CN115504780A - 一种在高温超导材料中均匀地掺杂纳米颗粒的方法 - Google Patents
一种在高温超导材料中均匀地掺杂纳米颗粒的方法 Download PDFInfo
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Abstract
本发明属于超导材料技术领域，提供了一种在高温超导材料中均匀地掺杂纳米颗粒的方法。本发明提供的方法利用柠檬酸和乙二醇混合的有机凝胶将纳米颗粒分散开，保证纳米颗粒不团聚，且通过固化粉碎后的有机凝胶固化物粉末的尺寸与单相高温超导体粉末的尺寸相近，从而能使两者均匀地混合，之后将柠檬酸和乙二醇混合有机凝胶在430‑500℃下保温数个小时使其完全分解，制备得到掺杂纳米颗粒的单相高温超导体。本发明提供的方法简单方便，效率高，可控性好，能够使纳米颗粒在掺杂的单相高温超导体中均匀分布。
Description
本申请是申请日为2021年01月09日、申请号为202110028075.0、发明名称为《在高温超导材料中均匀地掺杂纳米颗粒的方法》的分案申请。
技术领域
本发明属于超导材料技术领域，具体涉及一种在高温超导材料中均匀地掺杂纳米颗粒的方法。
背景技术
超导材料按超导现象出现的温度范围可分为两类：液氦温区的低温超导体和液氮温区的高温超导体。由于低温超导体的超导转变温度很低且运行时需要极昂贵的液氦，它们在实际应用中就受到很大限制。高温超导材料主要是铜氧化物陶瓷材料，由于它们具有很大的各向异性和低的载流子密度，它们的临界电流密度Jc较低且随磁场增高而很快下降。由于它们是陶瓷材料，难以形成高质量的线材或带材，从而阻碍了它们的广泛应用。
高温超导体的实际应用必须解决一个关键问题：提高临界电流密度和不可逆临界磁强。当磁通钉扎力较弱时，高场下的临界电流密度就较低，这影响了高温超导体在高温(比如77K)和高磁场(比如>4T)下的实际应用。解决上述关键问题的途径之一是增加磁通钉扎中心的密度。在高温超导材料中引入弥散分布的纳米颗粒，使它们成为有效的磁通钉扎中心，从而有效地提高高温超导材料的临界电流密度和不可逆临界磁强。
E.Hannachi等人[1]在YBa2Cu3Oy高温超导体中掺入TiO2纳米颗粒来提高其临界电流密度；M.K.BenSalem等人[2]通过掺入SiO2纳米颗粒来提高YBa2Cu3Oy高温超导体的临界电流密度；M.Hafiz等人[3]在(Bi,Pb)2Sr2Ca2Cu3O10高温超导体中掺入CoFe2O4磁性纳米颗粒来提高其临界电流密度；N.A.A.Yahya等人[4]通过掺入Bi2O3纳米颗粒来提高Bi1.6Pb0.4Sr2Ca2Cu3O10高温超导体的临界电流密度。这些研究都没有考虑到纳米颗粒会团聚且纳米颗粒的尺寸远小于超导粉末的尺寸，从而导致两者混合不均匀。包括在CN101450859B专利中，一种用BaCeO3纳米颗粒掺杂来提高Y-Ba-Cu-O高温超导体性能的方法，也只是将BaCeO3纳米颗粒直接加入Y1.8Ba2.4Cu3.4Oy粉末中进行球磨混合，并没有考虑纳米颗粒的团聚和极小尺寸会导致掺杂不均匀的问题。
团聚是指当材料颗粒间的作用力远大于重力时，此时颗粒的行为已不再受重力的束缚，而在颗粒间作用力的影响下相互靠拢从而发生聚集的现象。纳米颗粒与高温超导前驱粉末混合时会发生团聚且由于两者的尺寸相差甚远，两者的混合不可能均匀，进而会影响到高温超导复合材料的临界电流密度。为了获得高临界电流密度的高温超导复合材料，必须避免纳米颗粒的团聚和混合的不均匀性。
发明内容
