Bi系超导相形成的化学动力学研究

用化学动力学探讨了Bi系超导相形成的机理,提出反应活化能是控制超导相形成的关键因素。在纯Bi系2223名义成份下,2212相的形成满足“晶核形成生长”自催化动力学模型,其动力学方程为α_(2212)=1—exp(—k_(2212)t~(2.5))。2223相的形成较好地符合“收缩晶核界面”反应模型,动力学方程为1—(1—α_(2223))~(1/3)=k_(2223)t。以0.35molPb替代Bi后,2212相形成的动力学规律没有本质改变,但是2223相的形成表现出区域反应的自催化效应,其相应的动力学方 关键词：     

Bi系超导体高T_c相的形成机制

本文研究Bi系超导体高Tc(2223)相的形成机制。提出Bi系氧化物超导体高Tc相的形成过程是:首先Sr-Ca-Cu氧化物(Ca_(0.85)Sr_(0.15)CuO_2)与低Tc(2212)相反应形成高Tc相的核,然后样品内2223相核通过象结晶学中晶体生长那样的方式长大成2223相晶粒。2223相成核过程中Sr-Ca-Cu氧化物的形成途径有两条:一条是通过固相反应从Ca_2CuO_3和SrCaCu_5O_8的平衡中形成;另一条是通过液相反应从2212相,Ca_2PbO_4和CuO之间的反应直接形成。固相反应的速度远小于液相反应的速度,从而2223相核的形成速度在液相反应下得到加快。通过高Tc相的形成机制,提出Pb对Bi系超导体高Tc相形成的作用是:它只加速2223相的成核,而对2223相的成长不起作用。最后利用2223相形成机制,烧制出具有织构的样品。     

Bi-2223/Ag超导带HT1降温工艺与Ic关系研究

热处理工艺对于Bi-2223/Ag超导带性能具有决定性作用,热处理过程中不适当的处理温度、保温时间以及在特定温区内不合适的升降温速率,都会导致Bi-2223/Ag带超导性能的降低.本文研究了在2223相基本生成之后第一次热处理(HT1)降温过程中影响临界电流Ic的温度范围和降温速率.实验证明,HT1 的降温过程对Ic有着不可忽视的影响.在800℃～200℃范围内任何附加的保温都会使Ic降低,其中尤以710℃～350℃严重.在此温度范围内,于21%O2分压气氛下,当2223相成相率为～80%时,小于70℃/h的降温速率将使Ic明显下降.XRD的结果发现,较高Ic样品总是含有相对含量为1.8%左右的2212相,在Ic较低的样品中却没有发现2212相,只是3221相稍多.SEM揭示:HT1后经附加热处理的样品中,2223相微裂纹增多,所析出的CuOy尺寸增大而且分布不均匀,这些都造成2223相的连接性变差,使Ic降低.     

Bi系高温超导体中2212相和2223相的性质分析

本文对 Bi 系中可能存在一种 T_c>100K 的2212相作了进一步的论证.化学分析显示普通的2212相中 Cu~(3+)含量为～10%,而2223相和 T_c>100K 的2212相中 Cu~(3+)的含量却大于30%.从 DTA-TG 实验中观察到普通2212相和2223相失去晶格氧的量为0.8%,而含 T_c>100K 的2212相的样品失去晶格氧的量为～2%,说明这种2212相受氧含量影响更大.文中还介绍了一种简易判断样品中是否存在2223相和普通2212相的经验方法.     

Bi-2223／Ag超导带HT1降温工艺与Ic关系研究

热处理工艺对于Bi-2223／Ag超导带性能具有决定性作用，热处理过程中不适当的处理温度、保温时间以及在特定温区内不合适的升降温速率，都会导致Bi-2223／Ag带超导性能的降低．本文研究了在2223相基本生成之后第一次热处理（HT1）降温过程中影响临界电流Ic的温度范围和降温速率．实验证明，HT1的降温过程对Ic有着不可忽视的影响．在800℃～200℃范围内任何附加的保温都会使Ic降低，其中尤以710℃～350℃严重．在此温度范围内，于21％O2分压气氛下，当2223相成相率为～80％时，小于70℃／h的降温速率将使Ic明显下降．XRD的结果发现，较高Ic样品总是含有相对含量为1．8％左右的2212相，在Ic较低的样品中却没有发现2212相，只是3221相稍多．SEM揭示：HT1后经附加热处理的样品中，2223相微裂纹增多，所析出的CuOy尺寸增大而且分布不均匀，这些都造成2223相的连接性变差，使Ic降低．     

