CN101450859B - 用BaCeO3掺杂提高YBaCuO超导体性能的方法 - Google Patents

用BaCeO3掺杂提高YBaCuO超导体性能的方法 Download PDF

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CN101450859B
CN101450859B CN2007101784425A CN200710178442A CN101450859B CN 101450859 B CN101450859 B CN 101450859B CN 2007101784425 A CN2007101784425 A CN 2007101784425A CN 200710178442 A CN200710178442 A CN 200710178442A CN 101450859 B CN101450859 B CN 101450859B
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肖玲
焦玉磊
郑明辉
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GRIMN Engineering Technology Research Institute Co Ltd
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Abstract

一种用BaCeO3掺杂提高YBaCuO超导体性能的方法，其特征在于，将平均粒度为1nm～100nm的BaCe1-xGdxO3粉末加入Y1.8Ba2.4Cu3.4Oy粉末中，经球磨混合均匀后，用单轴模压成型，再采用顶部籽晶辅助熔融织构生长工艺(TSMTG)生成单畴结构的YBaCuO超导块，其中，BaCe1-xGdxO3粉末加入量为Y1.8Ba2.4Cu3.4Oy粉末的0.25wt％～1.00wt％。用本发明的方法制备的单畴YBaCuO超导块的临界电流密度均高于未掺杂的单畴YBaCuO超导块。掺杂量为0.50wt％的超导块的临界电流密度达到了掺杂0.2wt％贵金属Pt样品的同等水平。

