CN106431403A - Preparation method of yttrium-barium-copper-oxide superconductive block doped with nano bismuth ferrite - Google Patents

Preparation method of yttrium-barium-copper-oxide superconductive block doped with nano bismuth ferrite Download PDF

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CN106431403A
CN106431403A CN201610904234.8A CN201610904234A CN106431403A CN 106431403 A CN106431403 A CN 106431403A CN 201610904234 A CN201610904234 A CN 201610904234A CN 106431403 A CN106431403 A CN 106431403A
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李国政
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天津师范大学
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Abstract

The invention discloses a preparation method of a yttrium-barium-copper-oxide superconductive block doped with nano bismuth ferrite. The preparation method comprises the following steps of preparing mixed powder, pressing a precursor block, assembling the precursor block, carrying out high-temperature heat treatment and carrying out oxygen-permeation treatment. The preparation method disclosed by the invention has the advantages that nano bismuth-ferrite particles are doped in a solid-phase block, grow after high-temperature melting, liquid-phase permeation and slow cooling, Y2Ba4CuBiOx phase is generated in the yttrium-barium-copper-oxide superconductive block as a second-phase particle, so that delta1-type pinning is improved; in addition, elemental substitution of Fe for the Cu site of YBa2Cu3O7-delta phase is initiated, so that the component fluctuation and weak superconductive areas in a superconductive matrix are caused, the delta Tc-type pinning of a sample is improved and finally better superconductive performance is obtained.

Description

一种纳米铁酸铋掺杂的钇钡铜氧超导块材的制备方法 Method for preparing bismuth nanoscale iron-doped YBCO superconductor material

技术领域 FIELD

[0001] 本发明属于高温铜氧化物超导材料技术领域,具体涉及到一种纳米铁酸铋掺杂的钇钡铜氧超导块材的制备方法。 [0001] The present invention belongs to the technical field of high-temperature superconducting cuprate material, particularly to a method for preparing nanoscale iron bismuth doped YBCO superconductor material.

背景技术 Background technique

[0002]由于在液氮温区(77K)具有更强的磁通钉扎能力及在高场下能保持更高的临界电流密度(J。),钇钡铜氧(Y-Ba-Cu-O)高温超导材料及其应用技术一直是国际上高新技术材料与高新技术应用研究领域中的热点之一。 [0002] Since a stronger magnetic flux pinning ability liquid nitrogen temperature (77K) and at high field can maintain a higher critical current density (J.), YBCO (Y-Ba-Cu- O) high-temperature superconducting material and its application technology has been one of the hot high-tech materials and applied research in the international high-tech fields. 然而,当高温超导体在液氮温区工作时,内部会出现因热激活而产生的磁通蠕动,从而导致超导性能(如捕获磁通、磁悬浮力等)随时间衰减严重的问题。 However, when working in high-temperature superconductors at liquid nitrogen temperature, the interior will be activated flux creep due to the generated heat, thereby causing the superconducting properties (e.g., capture flux, magnetic force, etc.) attenuation serious problems over time. 因此,向超导体内引入更有效的磁通钉扎中心以保证其性能稳定性对提高超导材料的实用价值、扩大超导体的应用规模至关重要。 Therefore, the introduction of more effective magnetic flux pinning centers into the superconductor in order to ensure the stability of its performance to improve practical superconducting materials, superconductor applications is essential to expand the scale.

[0003] 在高温超导体中,存在两种主要的磁通钉扎机制,一种是由非超导的正常芯(如绝缘的第二相内含粒子)引起的幻型钉扎,另一种是由超导基体中化学成分波动引起的<5TC型钉扎。 [0003] In the high-temperature superconductors, there are two major flux pinning mechanisms, phantom-nail one is caused by the normal non-superconducting core (e.g., a second phase containing insulating particles) bar, another a superconducting matrix chemical composition fluctuations <5TC type pinning. 在我们的前期工作中,发明了一种由粉末熔化-液相渗透组合方式制备纳米复合钇钡铜氧超导块材的方法(201510339626.X),通过使用Y2O3纳米粉与Ba0、Cu0、Ce02初始粉的混合物压制固相块在样品内成功引入纳米级的Y2BaCu05粒子,获得了较好的性能(直径16mm的样品,磁悬浮力为24.48N)。 In our previous work, invented a powder from the melt - Liquid permeability nanocomposite YBCO superconducting bulk method (201510339626.X) combination, by using a nano-powder and Y2O3 Ba0, Cu0, Ce02 the initial powder mixture was compressed solid block Y2BaCu05 successfully introduced nanoscale particles within a sample, to obtain a better performance (16mm diameter sample, levitation force is 24.48N). 而且该方法无需使用任何前驱粉,实现了直接利用市场购置的初始材料制备超导块材的最简化工艺,具有极大潜力。 And the method without using any precursor powder prepared in a simplified process to achieve the most direct use of superconductor material a commercially available starting material, has great potential. 在此基础上,我们仍有必要进一步发明新的方法向超导体内引入新的第二相粒子或组分起伏,以进一步提高材料的性能和实用价值。 On this basis, we still need a new method of the invention further introduction of new second phase particles or undulations superconductor component, to further improve performance and practical material.

发明内容 SUMMARY

[0004] 本发明所要解决的技术问题在于提供一种能在超导基体中引入更有效的磁通钉扎中心从而进一步提尚样品超导性能的、纳米铁酸秘惨杂的乾锁铜氧超导块材的制备方法。 [0004] The present invention solves the technical problem is to provide a more effective introduction of pinning centers in the superconducting base body is still further improved so that the superconducting properties of samples, nano ferrite secret lock miserable heteroaryl dry oxygen copper preparation superconductor material.

