CN1021176C - 陶瓷高温超导零件连接法 - Google Patents

陶瓷高温超导零件连接法 Download PDF

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CN1021176C
CN1021176C CN91100970A CN91100970A CN1021176C CN 1021176 C CN1021176 C CN 1021176C CN 91100970 A CN91100970 A CN 91100970A CN 91100970 A CN91100970 A CN 91100970A CN 1021176 C CN1021176 C CN 1021176C
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艾伯德·普莱瑟
约克·布克
约翰司·霍兹姆
万尼尔·霍斯特
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Abstract

为使由成分为Bi(2+a-b)(Sr(1-c)Cac)PbbCu(2+d)OX(其中a＝0～0.3，b＝0～0.5，C＝0.1-0.9，d＝0-2，X决定于所含金属的氧化状态)的陶瓷高温超导材料制成的零件连接在一起，将其端面相隔一定的间隙放置，用燃气-氧焰加热至750-875℃。与此同时，将一相同材料制得的棒置于间隙上方，加热至熔化并滴入间隙将其完全填满，然后，至少将两零件的接头置于780-850℃进行7-100小时。

Description

本发明涉及由成分为Bi（2+a-b）（Sr（1-c）Cac）（3-a）PbbCu（2+d）Ox（其中a＝0～0.3，b＝0～0.5，c＝0.1～0.9，d＝0～2，X决定于所含金属的氧化状态）的陶瓷高温超导材料制造的零件的连接方法。
德国专利申请书P3，830，092，3，（不属本发明现有技术出版物）揭示了成分为Bi2（Sr，Ca）3Cu2Ox（x值为8～10）的高温超导体的制造方法，其方法是：将铋、锶、钙和铜的碳酸盐或氧化物的化学计量混合物加热至870～1100℃，形成均匀的熔融物。将其注入铸模并固化，再将其取出在780～850℃下进行6～30小时的热处理。然后，置于氧气中，在温度为600～830℃下至少处理6小时。用这种方法可以生产晶面长度或直径达几厘米的片晶和长度达50cm，直径达10mm的棒晶，它们均由纯化合物构成。
该方法的缺点在于，上述陶瓷高温超导体很脆，不能卷装入大直径（例如2m）鼓盘内进行运输，而免于受到损坏。尤其是对传送大电流的高温超导体，问题更为突出。
将高温超导体粉末充入银管，然后将其用挤压或冲压方法得到所需直径的线材。在银管内部的高温超导体粉末可经热处理锻烧而形成一种粘合的型芯。此时，为形成超导体所需的氧通过银管壁而扩散。
上述管内的粉末导体可以经得起某种程度的弯曲，原则上可用于 大电流传输。然而，他们有一个缺点。就是只有在小直径时才能弯曲而不被损坏，并且不能连成复杂的构件。
本发明的目的就是揭示一种由陶瓷高温超导体制成的零件的连接方法，以获得更复杂的构件。此时接头也是超导的。按照本发明，将零件相隔一段间隔，用煤气-氧焰加热零件的两个端面，温度为750～875℃。与此类似，再将一根由相同材料制成的棒进行加热，此棒是置于两零件间隙上方的，加热直至其熔化并滴入间隙将其完全充满，然后将二零件的接头在780～850℃进行7～100小时的热处理。
本发明所述的方法可进一步详述如下：
a）热处理温度为815～830℃。
b）热处理时间取决于接头的厚度，接头越厚，时间要求越长，反之亦然。
c）需连接的两零件端面可以是相互平行的。
d）需连接的两零件端面可以是相互成楔形的。
e）陶瓷高温超导零件可用银管套起来。
本发明所使用的化合物，如：Bi2（Sr，Ca）3Cu2Ox（X约为8.2）熔点是不一致的，而是有一定的间隔，而且，这些熔融物在空气中对于固相的表面张力很大，以至使他们不能立即从固相中脱出。这两个特征对于连接是很好的先决条件，与气焊连接金属相似。
化合物Bi2（Sr，Ca）3Cu2Ox（X大约为8.2）的熔点高于875℃，当X为7.5时降至大约780℃。该熔融物固化后形成的固体不再是超导体。但是，将其在空气中进行约800℃ 的热处理，又可再度恢复为超导体。
根据本发明的方法，应注意保证需连接的两零件端面加热到能使其将从加热棒滴出的熔料焊住。
按照本发明的方法，薄接头热处理8-15小时，而厚接头则达100小时。
两零件接头的热处理：将成形零件放入炉内热处理，这种处理可能是有效的。热处理也可以局部进行，即在接点周围安置一个具有精密温度测量和控制的小型电炉，或用局部高频感应加热，或用电极横在接点间对其直接加热，另外还可使用激光脉冲。
按照本发明焊接用银管套起来的由高温超导陶瓷材料制成的成形零件时，应特别注意不要将煤气-氧焰同银套接触，因为银的熔点和高温超导化合物的熔点相差很大，会将银套烧化。无银接头必要时可以事后加套。
本发明方法的应用可以用图例说明，附图为截面图：
图1：表示端面相互平行的两根圆棒的连接，
图2：表示端面相互成楔形的两根粗圆棒的连接。
图3：表示端面互相平行的两根不同粗细的圆棒连接。
图4：表示一薄圆盘与一端面与其平行的圆棒连接。
图5：表示对圆棒接点进行局部热处理的装置。
图6：表示温度/电阻图。
图1中，阴影线A表示固化和非超导熔料，阴影线B表示经进一步热处理后的超导化合物。
图1a表示在熔体滴入间隙固化后的两圆棒接头，而图1b表示在815℃热处理24小时后的接头。
图3中，沿粗细圆棒纵轴有一空腔区域。
图5中，1为载热体，其中包含热阻线圈2，经管4固定于支座3内，5表示两根陶瓷高温超导材料制成的圆棒接缝，热电偶6放在靠近接缝5的地方。
图6中，有三组测量曲线，是在按本发明例1方法连接的零件上测得的。详细地说，曲线1和2是在相互连接的每个零件上测得的，曲线3是超出接头区测得的。
例1.
按德国专利申请书P3，830，092，3准备两根直径5mm，长150mm的圆棒，将其置于一陶瓷基底上，中间留一间隙，并使其端面相互平行。用天然气-氧焰将两端面加热至亮红色。与此同时，将一相同材料制得的圆棒置于间隙上方加热，并使熔料滴入间隙。缓慢地旋转二圆棒使熔料均匀充满间隙（参见图1a）。将连接的圆棒置于炉内进行815℃、12小时的热处理，两棒连接区成为超导体（参见图1.b）。
两圆棒连接区的临界温度为85.5K，连接区左右分别为86.0K和86.5K（参见图6）。
例2
两根直径12mm，长300mm的圆棒，它们是按德国专利申请书P3，830，092，3准备的，将其端面互成楔形位置。用丙烷气-氧焰在其开端加热，从基底部开始熔化，再将相同材料圆棒熔化后的熔料滴入楔形间隙并完全充满（见图2），然后将连接的圆棒在炉内进行800℃、24小时的热处理。
为检查两圆棒的接点是否是超导体，可测量其比电阻：
热处理前，293K：1Ω×Cm
热处理后，293K：0.001Ω×Cm
热处理后，77K：0Ω×Cm
例3
同例2，但作如下修改：一根圆棒直径为5mm，长120mm另一根直径16mm，长40mm，卡入支撑装置，使它们同心，端面互相平行。（见图3）。
测量圆棒连接头的比电阻：
热处理前，293K：2.8Ω×Cm
热处理后，293K：0.0015Ω×Cm
热处理后，77K：0Ω×Cm
例4
同例2，但做如下修改，圆棒直径为5mm，长80mm，垂直地连接于直径为20mm，厚度为5mm的圆盘（见图4），此时应注意保证薄圆盘比圆棒的受热相对要弱些。
例5
同例2，但做如下修改：两根直径为8mm的圆棒相互连接，在接头处进行局部热处理。为此，使用小电炉，围绕圆棒的接头区，并用氧化铝棉进行热绝缘，侧面安装的热偶是用于温度控制的（见图5）。

