WO2022148214A1 - 在高温超导材料中均匀地掺杂纳米颗粒的方法 - Google Patents

在高温超导材料中均匀地掺杂纳米颗粒的方法 Download PDF

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WO2022148214A1
WO2022148214A1 PCT/CN2021/137694 CN2021137694W WO2022148214A1 WO 2022148214 A1 WO2022148214 A1 WO 2022148214A1 CN 2021137694 W CN2021137694 W CN 2021137694W WO 2022148214 A1 WO2022148214 A1 WO 2022148214A1
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nanoparticles
temperature
ethylene glycol
uniformly
citric acid
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邵玲
陈英伟
赵国盟
柳琦杰
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浙江大学台州研究院
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  • the invention belongs to the technical field of superconducting materials, and particularly relates to a method for uniformly doping nanoparticles in high-temperature superconducting materials.
  • Superconducting materials can be divided into two categories according to the temperature range in which superconductivity occurs: low temperature superconductors in the liquid helium temperature region and high temperature superconductors in the liquid nitrogen temperature region.
  • Low-temperature superconductors are severely limited in practical applications due to their low superconducting transition temperatures and the need for extremely expensive liquid helium to operate.
  • High-temperature superconducting materials are mainly copper oxide ceramic materials. Due to their large anisotropy and low carrier density, their critical current density Jc is low and decreases rapidly with increasing magnetic field. Since they are ceramic materials, it is difficult to form high-quality wires or tapes, which hinders their widespread use.
  • high-temperature superconductors must solve a key problem: increasing the critical current density and the irreversible critical magnetic intensity.
  • the critical current density under high field is lower, which affects the practical application of high temperature superconductors at high temperature (such as 77K) and high magnetic field (such as >4T).
  • One way to improve is to increase the density of flux pinning centers. Introducing dispersed nanoparticles into high-temperature superconducting materials makes them effective magnetic flux pinning centers, thereby effectively increasing the critical current density and irreversible critical magnetic intensity of high-temperature superconducting materials.
  • E.Hannachi et al. [1] incorporated TiO 2 nanoparticles into YBa 2 Cu 3 O y high-temperature superconductors to improve its critical current density; MKBen Salem et al. [2] improved YBa 2 Cu by doping SiO 2 nanoparticles Critical current density of 3 O y high temperature superconductors; M.Hafiz et al. [3] incorporated CoFe 2 O 4 magnetic nanoparticles into (Bi,Pb) 2 Sr 2 Ca 2 Cu 3 O 10 high temperature superconductors to improve its critical current Density; NAAYahya et al.
  • Agglomeration refers to the phenomenon that when the force between material particles is much greater than gravity, the behavior of the particles is no longer bound by gravity, and the phenomenon of aggregation occurs under the influence of the force between particles.
  • the nanoparticles are mixed with the HTS precursor powder, agglomeration will occur, and because the sizes of the two are very different, the mixing of the two cannot be uniform, which will affect the critical current density of the HTS composite material.
  • agglomeration of nanoparticles and inhomogeneity of mixing must be avoided.
  • the purpose of the present invention is to solve the problem of inhomogeneity of doping nanoparticles in high temperature superconducting materials by using a mixture organogel of citric acid (CA) and ethylene glycol (EG).
  • CA citric acid
  • EG ethylene glycol
  • the present invention provides a method for uniformly doping nanoparticles in a high-temperature superconducting material, comprising the following steps:
  • the molar ratio of citric acid and ethylene glycol is in the range of 1:2 and 1:4.
  • a magnetic stirrer is used to stir the mixture uniformly.
  • the curing mold in the step (2) is a soft silicone mold that is easy to demould and take out the cured product after curing and is resistant to a curing temperature of 130-150°C.
  • the high-temperature superconductor after the mixing treatment in the step (5) is still a single-phase high-temperature superconductor.
  • the method for uniformly doping nanoparticles in the high-temperature superconducting material of the present invention skillfully utilizes citric acid and ethylene glycol mixed with organic gel to disperse the nanoparticles, so as to ensure that the nanoparticles do not agglomerate, and the size of the solidified organogel powder is
  • the size of the superconducting powder is similar to that of the superconducting powder, so that the two can be mixed evenly, and then the mixed organogel of citric acid and ethylene glycol is kept at 430-500 ° C for several hours to completely decompose.
  • Phase high temperature superconductors and homogeneously doped nanoparticles This method has the advantages of simple and convenient operation, high efficiency and good controllability.
  • FIG. 1 is a process flow diagram of an embodiment of the present invention.
  • the high-temperature superconductor is a bismuth-based Bi 2-x Pb x Sr 2 Ca 2 Cu 3 O 10+y (Bi-2223) single-phase High temperature superconductor, the process flow is as follows:
  • the CoFe 2 O 4 magnetic nanoparticles are dispersed by cleverly using the mixed organogel of citric acid and ethylene glycol, so that the CoFe 2 O 4 magnetic nanoparticles are not agglomerated and then mixed with the Bi-2223 single-phase high temperature superconductor uniformly.
  • the mixed organogel of citric acid and ethylene glycol was incubated at 430 °C for 3 h to completely decompose, and the last remaining were Bi-2223 single-phase high - temperature superconductors and uniformly doped CoFe2O4 magnetic nanoparticles.
  • This method has the advantages of simple and convenient operation, high efficiency, good controllability, and can ensure that the final obtained Bi-2223 single-phase high temperature superconductor and CoFe 2 O 4 magnetic nanoparticles have achieved uniform mixing and so on.
  • the high-temperature superconductor is a yttrium-based YBa 2 Cu 3 O 7-y (Y-123) single-phase high-temperature superconductor, and the process flow is as follows:
  • the NiFe 2 O 4 magnetic nanoparticles are dispersed by cleverly using the mixed organogel of citric acid and ethylene glycol, so that the NiFe 2 O 4 magnetic nanoparticles are not agglomerated and then mixed with the Y-123 single-phase high temperature superconductor evenly, and then The mixed organogel of citric acid and ethylene glycol was incubated at 430 °C for 3 h to make it completely decomposed, and finally the Y-123 single-phase high-temperature superconductor and uniformly doped NiFe 2 O 4 magnetic nanoparticles were left.
  • This method has the advantages of simple and convenient operation, high efficiency, good controllability, and can ensure that the final obtained Y-123 single-phase high temperature superconductor and NiFe 2 O 4 magnetic nanoparticles have achieved uniform mixing.
  • Doping nanoparticles in high-temperature superconducting materials is generally the direct mixing of nanoparticles and high-temperature superconducting powders, without considering that the nanoparticles will agglomerate and the size of the nanoparticles is much smaller than that of the superconducting powder, resulting in ineffective mixing of the two. Uniform question. When the nanoparticles are mixed with the HTS precursor powder, agglomeration will occur, and because the sizes of the two are very different, the mixing of the two cannot be uniform, which will affect the critical current density of the HTS composite material. In order to obtain high-temperature superconducting composites with high critical current densities, agglomeration of nanoparticles and inhomogeneity of mixing must be avoided.
  • the patent of the present invention cleverly uses the mixed organic gel of citric acid and ethylene glycol to disperse the nanoparticles to ensure that the nanoparticles do not agglomerate, and the size of the solidified organogel powder is similar to the size of the superconducting powder, so that the two After mixing uniformly, the citric acid and ethylene glycol mixed organogel was incubated at 430-500°C for several hours to completely decompose, and finally the single-phase high-temperature superconductor and uniformly doped nanoparticles were left.

