降温速率对Ag-SmBCO单畴生长中自发成核的影响

在前期的研究中曾通过Ag掺杂降低Sm123/Sm211体系熔点,利用Nd123冷籽晶技术成功制备出具有理想织构的SmBCO/Ag单畴块材.但在实验结果中发现相比于未掺杂坯体,掺入Ag后的SmBCO坯体生长速率下降,在所考察的慢冷温区里,生长速率呈不断减小趋势,最终因自发成核而无法继续生长,使得SmBCO单畴区域局限于15×15mm2范围内.为了抑制单畴生长中的自发成核现象,本文研究了降温速率对SmBCO/Ag单畴自发成核的影响.在两组不同条件下的降温速率实验中发现,不同的降温速率对体系自发成核的抑制效果是不同的.利用降低降温速率,成功地将掺Ag SmBCO单畴面积从15×15mm2增大至26×26mm2.     

Ag掺杂SmBCO熔融织构单畴生长工艺研究

通过Ag掺杂降低Sm123/Sm211体系熔点,利用Nd123冷籽品技术成功制备出具有理想织构的smBCO/Ag单畴块材.研究了smBco/Ag单畴的生长过程,结果发现,相比于未掺杂坯体,掺入Ag后的smBcO坯体生长速率下降,在所考察的慢冷温区里,生长速率呈不断减小趋势,最终因自发成核而无法继续生长.实验还发现,SmBCO/Ag 单畴生长温度窗口随Ag掺量增加向低温区平移.对样品剖面的观察发现,在最高熔化温度保温阶段大量气体未能排出SmBcO/Ag坯体,这些气体在单畴慢冷生长过程中不断向外侧迁移、合并形成宏观可见的孔洞.在单畴生长过程中,这些位于生长前沿的高密度气孔,一定程度上影响了液相和sm3+离子向生长前沿的供应,是单畴生长速率较低的可能原因.微结构分析表明熔融生长过程中Sm211粒子发生二次晶粒长大现象,长大后的Sm211粒子提供Sm3+离子的能力减弱,导致慢冷生长后期阶段生长速率呈下降趋势.     

多籽晶技术生长大尺寸YBCO单畴超导块材的研究

本文利用多籽晶技术成功地生长出直径53mm的大尺寸YBCO单畴超导块材.与传统的单籽晶引导生长相比,该多籽晶技术在大尺寸YBCO单畴生长方面更有效.通过同时使用四个SmBCO籽晶引导生长,大尺寸YB-CO单畴的生长时间得以缩减.实验结果显示多籽晶生长的大尺寸YBCO单畴块材比传统的单籽晶生长的同尺寸块材在超导性能上有所提高.磁通俘获场测量显示多籽晶样品的磁通俘获场比单籽晶样品的峰值更高,均匀性更好.在77K零场冷的环境下,多籽晶的磁悬浮力密度可达到14.6N/cm2,相比单籽晶的12.5N/cm2的磁悬浮力密度有了很大的提高.     

单畴熔融织构YBCO/Ag样品的生长工艺研究

本文研究了用冷籽晶技术制备掺Ag单畴熔融织构YBCO超导块材的工艺.通过引入有效的隔离层避免了籽晶的熔化.使用纯Y1.8粉作为隔离层的材料,并探索出同时施加两个隔离层的方法.对施加隔离层后大块单畴YBCO/Ag样品生长窗口的研究发现,加入隔离层后使慢降温上限温度升高,970℃到955℃是Y123/Ag系单畴生长的主要窗口.制备的直径26mm单畴超导块材的磁浮性能已达到12N/cm2(77K,0.5T).认为如果进一步提高熔化温度或延长保温时间将有助于抑制自发成核.     

最高熔化温度对GdBaCuO单畴块材生长及磁悬浮性能的影响

采用熔融织构生长工艺结合冷籽晶法,通过调整最高熔化温度,成功制备出直径53mm的GdBCO单畴超导块材.不同高温下淬火坯体的XRD图谱表明,提高最高熔化温度对Gd123相的充分熔解和大单畴的生长具有重要意义.最高熔化温度对块材的磁悬浮性能有重要影响,最高温度偏低不利于熔体中气体排出,制成的单畴存在大量孔洞,使磁悬浮力下降;适当提高最高熔化温度,可减少单畴内部的孔洞,使材料致密从而提高磁悬浮力.     