[0005] 解决上述技术问题所采用的技术方案由下述步骤组成: [0005] Problem to solve the above technical solution consisting of the steps:

(1)配制混合粉: (1) Preparation of mixed powder:

将平均粒径50nm的Y2O3纳米粉与Ba0、Cu0初始粉按摩尔比为I: I: I的比例混合,同时添加0.5%〜I.5% (w/w)的CeO2初始粉和0.1%〜0.3% (w/w)的、粒径介于50nm_200nm的BiFeO3纳米粉,混合均勾,作为固相混合粉;将平均粒径50nm的Y2O3纳米粉与Ba0、Cu0初始粉按摩尔比为1:10:16的比例混合均匀,作为液相混合粉;其中所用BiFeO3纳米粉由溶胶-凝胶方法制得(参见参考文南犬:Novel electrical conductivity properties in Ca-doped BiFe〇3nanoparticles, J.Nanopart.Res.(2015) 17:209); The average particle diameter of 50nm and Y2O3 nanopowder Ba0, Cu0 starting powder in a molar ratio I: I: I ratio of mixing, while adding 0.5% ~I.5% (w / w) of the initial powder and CeO2 - 0.1% 0.3% (w / w), the particle size of between 50nm_200nm BiFeO3 nano powder, are mixed hook, a mixed powder as a solid phase; 50nm average particle size of Y2O3 powder and nano Ba0, Cu0 starting powder in a molar ratio 1: the mixed ratio of 10:16, a mixed powder as a liquid phase; wherein BiFeO3 nanopowder used by the sol - gel method was prepared (see Venant dogs: Novel electrical conductivity properties in Ca-doped BiFe〇3nanoparticles, J.Nanopart. . Res (2015) 17: 209);

(2)压制前驱块: (2) compression block precursors:

取固相混合粉放入圆柱型模具I中,压制成固相块;取液相混合粉放入圆柱型模具2中,压制成液相块;其中所用固相混合粉与液相混合粉的质量比为1:2.5〜3.5,圆柱型模具2的直径为比圆柱型模具I大1mm;再取Yb2O3初始粉放入圆柱型模具2中,压制成厚约2mm的薄片,作为支撑块; Take the solid mixed powder into a cylindrical mold I, and compressed into a solid mass; take liquid into the mixed powder in a cylindrical mold 2, the liquid pressed into blocks; wherein the solid phase with the liquid phase mixed powder mixing powder mass ratio of 1: 2.5~3.5, the diameter of the cylinder mold 2 to mold than I large cylindrical 1mm; Yb2O3 then take an initial powder into a cylindrical mold 2, pressed into a sheet of 2mm thickness, a support block;

(3)装配前驱块: (3) mounting the precursor block:

将液相块、固相块自下而上依次同轴放置在支撑块的正上方,再将一块钕钡铜氧籽晶置于固相块的上表面中心位置,完成前驱块的装配;其中所用钕钡铜氧籽晶为从多畴钕钡铜氧块材上解理下的晶片(参见参考文献:Infiltrat1n growth of Mg-doped Nd-Ba-Cu-0 seed crystals for the fabricat1n of large grain RE-Ba-Cu-O bulksuperconductors , Supercond.Sc1.Technol.(2013) 26:055019),其尺寸约为3mmX3mmX 1.5mm; The liquid phase mass, in this order from the solid phase block coaxially disposed immediately above the support block, and then a seed crystal neodymium barium copper oxide disposed on the surface of the solid phase center position of the block, to complete the assembly of the precursor block; wherein the neodymium barium copper oxide seed from the multi-domain neodymium barium copper oxide bulk wafer (see references in cleavage: Infiltrat1n growth of Mg-doped Nd-Ba-Cu-0 seed crystals for the fabricat1n of large grain RE -Ba-Cu-O bulksuperconductors, Supercond.Sc1.Technol (2013) 26: 055019), which is about the size 3mmX3mmX 1.5mm;.

(4)高温热处理: (4) high-temperature heat treatment:

将装配好的前驱块放在Al2O3垫片上,中间隔以5个等高的MgO单晶粒,然后整体放入井式炉中,以每小时3000C的升温速率升温至800〜900°C,保温5〜15小时;再以每小时60°C的升温速率升温至1030〜10400C,保温0.5〜1.5小时;然后以每小时60°C的降温速率降温至1000〜1010 °C,再以每小时0.2〜0.5 °C的降温速率慢冷至970〜980 V,随炉冷却至室温,得到钇钡铜氧单畴块材; The assembled blocks on the Al2O3 precursor pad, the contour interval 5 of MgO single crystal, and the whole was placed in a pit furnace, at a ramp rate of 3000C per hour, warmed to 800~900 ° C, incubated 5~15 hours; then heating rate of 60 ° C per hour, warmed to 1030~10400C, incubated 0.5~1.5 hours; then cooled to 1000~1010 ° C at a cooling rate of 60 ° C per hour, and then hourly 0.2~0.5 ° C the cooling rate slowly cooled to 970~980 V, furnace cooling to room temperature, YBCO single domain block material;

(5)渗氧处理: (5) oxygen diffusion process:

将钇钡铜氧单畴块材放入石英管式炉中,在流通氧气气氛中,450 °C-400 °C的温区中慢冷200小时,得到钇钡铜氧超导块材。 The YBCO single domain block material into a quartz tube furnace in an oxygen atmosphere in the flow, temperature area 450 ° C-400 ° C in the slow cooling for 200 hours to obtain YBCO superconductor material.

[0006] 在本发明的配制混合粉步骤⑴中,将Y2O3纳米粉与Ba0、Cu0初始粉按摩尔比为1:1:1的比例混合,最佳添加l%(w/w)的Ce02初始粉和0.2%(w/w)的BiFe03纳米粉;在压制前驱块步骤(2)中,所用固相混合粉与液相混合粉的最佳质量比为1:3;在高温热处理步骤(4)中,最佳以每小时300°C的升温速率升温至850 °C,保温10小时;再以每小时60 °C的升温速率升温至1035°C,保温I小时;然后以每小时600C的降温速率降温至1005°C,再以每小时0.33°C的降温速率慢冷至975°C,随炉冷却至室温,得到钇钡铜氧单畴块材。 [0006] In step ⑴ mixed powder formulation of the present invention, nano powder and the Y2O3 Ba0, Cu0 starting powder in a molar ratio 1: 1: 1 mixing ratio, the optimum addition l% (w / w) of the initial Ce02 powder and 0.2% (w / w) of BiFe03 nanopowder; best quality pressing block precursors in step (2), the solid-liquid mixed powder and mixed powder with a ratio of 1: 3; the high temperature heat treatment step (4 ), the optimum heating temperature rising rate of 300 ° C per hour to 850 ° C, held for 10 hours; then heated at a heating rate of 60 ° C per hour to 1035 ° C, incubated I hour; then at 600C per hour cooling rate cooling to 1005 ° C, and then at a cooling rate of 0.33 ° C per hour, slowly cooled to 975 ° C, the furnace was cooled to room temperature to obtain a monodomain YBCO bulk.