本发明的目的是针对在高温超导材料中掺杂纳米颗粒的不均匀性问题，通过利用柠檬酸(citricacid，CA)和乙二醇(ethyleneglycol，EG)的混合物有机凝胶，来解决纳米颗粒在高温超导材料中团聚和不均匀分散的问题。
为实现以上发明目的，本发明提供一种在高温超导材料中均匀地掺杂纳米颗粒的方法，步骤为：
(1)按一定的比例称取柠檬酸和乙二醇，将乙二醇放入玻璃容器中在70-100℃的恒温水浴或油浴中预热后，往水浴或油浴中的乙二醇倒入柠檬酸并搅拌一定的时间达到完全互溶，形成有机凝胶，此时再往水浴或油浴中的有机凝胶倒入适量的纳米颗粒持续搅拌一定的时间达到均匀混合；
(2)将混合均匀的乙二醇和柠檬酸有机凝胶与纳米颗粒混合物倒进固化模中，再放入鼓风干燥箱在130-150℃固化，固化时间大于8h；
(3)等混合物完全固化后取出，用粉碎机将其粉碎，粉碎的粉末与一定比例的单相高温超导体粉末均匀混合，再用压片机将其混合物压成块体；
(4)将压好的块体放进热处理炉在430-500℃保温数个小时后冷却到室温；
(5)取出热处理后的块体再将其压实，后放回热处理炉在高温超导体烧结温度下烧结一定的时间，经过这样的混合处理后达到高温超导体与纳米颗粒均匀混合。
优选的，所述步骤(1)中柠檬酸和乙二醇的摩尔比在1：2与1：4的范围之间。
优选的，所述步骤(1)中采用磁力搅拌器将混合物搅拌均匀。
优选的，所述步骤(2)中固化模用的是固化后容易将固化物脱模取出且耐130-150℃固化温度的硅胶软模。
优选的，所述步骤(5)中混合处理后的高温超导体仍是单相高温超导体。
优选的，当所述步骤(1)中所述纳米颗粒为CoFe2O4磁性纳米颗粒时，所述步骤(5)中单相高温超导体粉末为铋系Bi2-xPbxSr2Ca2Cu3O10+y(Bi-2223)单相高温超导体粉末；或：当所述步骤(1)中所述纳米颗粒为NiFe2O4磁性纳米颗粒时，所述步骤(5)中单相高温超导体粉末为钇系YBa2Cu3O7-y(Y-123)单相高温超导体粉末。
本发明在高温超导材料中均匀地掺杂纳米颗粒的方法巧妙地利用柠檬酸和乙二醇混合有机凝胶将纳米颗粒分散开，保证纳米颗粒不团聚，且有机凝胶固化物粉末的尺寸与超导粉末的尺寸相近，从而能使两者均匀地混合，再让柠檬酸和乙二醇混合有机凝胶在430-500℃下保温数个小时使其完全分解，最后剩下的是单相高温超导体和掺杂均匀的纳米颗粒。此方法具有操作简单方便，效率高，可控性好等优点。
附图说明
图1是本发明一个实施例的工艺流程图。
具体实施方式
下面结合附图和具体实施例对本发明作优选说明。
实施例1
如图1所示，一种高温超导材料中均匀地掺杂纳米颗粒的方法，高温超导体是铋系Bi2-xPbxSr2Ca2Cu3O10+y(Bi-2223)单相高温超导体，工艺流程如下：
(1)按摩尔比为1：2称取柠檬酸和乙二醇，将乙二醇放入玻璃容器中在90℃的水浴中预热后，往水浴中的乙二醇倒入柠檬酸并用磁力搅拌器搅拌15min达到完全互溶，此时再往水浴中的乙二醇和柠檬酸混合物倒入适量的CoFe2O4磁性纳米颗粒，持续搅拌30min的时间达到均匀混合，磁力搅拌的转速为900r/min；
(2)将混合均匀的乙二醇、柠檬酸和CoFe2O4磁性纳米颗粒混合物倒进硅胶软模中，再放入鼓风干燥箱在130℃固化12h；
(3)等混合物完全固化后取出，用粉碎机将其粉碎，粉碎的粉末与一定比例的Bi-2223单相高温超导体粉末均匀混合，再用压片机将其混合物压成块体；
(4)将压好的块体放进热处理炉在430℃下保温3h后冷却到室温；