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Abstract

本发明是在高温超导材料中均匀地掺杂纳米颗粒的方法，步骤为：(1)将乙二醇放入玻璃容器中在70-100℃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达到完全互溶，再往水浴或油浴中的乙二醇和柠檬酸混合物倒入纳米颗粒持续搅拌达到均匀混合；(2)将混合物倒进固化模中；(3)等混合物完全固化后取出，用粉碎机粉碎，粉碎的粉末与一定比例的单相高温超导体粉末均匀混合，再压成块体；(4)将块体放进热处理炉保温数个小时后冷却到室温；(5)取出块体后放回热处理炉在高温超导体烧结温度下热处理一定的时间，达到高温超导体与纳米颗粒均匀混合，并且高温超导体仍是单相高温超导体。本发明操作简单方便，效率高，可控性好。

Description

在高温超导材料中均匀地掺杂纳米颗粒的方法 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大大的限制。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J c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。提高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YBa 2Cu 3O y高温超导体中掺入TiO 2纳米颗粒来提高其临界电流密度；M.K.Ben Salem等人 [2]通过掺入SiO 2纳米颗粒来提高YBa 2Cu 3O y高温超导体的临界电流密度；M.Hafiz等人 [3]在(Bi,Pb) 2Sr 2Ca 2Cu 3O 10高温超导体中掺入CoFe 2O 4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Bi 2O 3纳米颗粒来提高Bi 1.6Pb 0.4Sr 2Ca 2Cu 3O 10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BaCeO 3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BaCeO 3纳米颗粒直接加入Y 1.8Ba 2.4Cu 3.4O y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(citric acid，CA)和乙二醇(ethylene glycol，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，包括如下步骤：
(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，此时再往水浴或油浴中的乙二醇和柠檬酸混合物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、柠檬酸和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℃下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热处理一定的时间，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。
进一步地，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。
进一步地，所述步骤(1)中采用磁力搅拌器将混合物搅拌均匀。
进一步地，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。
进一步地，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。
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Bi 2-xPb xSr 2Ca 2Cu 3O 10+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CoFe 2O 4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CoFe 2O 4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CoFe 2O 4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CoFe 2O 4磁性纳米颗粒分散开，使CoFe 2O 4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CoFe 2O 4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CoFe 2O 4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YBa 2Cu 3O 7-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NiFe 2O 4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NiFe 2O 4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NiFe 2O 4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NiFe 2O 4磁性纳米颗粒分散开，使NiFe 2O 4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NiFe 2O 4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NiFe 2O 4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。本发明专利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-granular and inter-granular performances of YBCO superconductor with TiO 2nano-sized particles 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.SiO2nanoparticles addition effect on microstructure and 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 nanosized CoFe2O4,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.Enhanced transport critical current density of(Bi,Pb)-2223/Ag superconductor tapes added with nano-sized Bi 2O 3,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 (5)

  1. 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，包括如下步骤：(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，此时再往水浴或油浴中的乙二醇和柠檬酸混合物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、柠檬酸和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℃下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热处理一定的时间，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。
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