[0007] 本发明公开的纳米铁酸铋掺杂的钇钡铜氧超导块材的制备方法与现有技术相比所具有的积极效果在于: [0007] nanoscale iron bismuth doping of the present invention disclosed a method for preparing YBCO superconductor material it has positive effects as compared with the prior art in that:

本发明采用粉末熔化-液相渗透方式制备纳米铁酸铋掺杂的钇钡铜氧超导块材,通过在固相块中掺杂铁酸铋纳米粒子,经过高温熔化、液相渗透及慢冷生长后,在钇钡铜氧超导块材内一方面生成Y2Ba4CuB1x相作为新的第二相粒子,提高了W型钉扎;另一方面引发Fe对YBa2Cu3O7-S相Cu位的元素替代,从而在超导基体中出现组分起伏和弱超导区,提高了样品的<5T。 The present invention uses powder melts - liquid permeable manner to the preparation of nanoscale iron bismuth doped YBCO superconducting bulk material, through an iron-doped bismuth nanoparticles solid block, high temperature melting, liquid penetration and slow after cooling the growth of, on the one hand to generate in a superconducting YBCO Y2Ba4CuB1x bulk phase as a new second phase particles, the W-type pinning improved; on the other hand lead to YBa2Cu3O7-S phase Fe Cu element substitution position, fluctuation component which appears in the superconducting region and weak superconducting matrix, improved sample <5T. 型钉扎,最终获得了更优越的超导性能。 Pinning type, ultimately superior superconducting properties. 此外,整个制备过程无需使用任何前驱粉,工艺简单高效。 In addition, the whole preparation process without using any precursor powder, simple and efficient process. 本发明也可用于制备纳米铁酸铋掺杂的Nd、Sm、Gd等其他系列的超导块材。 The present invention may also be used to prepare nanoscale iron bismuth doped Nd, Sm, Gd, and other series of superconductor material.

[0008] [0008]

附图说明: BRIEF DESCRIPTION OF:

图1是实施例1制备的0.1%纳米BiFeO3掺杂的钇钡铜氧超导块材的表面形貌图; FIG 1 is a surface topography doped YBCO superconducting bulk material prepared in Example 1 0.1% nano BiFeO3 embodiment;

图2是实施例1制备的0.1%纳米BiFeO3掺杂的钇钡铜氧超导块材的磁悬浮力曲线; FIG 2 is a 0.1% BiFeO3 levitation force curve nano-doped YBCO superconducting bulk material prepared according to Example 1;

图3是实施例2制备的0.2%纳米BiFeO3掺杂的钇钡铜氧超导块材的表面形貌图; Example 3 is 0.2% nano BiFeO3 surface topography doped YBCO superconductor material 2 is prepared;

图4是实施例2制备的0.2%纳米BiFeO3掺杂的钇钡铜氧超导块材的磁悬浮力曲线; FIG 4 is a nano-2 0.2% BiFeO3 levitation force doped YBCO superconducting bulk material prepared according to Example curves;

图5是实施例3制备的0.3%纳米BiFeO3掺杂的钇钡铜氧超导块材的表面形貌图; 图6是实施例3制备的0.3%纳米BiFeO3掺杂的钇钡铜氧超导块材的磁悬浮力曲线; FIG 5 is a surface topography doped YBCO superconducting bulk material prepared in Example 3 0.3% nanometer BiFeO3 embodiment; FIG. 6 is a 0.3% nano BiFeO3 doped YBCO superconducting prepared in Example 3 Embodiment levitation force curve block material;

图7是实施例4制备的5%纳米BiFeO3掺杂的钇钡铜氧超导块材的表面形貌图; FIG. 7 is a surface topography doped YBCO superconducting bulk material prepared in Example 45% nano BiFeO3 embodiment;

图8是实施例4制备的5%纳米BiFeO3掺杂的钇钡铜氧超导块材的XRD图谱。 8 is an XRD pattern of Example 5% nano 4 BiFeO3 doped YBCO superconductor material produced.

具体实施方式 Detailed ways

[0009] 下面结合附图和实施例对本发明进一步详细说明,但本发明不限于这些实施例。 [0009] The following embodiments of the present invention is described in further detail in conjunction with the accompanying drawings and embodiments, but the present invention is not limited to these embodiments. 其中所用到的纳米Υ2θ3 (平均粒径50nm)、Yb2O3、CeO2、BaO和CuO化学原料均有市售。 Wherein the nanoparticles used Υ2θ3 (average particle diameter 50nm), Yb2O3, CeO2, BaO and CuO chemical materials are commercially available. 所用到的纳米別? The use of nano do? 603由溶胶-凝胶方法制得(参见参考文献:Novel electrical conductivityproperties in Ca-doped BiFe〇3 nanoparticles, J.Nanopart.Res.(2015) 17:209),其粒径介于50nm-200nm。 603 by the sol - gel method was prepared (see reference: Novel electrical conductivityproperties in Ca-doped BiFe〇3 nanoparticles, J.Nanopart.Res (2015) 17: 209.), A particle size of between 50nm-200nm. 所用到的钕钡铜氧籽晶为从多畴钕钡铜氧块材上解理下的晶片(参见参考文献:Inf iltrat1n growth of Mg-doped Nd-Ba-Cu-O seed crystalsfor the fabricat1n of large grain RE-Ba-Cu-O bulk superconductors,Supercond.Sc1.Technol.(2013) 26:055019),其尺寸约为3mmX3mmX 1.5mm。 The use of neodymium barium copper oxide seed from the multi-domain neodymium barium copper oxide bulk wafer under the cleavage (see reference: Inf iltrat1n growth of Mg-doped Nd-Ba-Cu-O seed crystalsfor the fabricat1n of large grain RE-Ba-Cu-O bulk superconductors, Supercond.Sc1.Technol (2013) 26:. 055019), which is about the size 3mmX3mmX 1.5mm.

