外的稀土氧化物稳定化了的Si3N4或其混合物。
18.根据权利要求17的方法，其特征在于：所述任选地用Y2O3、HfO2、CeO2、MgO和/或CaO稳定化了的Al2O3-ZrO2混合陶瓷包含30～70重量％的Al2O3和相应的70～30重量％的ZrO2。
19.根据权利要求1～4中任一项的方法，其特征在于：在所述悬浮液中存在的所述陶瓷颗粒的量为60～70重量％。
20.根据权利要求1～4中任一项的方法，其特征在于：所述陶瓷颗粒的颗粒尺寸小于印刷头喷嘴的开口和进料管线的开口，并且d90值在0.01～3μm范围中。
21.根据权利要求1～4中任一项的方法，其特征在于：所述悬浮液的pH值为4～11，并且在25℃下在γ＞400的剪切速率下的粘度为5～25mpas以及在低的剪切速率γ＜50下的粘度为100～500mPas。
22.根据前述权利要求21的方法，其特征在于：所述悬浮液的pH值为7～9。
23.根据权利要求1～4中任一项的方法，其特征在于：将所述层印刷到平面基材上。
24.根据权利要求23的方法，其特征在于：将所述层印刷到作为基材的具有开孔孔隙率为0～10％的石墨薄片、铂片、陶瓷上。
25.根据权利要求23的方法，其特征在于：将所述层印刷到作为基材的具有开孔孔隙率为0～10％的玻璃陶瓷上。
26.根据权利要求1～4中任一项的方法，其特征在于：将所述层印刷到基材上，在所述基材上事先使用所述悬浮液印刷一个或更多个在所述复合层硬化时可以除去的具有规定尺寸的层，所用悬浮液在前述的分散介质中包含在所述复合层硬化期间挥发的材料。
27.根据权利要求1～4中任一项的方法，其特征在于：在利用第一印刷头印刷的层之间或除利用第一印刷头印刷的层之外，利用第二印刷头使用悬浮液印刷一个或更多个在所述复合层硬化时可以除去的具有规定尺寸的层，所用悬浮液在前述的分散介质中包含在所述复合层硬化期间挥发的材料。
28.根据权利要求26的方法，其特征在于：将在高于200℃的温度蒸发或在氧存在下在高于400℃的温度热解的材料用作所述在所述复合层硬化期间挥发的材料。
29.根据权利要求27的方法，其特征在于：将在高于200℃的温度蒸发或在氧存在下在高于400℃的温度热解的材料用作所述在所述复合层硬化期间挥发的材料。
30.根据权利要求1～4中任一项的方法，其特征在于：印刷一个或更多个层之后，利用包含水、低分子量醇和多元醇的清洗液清洗所述印刷头的喷嘴。
31.根据权利要求30的方法，其特征在于：使用水∶乙醇∶多元醇重量比为(6～10)∶(1～4)∶(1～3)的水、乙醇和至少一种多元醇的混合物作为清洗液。
32.根据权利要求31的方法，其特征在于：使用水∶乙醇∶多元醇重量比为8∶1∶1的水、乙醇和至少一种多元醇的混合物作为清洗液。
33.根据权利要求27的方法，其特征在于：进行所述印刷头的喷嘴的清洗，使得清洗液进入所述喷嘴和所述喷嘴的前室。
34.根据权利要求33的方法，其特征在于：在包含所述悬浮液的印刷墨盒中的减压或升高的外压力作用下，使得所述清洗液进入所述喷嘴和所述喷嘴的前室。
35.根据权利要求34的方法，其特征在于：在所述清洗液浸渍的物体的作用下进行所述印刷头的喷嘴的清洗，所述物体在0.01～1N/mm2的压力下在所述印刷头上的喷嘴区域周期性地传送。
36.根据权利要求35的方法，其特征在于：所述物体在0.02～0.05N/mm2的压力下在所述印刷头上的喷嘴区域周期性地传送。
37.根据权利要求1～4中任一项的方法，其特征在于：所述印刷头的喷嘴的清洗在超声的作用下进行。
38.根据权利要求37的方法，其特征在于：所述印刷头的喷嘴的清洗在所述印刷墨盒中或所述印刷头处的压力循环之间的超声的作用下周期性地进行。
39.根据权利要求1～4中任一项的方法，其特征在于：所印刷的层在65～105℃的温度下干燥。
40.根据权利要求39的方法，其特征在于：每个单个层在印刷之后进行干燥。
41.根据权利要求40的方法，其特征在于：每个单个的印刷的层通过加热至65～105℃的温度在所述喷墨式印刷机的印刷区域中干燥。
42.根据权利要求40的方法，其特征在于：使用鼓风机、施加真空或采用对流以排出液体的蒸气。
43.根据权利要求41的方法，其特征在于：每个单个的印刷的层通过加热至68～85℃的温度在所述喷墨式印刷机的印刷区域中干燥。
44.根据权利要求41的方法，其特征在于：通过用卤素灯、红外线灯的辐射、离子辐射、激光辐射或使用布置在所述印刷区域中的加热元件来实施加热。
45.根据权利要求1～4中任一项的方法，其特征在于：由陶瓷材料构成的单个的印刷的层在干燥之后具有1μm～30μm，由在所述复合层硬化期间蒸发的材料构成的单个的印刷的层的厚度为0.05μm～5μm。
46.根据权利要求1～4中任一项的方法，其特征在于：由陶瓷材料构成的单个的印刷的层在干燥之后具有0.05μm～10μm的厚度。
47.根据权利要求1～4中任一项的方法，其特征在于：已干燥的复合层的硬化通过烧结所述陶瓷材料来进行。
48.根据权利要求47的方法，其特征在于：在80℃的干燥箱中储存之后烧结所述陶瓷材料。
49.根据权利要求47所述的方法，其特征在于：所述烧结在800℃～1500℃的温度下进行。
50.根据权利要求47的方法，其特征在于：进行烧结直至烧结密度为理论密度的100％。
51.根据权利要求47所述的方法，其特征在于：进行烧结直至烧结密度为理论密度的98％。
52.根据前述权利要求1～4中任一项的方法，其特征在于：制造医学陶瓷假体作为三维陶瓷成型体。
53.根据权利要求52的方法，其特征在于，所述医学陶瓷假体包括躯体、四肢、头、面部、口腔范围内的假体。
54.根据权利要求53方法，其特征在于，所述口腔范围内的假体包括牙齿植入物。
55.根据权利要求54的方法，其特征在于，所述牙齿植入物包括牙齿嵌体、齿冠和齿桥。
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