(5)取出热处理后的块体再将其压实，后放回热处理炉在867℃下保温40h后冷却到室温，经过这样的混合处理后达到Bi-2223单相高温超导体与CoFe2O4磁性纳米颗粒的均匀混合。
本实施例巧妙地利用柠檬酸和乙二醇混合有机凝胶将CoFe2O4磁性纳米颗粒分散开，使CoFe2O4磁性纳米颗粒不团聚后与Bi-2223单相高温超导体混合均匀，再让柠檬酸和乙二醇混合有机凝胶在430℃下保温3h使其完全分解，最后剩下的是Bi-2223单相高温超导体和掺杂均匀的CoFe2O4磁性纳米颗粒。此方法具有操作简单方便，效率高，可控性好及能保证最后获得的是Bi-2223单相高温超导体和CoFe2O4磁性纳米颗粒且已达到均匀混合等优点。
实施例2
如图1所示，一种高温超导材料中均匀地掺杂纳米颗粒的方法，高温超导体是钇系YBa2Cu3O7-y(Y-123)单相高温超导体，工艺流程如下：
(1)按摩尔比为1：2称取柠檬酸和乙二醇，将乙二醇放入玻璃容器中在90℃的水浴中预热后，往水浴中的乙二醇倒入柠檬酸并用磁力搅拌器搅拌15min达到完全互溶，此时再往水浴中的乙二醇和柠檬酸混合物倒入适量的NiFe2O4磁性纳米颗粒持续搅拌30min的时间达到均匀混合，磁力搅拌的转速为900r/min；
(2)将混合均匀的乙二醇、柠檬酸和NiFe2O4磁性纳米颗粒混合物倒进硅胶软模中，再放入鼓风干燥箱在130℃固化12h；
(3)等混合物完全固化后取出，用粉碎机将其粉碎，粉碎的粉末与一定比例的Y-123单相高温超导体粉末均匀混合，再用压片机将其混合物压成块体；
(4)将压好的块体放进热处理炉在430℃下保温3h后冷却到室温；
(5)取出热处理后的块体再将其压实，后放回热处理炉在920℃下保温20h后冷却到室温，经过这样的混合处理后达到Y-123单相高温超导体与NiFe2O4磁性纳米颗粒的均匀混合。
本实施例巧妙地利用柠檬酸和乙二醇混合有机凝胶将NiFe2O4磁性纳米颗粒分散开，使NiFe2O4磁性纳米颗粒不团聚后与Y-123单相高温超导体混合均匀，再让柠檬酸和乙二醇混合有机凝胶在430℃下保温3h使其完全分解，最后剩下的是Y-123单相高温超导体和掺杂均匀的NiFe2O4磁性纳米颗粒。此方法具有操作简单方便，效率高，可控性好及能保证最后获得的依旧是Y-123单相高温超导体和NiFe2O4磁性纳米颗粒且已达到均匀混合等优点。
在高温超导材料中掺杂纳米颗粒一般都是直接将纳米颗粒与高温超导粉末直接混合，没有考虑纳米颗粒会团聚且纳米颗粒的尺寸远小于超导粉末的尺寸，从而导致两者混合不均匀的问题。纳米颗粒与高温超导前驱粉末混合时会发生团聚且由于两者的尺寸相差甚远，两者的混合不可能均匀，进而会影响到高温超导复合材料的临界电流密度。为了获得高临界电流密度的高温超导复合材料，必须避免纳米颗粒的团聚和混合的不均匀性。本发明巧妙地利用柠檬酸和乙二醇混合有机凝胶将纳米颗粒分散开，保证纳米颗粒不团聚，且有机凝胶固化物粉末的尺寸与超导粉末的尺寸相近，从而能使两者均匀地混合，再让柠檬酸和乙二醇混合有机凝胶在430-500℃下保温数个小时使其完全分解，最后剩下的是单相高温超导体和掺杂均匀的纳米颗粒。
背景技术部分引用的参考文献如下：
[1]E.Hannachi,Y.Slimani,F.Ben Azzouz,A.Ekicibil.Higher intra-granularand inter-granular performances of YBCO superconductor with TiO2 nan o-sizedparticles addition,Ceramics International 44(2018)18836-18843.