不同厚度的Nd123片层的2-2复合籽晶对SmBCO样品生长的影响

采用MgO单晶与NdBa2Cu3O7-δ(Nd123)粉体的2-2复合体籽晶可以充分利用MgO与NdBCO籽晶的优势,对SmBCO晶体的生长起到了很好的诱导作用,成功制备出单畴SmBCO超导块材.本文采用不同厚度的Nd123片层和MgO单晶作为2-2复合体籽晶通过顶部籽晶熔渗生长工艺(TSIG)制备SmBCO超导块材,研究了Nd123片层的厚度对SmBCO样品生长的影响.结果表明,随着Nd123片层厚度的增加,样品的单畴形貌逐渐消失,并且出现了随机成核.通过对样品的生长特性和微观结构的研究,阐明了不同厚度的Nd123片层对SmBCO晶体生长形貌的影响机制.     

单畴GdBaCuO块材生长工艺研究

在空气气氛中采用冷籽晶熔融织构工艺进行了单畴GdBaCuO块材生长.通过调整Gd123相与Gd211相配比的方法控制GdBaCuO块材的成分.为抑制稀土元素对钡位的替代,添加了低熔点的BaCuO2.探索了采用熔融织构工艺在空气条件下生长单畴GdBaCuO块材的工艺条件,找到了适合单畴GdBaCuO在空气气氛下生长的工艺制度.已成功生长出直径25mm左右的单畴样品.探索了单畴GdBaCuO块材的氧处理制度,并对生长出来的单畴GdBaCuO块材进行了性能测试及微观结构观察.样品的零电阻温度达到了94K,不可逆场比钇钡铜氧要高出很多.磁浮力密度达到了12N/cm2.     

直径53 mm熔融织构单畴YBCO块材制备研究

实验表明:通过对Y123/Y211前驱粉体粒度的调整以及采用Y123∶Y211=1∶0.3摩尔比的配制方案,在顶部籽晶诱导熔融织构生长条件下,可以提高单畴YBCO块材的起始生长温度Ts,从而有效地抑制了大尺寸单畴高温超导块材生长过程中的非籽晶成核现象. 利用这一技术,我们成功地生长出多块直径53 mm、厚18mm单畴YBCO高温超导块材,其中最大磁浮力达到302牛顿,最小为274牛顿,平均磁浮力密度达到12.9 N/cm2(77K、0.55T),达到和超过了该类材料的实用化国际标准.从宏观形貌上看,样品沿径向呈完全织构生长状态,沿轴向也基本呈完全生长状态. XRD和极图分析结果显示,整块样品具有较理想的织构化程度.这一结果意味着近期有望实现更大直径单畴YBCO超导块材的织构生长.     

MgO粒子掺杂对NdBCO超导块材熔化温度的影响

采用改进后的顶部籽晶熔渗生长(RE+011 TSIG) 工艺, 通过在固相先驱粉中掺杂不同含量的 MgO 来有效地提高 NdBCO 籽晶的熔化温度, 从而成功地制备出直径为32 mm 的大尺寸单畴 SmBCO 超导块材. 结果表明,MgO 的掺杂对 NdBCO 超导块材的熔化温度有着明显的提高, 随着固相先驱粉中 MgO 掺杂量的增加, Mg2 + 离子逐渐进入到 Nd123 相的晶格中, 当掺杂量达到16 wt% 时呈现出饱和状态, 且 NdBCO 超导块材的熔化温度提高近18 ℃ , 可有效地抑制在制备SmBCO 超导块材的过程中出现的 NdBCO 籽晶熔化现象.     

钇钡铜氧单畴超导块的多籽晶制备方法

顶部籽晶技术与熔融织构生长工艺的结合已经被证明是制备单一晶体取向的YBaCuO单畴超导体的成功方法.由于YBaCuO晶体的生长速度慢,使大尺寸单畴超导快的制备受到限制.采用多籽晶的方法可以减少生长大块材料的时间,但多籽晶诱导生长的大晶粒的边界通常是弱耦合的,材料的磁浮力和冻结磁场性能明显低于单籽晶生长的材料.本研究在采用多籽晶法制备YBCuO超导块时,通过在先驱物坯料的顶部增加成分梯度过渡层的方法成功地生长出单畴结构的超导材料.冻结磁通的分布为单峰状,证实材料为单畴结构,其磁浮力也达到单籽晶样品的水平.这些结果表明成分梯度层和多籽晶结合的工艺可以改善多籽晶生长样品的晶界耦合,是生长大尺寸单畴超导材料的一种可行方法.     