[0010] 实施例1 [0010] Example 1

(1)配制混合粉: (1) Preparation of mixed powder:

取49.2302g Y2O3纳米粉与33.4276g Ba0、17.3422g CuO初始粉混合,同时添加Ig CeO2初始粉和0.1g BiFeO3纳米粉,S卩Y2O3纳米粉与Ba0、Cu0初始粉的摩尔比为1: 1: 1,同时添加1% (w/w)的Ce02初始粉和0.1% (w/w)的BiFe03纳米粉,混合均勾,作为固相混合粉;取7.4481gY2O3纳米粉与50.5727g BaO,41.9792g CuO初始粉混合均匀,即Y2O3纳米粉与Ba0、Cu0初始粉的摩尔比为1:10:16,作为液相混合粉; Take 49.2302g Y2O3 nano powder is mixed with the starting powder 33.4276g Ba0,17.3422g CuO, while adding an initial Ig CeO2 powder and nano-powder 0.1g BiFeO3, S Jie Y2O3 powder and nano Ba0, the molar ratio of the initial Cu0 powder is 1: 1: 1, while adding 1% (w / w) of the initial Ce02 powder and 0.1% (w / w) of BiFe03 nano powder, are mixed hook, a mixed powder as a solid phase; take 7.4481gY2O3 nanopowders and 50.5727g BaO, 41.9792g CuO mixed starting powder, i.e. powder and Y2O3 nano BaO, the molar ratio of the initial Cu0 to 1:10:16 powder, a mixed powder as a liquid phase;

(2)压制前驱块: (2) compression block precursors:

取5g固相混合粉放入圆柱型模具I (直径16mm)中,压制成固相块;取15g液相混合粉放入圆柱型模具2 (直径26_)中,压制成液相块;即所用固相混合粉与液相混合粉的质量比为1: 3,圆柱型模具2的直径为比圆柱型模具I大1mm;再取3g Yb2O3初始粉放入圆柱型模具2(直径26mm)中,压制成厚约2mm的薄片,作为支撑块; 5g of mixed powder into a solid cylindrical mold I (diameter 16mm) and compressed into a solid mass; mixed powder into a liquid phase takes 15g cylindrical mold 2 (26_ diameter), the compressed block into a liquid phase; i.e., used mass ratio of the solid phase and liquid phase mixed powder mixing powder of 1: 3, the diameter of the cylinder mold 2 to be larger than the cylindrical mold I 1mm; 3g Yb2O3 then take an initial powder into a cylindrical mold 2 (diameter 26mm), the pressed into a sheet of 2mm thickness, a support block;

(3)装配前驱块: (3) mounting the precursor block:

将液相块、固相块自下而上依次同轴放置在支撑块的正上方,再将一块钕钡铜氧籽晶置于固相块的上表面中心位置,完成前驱块的装配; The liquid phase block, a block in this order from the solid phase support block disposed coaxially immediately above, and then a neodymium barium copper oxide seed was placed on a solid surface of the central position of the block, to complete the assembly of the precursor block;

(4)高温热处理: (4) high-temperature heat treatment:

将装配好的前驱块放在Al2O3垫片上,中间隔以5个等高的MgO单晶粒,然后整体放入井式炉中,以每小时300°C的升温速率升温至850°C,保温10小时;再以每小时60°C的升温速率升温至1035°C,保温I小时;然后以每小时600C的降温速率降温至1005°C,再以每小时0.33°C的降温速率慢冷至975°C,随炉冷却至室温,得到钇钡铜氧单畴块材; The assembled blocks on the Al2O3 precursor pad, the contour interval 5 of MgO single crystal, and the whole was placed in a pit furnace, at a heating rate of 300 ° C per hour temperature increase to 850 ° C, incubated for 10 hours; then heated at a heating rate of 60 ° C per hour to 1035 ° C, incubated I hour; then at a cooling rate of 600C per hour, cooled to 1005 ° C, and then cooling at a rate of 0.33 per hour, slowly cooled ° C. to 975 ° C, the furnace was cooled to room temperature to obtain YBCO single domain block material;

(5)渗氧处理: (5) oxygen diffusion process:

将钇钡铜氧单畴块材放入石英管式炉中,在流通氧气气氛中,450 °C-400 °C的温区中慢冷200小时,得到0.1%纳米BiFeO3掺杂的钇钡铜氧超导块材。 The YBCO single domain block material into a quartz tube furnace in an oxygen atmosphere in the flow, temperature area 450 ° C-400 ° C in the slow cooling for 200 hours to give 0.1% nano-doped yttrium-barium-copper BiFeO3 oxide superconductor material.

[0011] 所制备的0.1%纳米BiFeO3掺杂的钇钡铜氧超导块材,用照相机拍摄表面形貌,照片如图1所示。 [0011] 0.1% nano BiFeO3 doped YBCO superconductor material produced, with a surface morphology imaging camera photograph shown in Fig. 由图可见,样品表面四径清楚,无自发成核现象,但样品生长区并未长满整个上表面,说明BiFeO3掺杂会引起YBCO晶体生长速率的下降。 Seen from the figure, four sample surface diameter clarity, no spontaneous nucleation, but the growth region not covered with the sample on the entire surface, causes a reduction described BiFeO3 doped YBCO crystal growth rate.

[0012] 应用三维磁场与磁力测试装置对制备的0.1%纳米BiFeO3掺杂的钇钡铜氧超导块材在液氮温度下进行磁悬浮力性能的测试,结果如图2所示。 [0012] Application of the three-dimensional magnetic field measuring apparatus to 0.1% BiFeO3 prepared nano-doped YBCO superconducting bulk mechanical properties of the test magnetic levitation at liquid nitrogen temperature, the results shown in FIG. 由图可见,样品的最大磁悬浮力为28.37N,高于未掺杂样品(24.48N)。 Seen from the figure, the maximum magnetic floating force sample was 28.37N, higher than the non-doped sample (24.48N).