含铅铋系2223相成相规律的研究

本文通过X射线衍射、超导电性测量、差热分析、电镜等手段对块材Bi系超导体组元的挥发、组成、烧结温度、烧结时间、临界温度T_c与2223相的形成等进行了研究。结果表明:当烧结温度小于910℃时,除Pb外其他组元的挥发没有被观测到。制备2223相的最佳配料组成是Bi_(1.70)Pb_(0.30)Sr_2Ca_2Cu_3O_x,烧结温度在830—845℃之间,烧结时间大于72小时。低于825℃样品中主超导相为2212,高于860℃,2223相难以被观测到,而2201相含量相对增多。依照本文的工艺成功地合成出2223相含量大于90％,T_c近110K,均匀性很好的块材超导体。     

Bi系超导体高Tc相的形成机制

本文研究Bi系超导体高T_c(2223)相的形成机制。提出Bi系氧化物超导体高T_c相的形成过程是:首先Sr-Ca-Cu氧化物(Ca_0.85Sr_0.15CuO₂)与低T_c(2212)相反应形成高T_c相的核,然后样品内2223相核通过象结晶学中晶体生长那样的方式长大成2223相晶粒。2223相成核过程中Sr-Ca-Cu氧化物的形成途径有两条:一条是通过固相反应 关键词：     

T1系单相超导材料的高氧压合成及压力对超导性的影响

 系统地研究了在0~3 MPa氧压下T1系超导材料的制备过程及其超导性质。结果表明：0.25~0.90 MPa氧压下所制备的样品为纯2223相，T_c0最高可达125.3 K；1.45~3.00 MPa氧压下样品为纯2212相，T_c0在95~100 K之间；0.90~1.45 MPa氧压下样品为2223及2212两相共存。对两种单相样品的高压研究结果表明，2223相样品比2212相样品有着较强的压力效应，在0~0.52 GPa压力下分别为4.0 K/GPa及2.0 K/GPa。     

热处理条件对双粉工艺中Bi-2212粉末的相组成影响

实验研究了Bi-2212粉末在空气,8%O2和纯O2种处理的相组成特征,指出通过改变热处理温度和气氛可控制前驱粉中对2223成相影响较大的(Bi,Pb)-2212相,Ca2PbO4相,2201相和14∶24AEC等相.     

热处理条件对双粉工艺中Bi—2212粉末的相组成影响

实验研究了Bi-2212粉末在空气，8％O2和纯O2种处理的相组成特征，指出通过改变热处理温度和气氛可控制前驱粉中对2223成相影响较大的(Bi，Pb)-2212相，Ca2PbO4相，2201相和14：24AEC等相。     

Phase evolution during the melting and recrystallization of ceramic core in the (Bi,Pb)-2223 tape

The phase evolution during melting and recrystallization of (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ ((Bi,Pb)-2223) core in a Ag-sheathed monofilamentary tape has been investigated. The tape was fabricated by PIT process with powders containing nearly pure (Bi,Pb)-2223 phase. Short samples were melted at 805 °C, 808 °C, 812 °C, 816 °C, 831 °C, slowly cooled at 1.5 °C/h under flowing 1.6% O₂ balanced with argon and quenched in air at room temperature. X-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS) were applied for the phase identification. The results show that (Bi,Pb)-2223 core is partially melted into a liquid and alkaline earth cuprates (AECs), mainly 2:1-AEC, at 805 °C, 808 °C, 812 °C, and well reforms directly from the melt during the slow cooling. More (Bi,Pb)-2223 phase is decomposed at temperatures higher than 816 °C, but cannot recrystallize, indicating that a partial melting at some temperatures around a given temperature range is essential to (Bi,Pb)-2223 phase reformation. The melt composition moves from that between “2223” and “2212” stoichiometries towards 2212-like stoichiometry with increasing temperature. This seems to lead to the conclusion that (Bi,Pb)-2223 phase decomposes incongruently into a 2212-like liquid and (Ca,Sr)-cuprates. 2:1-AEC plays the most important role in (Bi,Pb)-2223 melt-recrystallization process. Our results also reveal that plate-like shape (Bi,Pb)-2223 grains can be obtained via melting and recrystallization if the optimum processing conditions are used.     