Growth and investigation of SmBCO/Ag single grain bulk for batch production of Sm123 seed crystals

Using NdBa₂Cu₃O_y (Nd123) bulk material as a seed, we report a success in the melt-textured growth of SmBCO/Ag bulks by cold-seeding melt-growth process. Very well-textured single domain bulks of SmBCO with 5 wt% Ag₂O addition can be fabricated reproducibly under ambient atmosphere. Microstructure analysis of the obtained SmBCO/Ag bulk sample reveals that no silver particle is trapped within the mono-domain region, where the peritectic decomposition temperature goes back to the one of the Ag-free SmBCO sample. This c-axis oriented mono-domain region can be easily separated into a large amount of Sm123 seeds. Therefore, a new approach to preparation of Sm123 seed crystals in high quantity and quality can be achieved in an uncomplicated way, which exhibits significant advantage in comparison with the conventional method for Sm123 seed fabrication by MgO cold-seeding process. Experimental results show that a batch of well-textured YBCO bulks has been grown successfully by using these new Sm123 seed crystals.     

Batch-processed GdBCO–Ag bulk superconductors fabricated using generic seeds with high trapped fields

Large, single grains of Y–Ba–Cu–O (YBCO) have been batch-processed to date by the top seeded melt growth (TSMG) process using NdBCO or SmBCO seed crystals. It has proved difficult, however, to economically batch-process light rare earth (LRE) LRE–Ba–Cu–O bulk high temperature superconductors, which have higher critical current densities and irreversibility fields than YBCO, and therefore greater potential for high field engineering applications. In this paper, we report a novel batch-process based on a cheap, readily available generic seed crystal, developed recently at Cambridge, and a TSMG melt processing technique based on cold seeding in air for the batch fabrication of Gd–Ba–Cu–O–Ag single grains. The superconducting properties of the (LRE)BCO single grains fabricated by this process are, in all respects, equivalent to those processed more conventionally in a reduced oxygen atmosphere.     

Study on single domain growth of Ag-doped Sm–Ba–Cu–O bulk using cold seeding technique

Attempts to prepare single grain SmBCO/Ag using NdBa₂Cu₃O_7?δ (Nd123) cold seeding technique have been performed. As silver decreases the melting temperature of SmBa₂Cu₃O_7?δ (Sm123) to approximately 1028 °C, it becomes possible to texture SmBCO/Ag samples with the Nd123 cold seeding technique, and very well textured mono-domain crystals with 15 mm on a side have been successfully obtained. However, the growth rate of SmBCO/Ag system is severely reduced compared with Ag free sample. A series of samples quenched at various lower limit temperatures of slow-cooling process were fabricated to investigate the single domain growth of SmBCO/Ag system. It is found that mono-domain growth exhibits a suppressed tendency within the slow-cooling temperature window considered, and then is hindered significantly by the spontaneous nucleation. The transversal slides of these samples show that large amount of entrapped gas did not escape from the samples during the dwell time at the maximum superheating temperature. During the slow-cooling process, the entrapped gas continued to move towards the edges of the samples, coalesced with each other and very large pores several millimeters in size were formed, which finally were released from the sample. The SEM analysis reveals that the coarsening of Sm₂BaCuO₅ (Sm211) precipitates has occurred during the growth of mono-domain. Large Sm211 cause decreased ability to supply samarium for the growth of Sm123 crystal, resulting in a gradual decrease in the growth rate.     