Description

用BaCeO<sub>3</sub>掺杂提高YBaCuO超导体性能的方法
技术领域
本发明涉及一种通过纳米颗粒掺杂提高钇钡铜氧(YBaCuO)超导块材性能的方法。
背景技术
YBaCuO超导块的成份以YBa2Cu3O7-y超导相(123相)为主，添加一定量的Y2BaCuO5-x非超导相(211相)。添加非超导的211相的主要目的是防止单畴超导块生长过程中液相的流失。YBaCuO超导块通过包晶反应生成c轴择优取向的晶体结构，最终产物中具有大量颗粒状的211相被俘获在层状123相基体中的特征。大量工艺研究的结果证实，细小的211相颗粒弥散分布在123相基体中可以增加超导材料的磁通钉扎能力，从而提高超导材料的性能。通常细化211相颗粒的方法是在YBaCuO的先驱粉末中掺杂0.2wt％～0.5wt％的铂粉(Pt)。由于Pt是价格昂贵的贵金属元素，Pt的掺杂增加了YBaCuO超导块的成本。
发明内容
本发明的目的是提供一种用BaCeO3掺杂提高YBaCuO超导体性能的方法，可以进一步细化单畴YBaCuO超导块中211颗粒，从而提高超导材料临界电流密度。
为实现上述目的，本发明采取以下技术方案：
一种用BaCeO3掺杂提高YBaCuO超导体性能的方法，将平均粒度为1nm～100nm的BaCeO3粉末加入Y1.8Ba2.4Cu3.4Oy粉末中，经球磨混合均匀后，用单轴模压成型，再采用顶部籽晶辅助熔融织构生长工艺(TSMTG)生成单畴结构的YBaCuO超导块，其中，BaCeO3粉末加入量为Y1.8Ba2.4Cu3.4Oy粉末的0.25wt％～1.00wt％。
本发明所采用的球磨混合、单轴模压成型、顶部籽晶辅助熔融织构生长工艺(TSMTG)均为公知工艺。
采用顶部籽晶辅助熔融织构生长工艺(TSMTG)，其中，TSMTG是顶部籽晶辅助熔融织构生长工艺英文Top Seeded Melt Textured Growth的缩写。本发明采用纳米数量级粒度的BaCeO3替代Pt掺杂在YBaCuO先驱粉中，采用顶部籽晶辅助熔融织构生长工艺(TSMTG)的工艺参数没有变化。
使用微米数量级粒度的BaCeO3替代Pt可以取得良好的效果，有细化211相颗粒和提高性能的作用，但总体效果不如Pt。纳米级粒度即平均粒度为1nm～100nm的BaCeO3掺杂在YBaCuO先驱粉中制备单畴YBaCuO超导块，可以进一步细化211相颗粒从而进一步提高超导块的性能。
本发明的优点为：本发明用纳米粒度的BaCeO3掺杂在YBaCuO先驱粉中，掺杂量为0.25wt％～1.00wt％。用其制备的单畴YBaCuO超导块的临界电流密度均高于未掺杂的单畴YBaCuO超导块。掺杂量为0.50wt％的超导块的临界电流密度达到了掺杂0.2wt％贵金属Pt样品的同等水平。
附图说明
图1为不同含量BaCeO3掺杂样品(A、B、C)的临界电流Jc与磁场B的关系及其与未掺杂样品D和掺Pt样品E的比较图。
具体实施方式
将相对于Y1.8Ba2.4Cu3.4Oy先驱粉末的0.25wt％～1.00wt％的平均粒度为1nm～100nm的BaCeO3加入Y1.8Ba2.4Cu3.4Oy粉末中，放入玛瑙罐中用玛瑙球研磨。按300～400目研磨粒度配球，球料重量比约为1∶1.2，研磨时间约4小时。经球磨混合均匀后，用150MPa的压强单轴模压成型。再采用顶部籽晶辅助熔融织构生长工艺(Top Seeded Melt Textured Growth，缩写为TSMTG工艺)生成单畴结构的YBaCuO超导块。TSMTG工艺过程和具体参数如下：将c轴取向的SmBaCuO或NdBaCuO小晶体放在模压成型的圆柱状YBaCuO块的顶表面中心位置，保持其c轴与园柱状材料的对称轴平行。将带有籽晶的成型块放入加热炉中，以250℃～350℃/小时的速率快速升温至1050℃±5℃，保温1～2小时后以400℃～600℃/小时的速率快速降温至1010℃～1015℃，再以0.3～0.5℃/小时的速率缓慢降温至975℃±5℃，然后以100～200℃/小时的速率冷却到室温，使YBaCuO块经历部分熔化后再凝固的过程，生成单畴结构的YBaCuO超导块。
实施例1
将平均粒度为60nm的BaCeO3粉按相对于Y1.8Ba2.4Cu3.4Oy先驱粉末0.25wt％，0.50wt％和1.00wt％的比例分别加入Y1.8Ba2.4Cu3.4Oy先驱粉末中，BaCeO3粉的经球磨混合均匀后，用单轴模压成型，再采用顶部籽晶辅助熔融织构生长工艺(TSMTG)生成三种不同成分的单畴YBaCuO超导块A、B和C。
从A、B和C三种超导块上取样，分别测量其在77K温度下的临界电流密度(Jc)，结果显示于图1。在0～2T的测量磁场范围内，样品B(掺杂量为0.50wt％)的Jc最高，样品A(掺杂量为0.25wt％)次之，样品C(掺杂量为1.00wt％)最低。在1.0T磁场下A、B样品的Jc均为1.3×104A/cm2，C样品为1.0×104A/cm2；在2.0T磁场下B样品的Jc仍然接近1.0×104A/cm2，而A样品和C样品分别下降为0.4×104A/cm2和0.2×104A/cm2。上述3种样品的Jc与未掺杂样品D相比，均有不同程度的提高。其中掺杂0.50wt％BaCeO3的效果最好，达到掺杂0.2wt％Pt样品E的同等水平。
实施例2
采用和实施例1相同的方法，将平均粒度为20nm的BaCeO3粉按相对于Y1.8Ba2.4Cu3.4Oy先驱粉末0.25wt％，0.50wt％和1.00wt％的比例分别加入Y1.8Ba2.4Cu3.4Oy先驱粉末中，BaCeO3粉的经球磨混合均匀后，用单轴模压成型，再采用顶部籽晶辅助熔融织构生长工艺(TSMTG)生成三种不同成分的单畴YBaCuO超导块A’、B’和C’。平均粒度为20nm的BaCeO3掺杂效果与上述平均粒度为60nm的掺杂效果相当。
实施例3
采用和实施例1相同的方法，将平均粒度为90nm的BaCeO3粉按相对于Y1.8Ba2.4Cu3.4Oy先驱粉末0.25wt％，0.50wt％和1.00wt％的比例分别加入Y1.8Ba2.4Cu3.4Oy先驱粉末中，BaCeO3粉的经球磨混合均匀后，用单轴模压成型，再采用顶部籽晶辅助熔融织构生长工艺(TSMTG)生成三种不同成分的单畴YBaCuO超导块A”、B”和C”。平均粒度为90nm的BaCeO3掺杂效果与上述平均粒度为60nm的掺杂效果相当。
比较例1
将Y1.8Ba2.4Cu3.4Oy粉末用单轴模压成型，再采用顶部籽晶辅助熔融织构生长工艺(TSMTG)生成单畴YBaCuO超导块D。
从D超导块上取样，测量其在77K温度下的临界电流密度(Jc)，结果也显示于图1。在1.0T磁场下Jc为0.7×104A/cm2，在2.0T磁场下Jc下降至0.1×104A/cm2以下。在0～2T的测量磁场范围内，样品D的Jc均低于掺杂纳米BaCeO3的样品。
比较例2
将Pt粉按0.2wt％的比例加入Y1.8Ba2.4Cu3.4Oy先驱粉末中，经球磨混合均匀后，用单轴模压成型，再采用顶部籽晶辅助熔融织构生长工艺(TSMTG)生成单畴YBaCuO超导块E。
从E超导块上取样，测量其在77K温度下的临界电流密度(Jc)，结果也显示于图1。在1.0T磁场下Jc为1.3×104A/cm2，在2.0T磁场下Jc为1.0×104A/cm2以下。在0～2T的测量磁场范围内，样品E的Jc均高于未掺杂样品D，与掺杂0.50wt％内米BaCeO3的样品B相同。
本发明用纳米粒度的BaCeO3掺杂在YBaCuO先驱粉中，掺杂量为0.25wt％，0.50wt％和1.00wt％。用其制备的单畴YBaCuO超导块的临界电流密度均高于未掺杂的单畴YBaCuO超导块。掺杂量为0.50wt％的超导块的临界电流密度达到了掺杂0.2wt％贵金属Pt样品的同等水平。因此，本发明的方法提高超导块材性能同时降低单畴超导块成本。

Claims (1)

1.一种用BaCeO3掺杂提高YBaCuO超导体性能的方法，其特征在于，将平均粒度为1nm～100nm的BaCeO3粉末加入Y1.8Ba2.4Cu3.4Oy粉末中，经球磨混合均匀后，用单轴模压成型，再采用顶部籽晶辅助熔融织构生长工艺生成单畴结构的YBaCuO超导块，其中，BaCeO3粉末加入量为Y1.8Ba2.4Cu3.4Oy粉末的0.25wt％～1.00wt％。
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