[0013] 实施例2 [0013] Example 2

在配制混合粉步骤(I)中,取49.2302g Y2O3纳米粉与33.4276g Ba0、17.3422g CuO初始粉混合,同时添加Ig &02初始粉和0.2g BiFeO3纳米粉,即Y2O3纳米粉与BaO、CuO初始粉的摩尔比为1:1: I,同时添加1%(w/w)的0602初始粉和0.2%&/\¥)的BiFe03纳米粉,混合均勾,作为固相混合粉;取7.4481g Y2O3纳米粉与50.5727g Ba0、41.9792g CuO初始粉混合均匀,即Y2O3纳米粉与Ba0、Cu0初始粉的摩尔比为I: 10:16,作为液相混合粉; In the mixed powder prepared in step (I), the initial take 49.2302g Y2O3 powder nano powder mixed with 33.4276g Ba0,17.3422g CuO, while adding Ig & 02 starting powder and 0.2g BiFeO3 nano powder, i.e. powder and Y2O3 nano BaO, CuO initial molar ratio of powder is 1: 1: I, while adding 1% (w / w) of the initial powder and 0602 0.2% & / \ ¥) of BiFe03 nano powder, are mixed hook, a mixed powder as a solid phase; take 7.4481g nano Y2O3 powder mixed starting powder with uniform 50.5727g Ba0,41.9792g CuO, Y2O3 i.e. nano powder and BaO, the molar ratio of the initial Cu0 powder is I: 10:16, a mixed powder as a liquid phase;

其他步骤与实施例1相同。 Other steps are the same as in Example 1. 制备得到0.2%纳米BiFeO3掺杂的钇钡铜氧超导块材。 0.2% nano prepared YBCO superconductor material BiFeO3 doped.

[0014] 所制备的0.2%纳米BiFeO3掺杂的钇钡铜氧超导块材,用照相机拍摄表面形貌,照片如图3所示。 [0014] 0.2% of the prepared nano BiFeO3 doped YBCO superconducting bulk material, surface topography captured by the camera, the photo shown in FIG. 由图可见,样品的生长区尺寸进一步变小,说明随着掺杂量的增加,YBCO晶体的生长速率进一步下降。 Seen from the figure, the size of the growth area of ​​the sample is further reduced, the amount of doping increases the description, YBCO crystal growth rate is further lowered.

[0015] 应用三维磁场与磁力测试装置对制备的0.2%纳米BiFeO3掺杂的钇钡铜氧超导块材在液氮温度下进行磁悬浮力性能的测试,结果如图4所示。 [0015] Application of the three-dimensional magnetic field measuring apparatus to 0.2% BiFeO3 prepared nano-doped YBCO superconducting bulk mechanical properties of the test magnetic levitation at liquid nitrogen temperature, the results shown in FIG. 由图可见,样品的最大磁悬浮力为31.33N,高于0.1%纳米BiFeO3掺杂的样品(28.37N)。 Seen from the figure, the maximum magnetic floating force sample was 31.33N, nano sample than 0.1% (28.37N) BiFeO3 doped.

[0016] 实施例3 [0016] Example 3

在配制混合粉步骤(I)中,取49.2302g Y2O3纳米粉与33.4276g Ba0、17.3422g CuO初始粉混合,同时添加Ig &02初始粉和0.3g BiFeO3纳米粉,即Y2O3纳米粉与BaO、CuO初始粉的摩尔比为1:1: I,同时添加1%(w/w)的0602初始粉和0.3%&/\¥)的BiFe03纳米粉,混合均勾,作为固相混合粉;取7.4481g Y2O3纳米粉与50.5727g Ba0、41.9792g CuO初始粉混合均匀,即Y2O3纳米粉与Ba0、Cu0初始粉的摩尔比为I: 10:16,作为液相混合粉; In the mixed powder prepared in step (I), the initial take 49.2302g Y2O3 powder nano powder mixed with 33.4276g Ba0,17.3422g CuO, while adding Ig & 02 starting powder and 0.3g BiFeO3 nano powder, i.e. powder and Y2O3 nano BaO, CuO initial molar ratio of powder is 1: 1: I, while adding 1% (w / w) of the initial powder and 0602 0.3% & / \ ¥) of BiFe03 nano powder, are mixed hook, a mixed powder as a solid phase; take 7.4481g nano Y2O3 powder mixed starting powder with uniform 50.5727g Ba0,41.9792g CuO, Y2O3 i.e. nano powder and BaO, the molar ratio of the initial Cu0 powder is I: 10:16, a mixed powder as a liquid phase;

其他步骤与实施例1相同。 Other steps are the same as in Example 1. 制备得到0.3%纳米BiFeO3掺杂的钇钡铜氧超导块材。 0.3% nano prepared YBCO superconductor material BiFeO3 doped.

[0017] 所制备的0.3%纳米BiFeO3掺杂的钇钡铜氧超导块材,用照相机拍摄表面形貌,照片如图5所示。 [0017] 0.3% nano BiFeO3 doped YBCO superconductor material produced, with a surface morphology imaging camera photographs shown in FIG. 由图可见,样品的生长区尺寸进一步变小,说明随着掺杂量的增加,YBCO晶体的生长速率进一步下降。 Seen from the figure, the size of the growth area of ​​the sample is further reduced, the amount of doping increases the description, YBCO crystal growth rate is further lowered.

[0018] 应用三维磁场与磁力测试装置对制备的0.3%纳米BiFeO3掺杂的钇钡铜氧超导块材在液氮温度下进行磁悬浮力性能的测试,结果如图6所示。 [0018] Application of the three-dimensional magnetic field measuring apparatus to 0.3% BiFeO3 prepared nano-doped YBCO superconducting bulk mechanical properties of the test magnetic levitation at liquid nitrogen temperature, the results shown in Fig. 由图可见,样品的最大磁悬浮力为23.16N,低于0.2%纳米BiFeO3掺杂的样品(31.33N),也低于未掺杂样品(24.48N)。 Seen from the figure, the maximum magnetic floating force sample was 23.16N, less than 0.2% nanometer-doped samples BiFeO3 (31.33N), lower than the undoped sample (24.48N). 这说明BiFeO3掺杂引发的钇钡铜氧单畴生长区尺寸减小开始使得块材性能下降。 This indicates that the initiator BiFeO3 doped YBCO growth region single domain size reduction such that the block material degradation began.