Recycling process for 123-type bulk superconductors

Bulk (RE)-Ba-Cu-O (RE is a rare earth element or yttrium) high temperature superconductors have contained a lot of precious substances such as Ag and Pt, which led to a significant increase in production cost. However, the bulk superconductors have been thrown away once they were fractured during characterization or failed to grow in the form of single grain. The material recycling of these samples is, therefore, a great important and leads to a cost-effective production. Hence we have attempted a recycling process for Ag-doped Gd-Ba-Cu-O (GdBCO/Ag) bulk samples. The single grain GdBCO/Ag bulk sample, however, could not be grown by the cold-seeded melt-process albeit the recycled precursor powder is chemically identical to a mixture of commercial powder (reference powder). On the other hand, the hot-seeding technique enables us to fabricate readily the single grain GdBCO/Ag bulk samples even with employing the recycled precursor powder. The recycle-processed GdBCO/Ag bulk sample showed a 10% decrease in the trapped magnetic field compared with the reference bulk sample. However, most importantly this study demonstrates clearly, and for the first time, that the recycling of GdBCO/Ag bulk samples is possible, nevertheless a small degradation of superconducting properties is recognized.     

BaO掺杂对单畴GdBCO超导块材性能的影响(二)

为了有效地抑制Gd BCO超导块材在生长过程中出现的Gd/Ba替换现象,在前期工作的基础上,本文采用顶部籽晶熔渗生长工艺,通过在固相先驱粉中添加不同含量的Ba O粒子成功地制备出了一系列高性能的单畴Gd BCO超导块材,并且对样品的微观形貌以及临界电流密度进行了研究和分析.结果表明,随着BaO掺杂量的增加,样品中的Gd_(1+x)Ba_(2-x)Cu_3O_(7-δ)固溶体(Gd123ss)相呈现出减少的趋势,并生成了纳米量级的Gd123ss,这对GdBCO超导样品中存在的Gd/Ba替换起到了很好的抑制作用,使得样品中的GdBa_2Cu_3O_(7-δ)(Gd123)超导相有所增加;同时当样品中BaO的添加量在2 wt%—4 wt%之间时,样品的临界电流密度在一定程度上得到了有效提高.     

掺银氧化锌纳米棒的水热法制备研究

利用水热法在直流磁控溅射制备的掺铝氧化锌 (AZO) 种子层上制备了不同形貌和光学性能的掺银ZnO纳米棒, 并采用XRD、扫描电镜、透射谱、光发射谱和EDS谱详细研究了Ag离子与Zn离子的摩尔百分比 (R_Ag/Zn) 及AZO种子层对掺银ZnO纳米棒的结构和光学性质的影响. 随着R_Ag/Zn的增加, 掺银ZnO 纳米棒的微结构和光学性质的变化与银掺杂诱导的纳米棒的端面尺寸变化有关. 平均端面尺寸的变化归结于种子层颗粒大小和颗粒数密度不同导致掺入的Ag离子的相对比例不同. 溅射15 min的AZO种子层上生长的ZnO纳米棒由于缺陷增多导致在可见光区的发光峰明显强于溅射10 min 的AZO种子层上、相同R_Ag/Zn 条件下生长的ZnO纳米棒. Ag掺杂产生的点缺陷增多导致可见光区PL波包较宽. 纯ZnO纳米棒的微结构与种子层厚度导致的结晶度和颗粒大小有关. 关键词： ZnO纳米棒 水热法 Ag掺杂 直流磁控溅射     

Ag-doped ZnO nanorods synthesized by two-step method

A two-step method is adopted to synthesize Ag-doped ZnO nanorods.A ZnO seed layer is first prepared on a glass substrate by thermal decomposition of zinc acetate.Ag-doped ZnO nanorods are then assembled on the ZnO seed layer using the hydrothermal method.The influences of the molar percentage of Ag ions to Zn ions(RAg/Zn) on the structural and optical properties of the ZnO nanorods obtained are carefully studied using X-ray diffractometry,scanning electron microscopy and spectrophotometry.Results indicate that Ag ions enter into the crystal lattice through the substitution of Zn ions.The<002>c-axis-preferred orientation of the ZnO nanorods decreases as RAg/Zn increases.At RAg/Zn >1.0%,ZnO nanorods lose their c-axis-preferred orientation and generate Ag precipitates from the ZnO crystal lattice.The average transmissivity in the visible region first increases and then decreases as R Ag/Zn increases.The absorption edge is first blue shifted and then red shifted.The influence of Ag doping on the average head face,and axial dimensions of the ZnO nanorods may be optimized to improve the average transmissivity at RAg/Zn <1.0%.