The formation mechanism of Bi2Sr2Ca2Cu3Ox superconducting phase

The mechanism and dynamic model of the formation of 2223 phase are presented and verified in the paper. It reveals that with the solubilization of part of the 2212 phase, 2223 phase is formed by the reaction being carried out according to a nucleation and growth mechanism in the presence of liquid phase, which conforms to the JMA dynamics equation. The addition of a little 2223 phase as nucleator, regrinding and resintering can promote the formation of 2223 phase. But the quick formation rate of 2223 phase may lead to irregularity of the 2223 phase structure, which degrades its electric and magnetic properties, while annealing treatment can improve its superconductivity.     

采用快速升温烧结方法生长Tl-1223超导薄膜的研究

报道了在铝酸镧(00l)衬底上生长Tl-1223超导薄膜的快速升温烧结方法以及铊(Tl)源陪烧靶的配比对Tl-1223薄膜晶体结构的影响.扫描电子显微镜观测表明,采用快速升温烧结方法生长的Tl-1223超导薄膜具有致密的晶体结构.X-射线衍射等测试表明,采用合适配比的陪烧靶在氩气环境下可以制备出纯c轴取向的Tl-1223超导薄膜,充氧退火后的薄膜具有较好的电学性能,其临界转变温度T_(c onset)达到116K,临界电流密度达到1.5MA/cm~2(77 K,0 T).实验结果表明,采用这一新的烧结方法制备Tl系超导薄膜具有升降温时间和恒温时间短、生产成本低等特点.     

固相反应时Bi1.92Pb0.32Sr2Ca1.7Mg0.3Cu3.07Ox超导体中2223相的生长

用固相反应法合成了名义组分为Bi_1.92Pb_0.32Sr₂Ca_1.7Mg_0.3Cu_3.07O_x的块状样品。X射线衍射谱(XRD)、扫描电子显微镜(SEM)和电子探计X射线分析(EDAX)结果以及块状和粉状试样的交流磁化率测量表明,样品中存在110和85K两个超导相;2223相(110K)首先在2212相(85K)晶体的晶界和外部区域生成。本文认为,最初存 关键词：     

Bi-Sr-Ca-Cu-O体系中的单斜相与掺Ba效应的研究

采用固相反应法合成名义组份为Bi₂Sr₂Ca_1-xBa_xCu₂O_y(A),Bi_1.7Pb_0.3Sr₂Ca_2-xBa_xCu₃O_y(B)的样品。此样品的物相和结构分析表明:在Bi系中存在着一种新的单斜相,其晶胞参量为a=24.8 关键词：     

Comparative photoemission study of Bi2(Sr,Ca)3Cu2O8+y and Bi1.7Pb0.3Sr2Ca2Cu3O10+y

The electronic structure of Bi-based 2223 single phase superconductor has been studied by ultraviolet and X-ray photoemission. By comparison with that of 2212 phase superconductor, we find a higher density of states nearE _F for 2223 phase. From analysis of the Cu 2p core-level spectroscopy, we obtain a relatively smaller charge transfer energy between copper and oxygen as well as the Coulomb repulsion energy on Cu site for 2223 phase. We relate these changes to the increase of hole concentration from 2212 to 2223 phase. The experimental results support the viewpoint that the transition temperature should be correlated with the density of states atE _F .     

高温超导体中磁通涡旋的量子隧道效应——TlBaCaCuO化合物磁弛豫的实验研究

本文报道了ＴｌＢａＣａＣｕＯ超导体（２２１２,２２２３单相,多晶及薄膜材料）中磁弛豫现象的实验结果。从实验上证实了通量运动由热激活到非热激活机制的转变。实验中得到的与温度无关的磁弛豫速率与由通量运动量子隧道效应理论计算结果相一致。同时讨论了各向异性和磁场对磁通的量子漂移速率的影响     

Texture relationships and interface structure in Ag-sheathed Bi(Pb)-Sr-Ca-Cu-O superconducting tapes

We have studied the phase composition, alignment, and bonding at the Ag/Bi-Sr-Ca-Cu-O (BSCCO) interface for silver-sheathed tapes of both the 2212 and 2223 compositions which have been processed under different conditions. Strong texturing of the (001) planes of the BSCCO phases parallel to the Ag interface was seen, regardless of the Ag orientation. Short facets of non-(001) BSCCO planes accommodate local misalignments between the Ag and the (001) planes of the BSCCO phases. Whether the 2212 composites are processed by complete melting or by sintering below the melting point, there is always a residual half-layer of 2201 at the interface. By contrast, 2223 composites exhibit 2223 layers right up to the interface without any transition phases. Both compounds bond strongly to Ag and cracks, when present, occur preferentially away from the interface.