Claims (7)

1、连接陶瓷高温超导材料零件的方法，该超导材料零件组成为
Bi(2+a-b)(Sr(1-c)Cac)(3-a)PbbCu(2+d)Ox，
其中a=0-0.3，b=0-0.5，c=0.1-0.9，d=0-2，而X为取决于所含金属氧化状态的值，其特征在于，将超导材料零件端面相互隔开一定的间隙放置，用燃气-氧焰将其加热到750-875℃，与此同时将一相同材料制成的棒置于间隙上方，将其加热熔化并使其滴入间隙，将间隙完全填满而在两零件之间形成接头，最后至少将该接头置于780-850℃下热处理7-100小时。
2、根据权利要求1所述的方法，其特征在于，热处理在815-830℃进行。
3、根据权利要求1所述的方法，其特征在于，热处理时间取决于接头的厚度，接头越厚，要求的热处理时间越长，反之亦然。
4、根据权利要求1所述的方法，其特征在于，待连接零件端面相互平行。
5、根据权利要求1所述的方法，其特征在于，待连接零件相互呈楔形放置。
6、根据权利要求1所述的方法，其特征在于，待连接陶瓷高温超导材料零件用银管套起来。
7、按照权利要求1所述方法连接而成的陶瓷高温起导材料连接件。
CN91100970A 1990-02-13 1991-02-09 陶瓷高温超导零件连接法 Expired - Fee Related CN1021176C (zh)

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