[0019] 实施例4 [0019] Example 4

为了明确纳米BiFeO3与钇钡铜氧体系的高温反应机制及其在样品内的最终存在方式,我们又制备了一个高掺杂量(5%)的样品,并利用XRD衍射仪对其进行物相分析。 In order to clarify the reaction mechanism of the high-temperature nano BiFeO3 YBCO system and its existence in the final samples, the we have a high doping (5%) of the samples were prepared and subjected to diffraction by XRD Phase analysis. 制备方法如下: It was prepared as follows:

在配制混合粉步骤(I)中,取49.2302g Y2O3纳米粉与33.4276g Ba0、17.3422g CuO初始粉混合,同时添加Ig &02初始粉和5g BiFeO3纳米粉,即Y2O3纳米粉与BaO、CuO初始粉的摩尔比为1:1: I,同时添加l%(w/w)的[602初始粉和5%&/\¥)的BiFe03纳米粉,混合均勾,作为固相混合粉;取7.4481g Y2O3纳米粉与50.5727g Ba0、41.9792g CuO初始粉混合均匀,SPY2O3纳米粉与Ba0、Cu0初始粉的摩尔比为I: 10:16,作为液相混合粉; 其他步骤与实施例1相同。 In the mixed powder prepared in step (I), the initial take 49.2302g Y2O3 powder nano powder mixed with 33.4276g Ba0,17.3422g CuO, while adding Ig & 02 starting powder and 5g BiFeO3 nano powder, i.e. powder and Y2O3 nano BaO, CuO starting powder molar ratio of 1: 1: I, while adding l% (w / w) of [602 starting powder and 5% & / \ ¥) of BiFe03 nano powder, are mixed hook, a mixed powder as a solid phase; take 7.4481g nano Y2O3 powder was mixed with the initial powder evenly 50.5727g Ba0,41.9792g CuO, the molar ratio of SPY2O3 nanopowders with Ba0, Cu0 initial powder is I: 10:16, a mixed powder as a liquid phase; the other steps are the same as in Example 1. 制备得到5%纳米BiFeO3掺杂的钇钡铜氧超导块材。 Preparation of a 5% nano YBCO superconductor material BiFeO3 doped.

[0020] 所制备的5%纳米BiFeO3掺杂的钇钡铜氧超导块材,用照相机拍摄表面形貌,照片如图7所示。 [0020] 5% of the prepared nano BiFeO3 doped YBCO superconducting bulk material, surface topography captured by the camera, the photo shown in Fig. 由图可见,样品仅在中心位置生长了一个尺寸约7mmX 7mm的单畴区,且样品边缘出现明显随机成核现象。 Seen from the figure, the sample grown only a single domain size of about 7mmX 7mm region at the center position, and the edge of the sample apparently random nucleation occurs.

[0021] 将样品中间的小生长区切割下来,用玛瑙研钵碾碎,然后进行XRD测试,结果如图8所示。 [0021] The intermediate region of small sample growth excised, crushed in an agate mortar and then subjected to XRD measurement results as shown in FIG. 由图可见,样品中YBa2Cu3O7-S (Y-123)超导相是主相,还包含了一定数量的Y2BaCuO5(Y-211)相,代表了在基体中捕获的Y-211粒子。 Seen from the figure, the sample YBa2Cu3O7-S (Y-123) superconducting phase is the main phase, but also contains a certain amount of Y2BaCuO5 (Y-211) phase, represents Y-211 particles trapped in the matrix. 然而,掺杂进去的BiFeO3相并没有发现,说明它已经在高温下分解转化了。 However, doping into the BiFeO3 phase was not found, it is already at the pyrolysis conversion. XRD结果同时表明,样品内出现了相当数量的Y2Ba4CuB i Ox(YB1-2411)相,这是由Bi元素在YB⑶体系内自发生成的,可以作为新的第二相粒子充当磁通钉扎中心,提高样品的型钉扎。 XRD results also show that there has been a considerable number of Y2Ba4CuB i Ox (YB1-2411) relative to the sample, which is an element of Bi in the YB⑶ system spontaneously, as a new second phase particles act as pinning centers, the increased sample type pinning. 然而并没有发现含有Fe元素的物相,说明Fe已进入YBCO的晶格中,以元素替代的形式占据Cu位,这会在超导基体中引发组分起伏和弱超导区,提高样品的<5T。 However, and it found no phase elements containing Fe, Fe is described into the crystal lattice of YBCO, an alternative form of elemental Cu occupies bits, which will lead to fluctuations and weak superconducting component in a superconducting matrix area, increase the sample <5T. 型钉扎。 -Type pinning.

[0022] 实施例5 [0022] Example 5

在配制混合粉步骤(I)中,取49.2302g Y2O3纳米粉与33.4276g Ba0、17.3422g CuO初始粉混合,同时添加0.5g CeO2初始粉和0.2g BiFeO3纳米粉,S卩Y2O3纳米粉与BaO、CuO初始粉的摩尔比为1:1: I,同时添加0.5% (w/w)的Ce02初始粉和0.2% (w/w)的BiFe03纳米粉,混合均匀,作为固相混合粉;取7.4481g Y2O3纳米粉与50.5727g Ba0、41.9792g CuO初始粉混合均匀,即Y2O3纳米粉与Ba0、Cu0初始粉的摩尔比为1:10:16,作为液相混合粉; In the mixed powder prepared in step (I), the initial take 49.2302g Y2O3 powder nano powder mixed with 33.4276g Ba0,17.3422g CuO, while adding 0.5g CeO2 starting powder and nano-powder 0.2g BiFeO3, S Jie nano Y2O3 powder and BaO, molar ratio of CuO starting powder is 1: 1: I, while adding 0.5% (w / w) of Ce02 initial powder and 0.2% (w / w) of BiFe03 nano powder, mixed, as the solid phase a mixed powder; take 7.4481 G nano Y2O3 powder mixed starting powder with uniform 50.5727g Ba0,41.9792g CuO, Y2O3 i.e. nano powder and BaO, the molar ratio of the initial Cu0 to 1:10:16 powder, a mixed powder as a liquid phase;

在压制前驱块步骤(2)中,取5g固相混合粉放入圆柱型模具I (直径16mm)中,压制成固相块;取12.5g液相混合粉放入圆柱型模具2(直径26mm)中,压制成液相块;即所用固相混合粉与液相混合粉的质量比为1:2.5,圆柱型模具2的直径为比圆柱型模具I大1mm;再取3gYb2O3初始粉放入圆柱型模具2 (直径26mm)中,压制成厚约2mm的薄片,作为支撑块。 Pressing the precursor block in step (2), 5g of mixed powder into a solid cylindrical mold I (diameter 16mm) and compressed into a solid mass; 12.5g liquid taken into the cylindrical mold powder mix 2 (diameter 26mm ), the compressed block into a liquid phase; i.e., the mass ratio of the solid phase of the mixed powder and a liquid phase mixed powder is 1: 2.5, diameter of the cylinder mold 2 is larger than the cylindrical mold I 1mm; then take an initial powder into 3gYb2O3 2 cylindrical mold (diameter 26mm), pressed into a sheet of 2mm thickness, a support block.