[2]M.K.Ben,Salem,E.Hannachi,Y.Slimani,A.Hamrita,M.Zouaoui,L.Bessais,M.Ben Salem,F.Ben Azzouz.SiO2 nanoparticles addition effect onmicrostructureand pinning properties in YBa2Cu3Oy,Ceramics International 40(2014)4953-4962.
[3]M.Hafiz,R.Abd-Shukor.Transport critical current density of(Bi1.6Pb0.4)Sr2Ca2Cu3O10/Ag superconductor tapes with addition of nanosizedCoFe2O4,Applied Physics A 120(2015)1573-1578.
[4]N.A.A.Yahya,A.Al-Sharabi,N.R.M.Suib,W.S.Chiu,R.Abd-Shukor.Enhancedtransport critical current density of(Bi,Pb)-2223/Agsuperconducto r tapesadded with nano-sized Bi2O3,Ceramics International 42(2016)18347-18351.
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。
Claims (6)
1.一种在高温超导材料中均匀地掺杂纳米颗粒的方法，其特征在于，步骤为：(1)按一定的比例称取柠檬酸和乙二醇，将乙二醇放入玻璃容器中在70-100℃的恒温水浴或油浴中预热后，往水浴或油浴中的乙二醇倒入柠檬酸并搅拌一定的时间达到完全互溶，形成有机凝胶，此时再往水浴或油浴中的有机凝胶倒入适量的纳米颗粒持续搅拌一定的时间达到均匀混合；
(2)将混合均匀的乙二醇和柠檬酸有机凝胶与纳米颗粒混合物倒进固化模中，再放入鼓风干燥箱在130-150℃固化，固化时间大于8h；
(3)等混合物完全固化后取出，用粉碎机将其粉碎，粉碎的粉末与一定比例的单相高温超导体粉末均匀混合，再用压片机将其混合物压成块体；
(4)将压好的块体放进热处理炉在430-500℃保温数个小时后冷却到室温；
(5)取出热处理后的块体再将其压实，后放回热处理炉在高温超导体烧结温度下烧结一定的时间，经过这样的混合处理后达到高温超导体与纳米颗粒均匀混合。
2.如权利要求1所述的在高温超导材料中均匀地掺杂纳米颗粒的方法，其特征在于，所述步骤(1)中柠檬酸和乙二醇的摩尔比在1：2与1：4的范围之间。
3.如权利要求1所述的在高温超导材料中均匀地掺杂纳米颗粒的方法，其特征在于，所述步骤(1)中采用磁力搅拌器将混合物搅拌均匀。
4.如权利要求1所述的在高温超导材料中均匀地掺杂纳米颗粒的方法，其特征在于，所述步骤(2)中固化模用的是固化后容易将固化物脱模取出且耐130-150℃固化温度的硅胶软模。
5.如权利要求1所述的在高温超导材料中均匀地掺杂纳米颗粒的方法，其特征在于，所述步骤(5)中混合处理后的高温超导体仍是单相高温超导体。
6.如权利要求1所述的在高温超导材料中均匀地掺杂纳米颗粒的方法，其特征在于，当所述步骤(1)中所述纳米颗粒为CoFe2O4磁性纳米颗粒时，所述步骤(5)中单相高温超导体粉末为铋系Bi2-xPbxSr2Ca2Cu3O10+y(Bi-2223)单相高温超导体粉末；
或：当所述步骤(1)中所述纳米颗粒为NiFe2O4磁性纳米颗粒时，所述步骤(5)中单相高温超导体粉末为钇系YBa2Cu3O7-y(Y-123)单相高温超导体粉末。
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Application publication date: 20221223 |