[0023] 在高温热处理步骤(4)中,将装配好的前驱块放在Al2O3垫片上,中间隔以5个等高的MgO单晶粒,然后整体放入井式炉中,以每小时300°C的升温速率升温至800°C,保温15小时;再以每小时60°C的升温速率升温至1030°C,保温1.5小时;然后以每小时60°(:的降温速率降温至1000 °C,再以每小时0.5 0C的降温速率慢冷至970 °C,随炉冷却至室温,得到钇钡铜氧单畴块材。 [0023] In the high temperature heat treatment step (4) in the assembled blocks on the Al2O3 precursor pad, the contour interval 5 of MgO single crystal, and the whole was placed in a pit furnace, per hour heating rate to 300 ° C temperature was raised to 800 ° C, incubated for 15 hours; then heated at a heating rate of 60 ° C per hour to 1030 ° C, incubated for 1.5 hours; then 60 h ° (: cooling the cooling rate to 1000 ° C, and then at a cooling rate of 0.5 0C per hour, slowly cooled to 970 ° C, the furnace was cooled to room temperature to obtain a monodomain YBCO bulk.

[0024] 其他步骤与实施例1相同。 [0024] Other steps are the same as in Example 1. 制备得到0.2%纳米BiFeO3掺杂的钇钡铜氧超导块材。 0.2% nano prepared YBCO superconductor material BiFeO3 doped.

[0025] 实施例6 [0025] Example 6

在配制混合粉步骤(I)中,取49.2302g Y2O3纳米粉与33.4276g Ba0、17.3422g CuO初始粉混合,同时添加1.5g CeO2初始粉和0.2g BiFeO3纳米粉,S卩Y2O3纳米粉与BaO、CuO初始粉的摩尔比为1:1: I,同时添加1.5% (w/w)的Ce02初始粉和0.2% (w/w)的BiFe03纳米粉,混合均匀,作为固相混合粉;取7.4481g Y2O3纳米粉与50.5727g Ba0、41.9792g CuO初始粉混合均匀,即Y2O3纳米粉与Ba0、Cu0初始粉的摩尔比为1:10:16,作为液相混合粉; In the mixed powder prepared in step (I), the initial take 49.2302g Y2O3 powder nano powder mixed with 33.4276g Ba0,17.3422g CuO, while adding 1.5g CeO2 starting powder and nano-powder 0.2g BiFeO3, S Jie nano Y2O3 powder and BaO, molar ratio of CuO starting powder is 1: 1: I, while adding 1.5% (w / w) of Ce02 initial powder and 0.2% (w / w) of BiFe03 nano powder, mixed, as the solid phase a mixed powder; take 7.4481 G nano Y2O3 powder mixed starting powder with uniform 50.5727g Ba0,41.9792g CuO, Y2O3 i.e. nano powder and BaO, the molar ratio of the initial Cu0 to 1:10:16 powder, a mixed powder as a liquid phase;

在压制前驱块步骤(2)中,取5g固相混合粉放入圆柱型模具I (直径16mm)中,压制成固相块;取17.5g液相混合粉放入圆柱型模具2(直径26mm)中,压制成液相块;即所用固相混合粉与液相混合粉的质量比为1:3.5,圆柱型模具2的直径为比圆柱型模具I大1mm;再取3gYb2O3初始粉放入圆柱型模具2 (直径26mm)中,压制成厚约2mm的薄片,作为支撑块。 Pressing the precursor block in step (2), 5g of mixed powder into a solid cylindrical mold I (diameter 16mm) and compressed into a solid mass; 17.5g liquid taken into the cylindrical mold powder mix 2 (diameter 26mm ), the compressed block into a liquid phase; i.e., the mass ratio of the solid phase of the mixed powder and a liquid phase mixed powder is 1: 3.5, diameter of the cylinder mold 2 is larger than the cylindrical mold I 1mm; then take an initial powder into 3gYb2O3 2 cylindrical mold (diameter 26mm), pressed into a sheet of 2mm thickness, a support block.

[0026] 在高温热处理步骤(4)中,将装配好的前驱块放在Al2O3垫片上,中间隔以5个等高的MgO单晶粒,然后整体放入井式炉中,以每小时300°C的升温速率升温至900°C,保温5小时;再以每小时60°C的升温速率升温至1040°C,保温0.5小时;然后以每小时60°(:的降温速率降温至11 °C,再以每小时0.2 °C的降温速率慢冷至980 °C,随炉冷却至室温,得到钇钡铜氧单畴块材。 [0026] In the high temperature heat treatment step (4) in the assembled blocks on the Al2O3 precursor pad, the contour interval 5 of MgO single crystal, and the whole was placed in a pit furnace, per hour heating rate to 300 ° C temperature was raised to 900 ° C, and incubated for 5 hours; then heated at a heating rate of 60 ° C per hour to 1040 ° C, for 0.5 hours; then 60 h ° (: cooling rate was lowered to 11 ° C, and then at a cooling rate of 0.2 ° C per hour, slowly cooled to 980 ° C, the furnace was cooled to room temperature to obtain a monodomain YBCO bulk.

[0027] 其他步骤与实施例1相同。 [0027] Other steps are the same as in Example 1. 制备得到0.2%纳米BiFeO3掺杂的钇钡铜氧超导块材。 0.2% nano prepared YBCO superconductor material BiFeO3 doped.

Claims (2)

1.一种纳米铁酸铋掺杂的钇钡铜氧超导块材的制备方法,其特征在于它由下述步骤组成: (1)配制混合粉: 将平均粒径50nm的Y2O3纳米粉与BaO、CuO初始粉按摩尔比为1:1:1的比例混合,同时添加0.5%〜I.5% (w/w)的CeO2初始粉和0.1%〜0.3%(w/w)的、粒径介于50nm_200nm的BiFeO3纳米粉,混合均勾,作为固相混合粉;将平均粒径50nm的Y2O3纳米粉与Ba0、Cu0初始粉按摩尔比为1:10:16的比例混合均匀,作为液相混合粉;其中所用BiFeO3纳米粉由溶胶-凝胶方法制得; (2)压制前驱块: 取固相混合粉放入圆柱型模具I中,压制成固相块;取液相混合粉放入圆柱型模具2中,压制成液相块;其中所用固相混合粉与液相混合粉的质量比为1:2.5〜3.5,圆柱型模具2的直径为比圆柱型模具I大1mm;再取Yb2O3初始粉放入圆柱型模具2中,压制成厚约2mm的薄片,作为支撑块; (3)装配前驱块: 将液相块、固相块自下而上依次 1. A method for preparing nano YBCO superconductor material doped bismuth ferrate, characterized in that it consists of the following steps: (1) Preparation of mixed powder: average particle diameter of 50nm Y2O3 powder and nano 1:: BaO, CuO powder initial molar ratio of 1 to 1 ratio, while adding 0.5% ~I.5% (w / w) of the initial powder and CeO2 0.1% ~0.3% (w / w) of particles diameter of between 50nm_200nm BiFeO3 nano powder, are mixed hook, a mixed powder as a solid phase; 50nm average particle size of Y2O3 powder and nano Ba0, Cu0 starting powder according to the molar ratio of 1:10:16 mixed as solution mixed powder; BiFeO3 nanopowder wherein the sol - gel was prepared; (2) compression block precursors: take the solid mixed powder into a cylindrical mold I, and compressed into a solid mass; liquid mixed powder takes place 2 into the cylindrical mold and compressed into block phase; wherein the solid mass of mixed powder and mixed powder with a liquid ratio of 1: 2.5~3.5, diameter of the cylinder mold 2 is larger than the cylindrical mold I 1mm; then take initial Yb2O3 powder into a cylindrical mold 2, pressed into a sheet of 2mm thickness, a support block; (3) mounting the precursor block: block the liquid phase, the solid phase block bottom to top 轴放置在支撑块的正上方,再将一块钕钡铜氧籽晶置于固相块的上表面中心位置,完成前驱块的装配;其中所用钕钡铜氧籽晶为从多畴钕钡铜氧块材上解理下的晶片,其尺寸约为3mmX3mmX 1.5mm; (4)高温热处理: 将装配好的前驱块放在Al2O3垫片上,中间隔以5个等高的MgO单晶粒,然后整体放入井式炉中,以每小时3000C的升温速率升温至800〜900°C,保温5〜15小时;再以每小时60°C的升温速率升温至1030〜10400C,保温0.5〜1.5小时;然后以每小时60°C的降温速率降温至1000〜1010 °C,再以每小时0.2〜0.5 °C的降温速率慢冷至970〜980 V,随炉冷却至室温,得到钇钡铜氧单畴块材; (5)渗氧处理: 将钇钡铜氧单畴块材放入石英管式炉中,在流通氧气气氛中,450°C-400 °C的温区中慢冷200小时,得到钇钡铜氧超导块材。 Immediately above the spindle in the support block, and then a seed crystal neodymium barium copper oxide disposed on the surface of the solid phase center position of the block, to complete the assembly of the precursor block; barium neodymium oxide seed Cu is used wherein the multi-domain neodymium barium copper cleaving the wafer in the bulk oxygen, which is about the size 3mmX3mmX 1.5mm; (4) high-temperature heat treatment: the assembled blocks on the Al2O3 precursor pad, the contour interval 5 of MgO single crystal, and the whole was placed in a pit furnace, at a ramp rate of 3000C per hour, warmed to 800~900 ° C, incubated 5~15 hours; 1030~10400C then heated to a temperature increase rate of 60 ° C per hour, holding 0.5~1.5 h; and then decreasing rate of 60 ° C per hour to cool to 1000~1010 ° C, and then at a cooling rate of 0.2~0.5 ° C per hour, slowly cooled to 970~980 V, furnace cooling to room temperature, YBCO oxygen single domain block material; (5) an oxygen permeability of treatment: YBCO single domain block material into a quartz tube furnace in an oxygen atmosphere in the flow, temperature area 450 ° C-400 ° C in 200 slowly cooled hours, to give YBCO superconductor material.
2.权利要求1所述的纳米铁酸铋掺杂的钇钡铜氧超导块材的制备方法,其特征在于:在配制混合粉步骤⑴中,将Y2O3纳米粉与Ba0、Cu0初始粉按摩尔比为1:1:1的比例混合,同时添加1% (w/w)的Ce02初始粉和0.2% (w/w)的BiFe03纳米粉,混合均勾,作为固相混合粉;在压制前驱块步骤(2)中,所用固相混合粉与液相混合粉的质量比为1:3;在高温热处理步骤(4)中,将装配好的前驱块放在Al2O3垫片上,中间隔以5个等高的MgO单晶粒,然后整体放入井式炉中,以每小时300°C的升温速率升温至850°C,保温10小时;再以每小时60°C的升温速率升温至1035°C,保温I小时;然后以每小时600C的降温速率降温至1005°C,再以每小时0.33°C的降温速率慢冷至975°C,随炉冷却至室温,得到钇钡铜氧单畴块材。 Bismuth nanoscale iron according to claim 1 of the production method of doped YBCO superconducting bulk material, characterized in that: in the formulating step ⑴ mixed powder, the powder and Y2O3 nano Ba0, Cu0 starting powder massage Seoul ratio of 1: 1: 1 ratio, while adding 1% (w / w) of Ce02 initial powder and 0.2% (w / w) of BiFe03 nano powder, mixing both hook, as a solid phase mixed powder; in press step precursor block (2), the mass ratio of the solid-liquid mixed phase is mixed with flour powder is 1: 3; the high temperature heat treatment step (4) in the assembled blocks on the Al2O3 precursor spacer, the spacer 5 to the high MgO single crystal, and the whole was placed in a pit furnace, at a heating rate of 300 ° C per hour temperature increase to 850 ° C, held for 10 hours; then at a heating rate of temperature rise of 60 ° C per hour to 1035 ° C, incubated I hour; then at a cooling rate of 600C per hour, cooled to 1005 ° C, and then at a cooling rate of 0.33 ° C per hour, slowly cooled to 975 ° C, the furnace was cooled to room temperature to obtain YBCO single domain bulk oxygen.
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CN1340216A (en) * 1999-02-17 2002-03-13 索尔瓦钡/锶有限公司 Superconductive bodies made of zinc-doped copper oxide material
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