在氧-水蒸气存在下单相Sr2(Gd,Ce)2Cu2RuO10的合成及其电学性质

传统固相反应所合成的锶系钌铜氧化物,通常总伴有少量铁磁性SrRuO3杂相.采用氧(或空气)-水蒸气混合气氛下的新型固相反应,既能成功合成锶系钌铜氧化物的前驱物纯相Sr2GdRuO6(211相), 也能进一步在相对低的温度下成功合成锶系钌铜氧1222纯相化合物RuSr2(Gd,Ce)2Cu2O10 (Ru-1222),使其中SrRuO3杂相含量大大减少.详细讨论了新型固相反应下产物的形成及其机理,并涉及SrRuO3杂相的存在对RuSr2(Gd,Ce)2Cu2O10产物电学性质的影响.结果表明,水蒸气的作用能抑制前驱物合成中SrRuO3杂相的形成,进而控制反应产物Ru-1222相中SrRuO3杂相的存在,而后者又有利于Ru-1222相超导电性的获得.     

高纯度超导氧化物RuSr2GdCu2O8的合成与超导电性

RuSr2GdCu2O8据报道是转变温度为30－40K的超导体，其合成的主要问题是，在合成过程中有相当多的铁磁性的SrRuO3杂相伴随着主相一起生成，本文报道了合成RuSr2GdCu2O8（Ru-1212相）纯相的新方法，即在O2和水蒸气气氛中首先合成纯相的Sr2GdRuO6(Ru-211相）先驱物，然后Sr2GcRuO6与CuO高温烧结，生成RuSr2GdCu2O8。合成的RuSr2GdCu2O8电阻为半导体温度行为，该体系的超导转变与生成的杂相有关。     

在氧-水蒸气存在下单相Sr2(Gd,Ce)2Cu2RuO10的合成及其电学性质

传统固相反应所合成的锶系钌铜氧化物，通常总伴有少量铁磁性SrRuO₃杂相.采 用氧(或空 气)_水蒸气混合气氛下的新型固相反应，既能成功合成锶系钌铜氧化物的前驱物纯相Sr₂G dRuO₆(211相), 也能进一步在相对低的温度下成功合成锶系钌铜氧1222纯相化 合物RuSr₂(Gd,Ce)₂Cu₂O₁₀ (Ru_1222）， 使其中SrRuO _{关键词： 水蒸气参与的新型固相反应 2}(Gd')" href="#">RuSr₂(Gd 2Cu_{2< /sub>O10纯相')" href="#">Ce)2Cu2< /sub>O10纯相 3杂相')" href="#">SrRuO3杂相 电学性质}     

SrRuO_3样品固相法的制备及性能研究

利用固相反应法制备了SrRuO3样品.X射线衍射确定样品为单相正交畸变钙钛矿结构.扫描电子显微镜观察了颗粒形貌基本成球形,颗粒直径约为1.8μm.SrRuO3样品在149K温度以下具有铁磁性,SrRuO3样品表现出金属导电性.     

(Hg,M)-1222相铜氧化合物的合成及其超导电性研究(M=W、Mo、Ti、V、Cr)

分别用固相反应和柠檬酸盐溶胶－凝胶法制备义组成为Sr2(Gd1.5Ce0.5)Cu2Oz的前驱物,再用真空烧结的方法合成了（Hg,M)－1222相铜氧化合物（Hg0.75M0.25)Sr2(Gd1.5Ce0.5)Cu2Oz(M=W,Mo,V,Cr,Ti)。溶胶－凝胶法同固相法相比混合更均匀,反应温度低,成相情况好,改进该方法后,用溶解度较高的Ce（NO3）3代替不溶于硝酸的CeO2,制得了纯1222相。研究了不同退火条件对样品电阻温度特性的影响的影响,发现高氧压退火有助于超导转变,M＝W,Mo时得到超导体,Tc(onset)在13－27K之间。     

SrCaCu3Ox相的X射线分析

用Bi系超导体制备方法得到了名义成份为 Sr:ca:Cu=1:1:3的新相 SrCaCu_3O_x.X射线衍射表明,该相属正交晶系,点阵参数为 a=11.37(?),b=12.84(?)和 c=19.54(?).该相的强衍射线与 Bi 系超导相的衍射线的位置相近,使得很难在 Bi 系超导体中检出这种杂相的存在.该相可能是种类似于 Sr_(14-x)Ca_xCu_(24)O_(41)相的非公度结构,在 c 方向含有7个 CuO_2和5个(Sr,Ca)_2Cu_2O_3.     

Ba2+掺杂对Sr3Al2O6:Eu2+红色荧光粉发光性能的影响

采用高温固相法合成了(Sr1-x-yBax)3Al2O6∶3yEu2+红色荧光材料,通过XRD、荧光光谱和热稳定性测试分析,分别研究了Eu2+、Ba2+掺杂对样品的晶体结构、发光性能和热稳定性的影响。XRD测试结果表明,在1 200℃保温3 h条件下合成了具有立方晶体结构、空间群为Pa3的Sr3Al2O6纯相样品,Eu2+、Ba2+的掺入并没有改变其基质晶格的结构类型。荧光光谱分析表明,Eu2+的摩尔分数为4%时,(Sr0.98-yBa0.02)3Al2O6∶3yEu2+样品的发射峰最强,Ba2+的掺入使样品的发射峰发生红移而发射强度降低,且随Ba2+浓度的增加红移越发明显。此外,Ba2+的掺杂提高了Sr3Al2O6∶Eu2+样品的热稳定性。     

DTA和XRD用于(14-x)SrCO3-xCaCO3-24CuO系统合成spin-ladder化合物Sr14-xCaxCu24O41的研究

采用差热分析(DTA)技术和粉末X射线衍射(XRD)技术研究了(14-x)SrCO3xCaCO324CuO体系(x=0、0.4、2.8、5.6、8.4、11.2、13.6和14)的热分解和固相反应过程,第一次详细地分析了该体系的热行为与合成纯spin ladder化合物Sr14-xCaxCu24O41的关系.实验结果表明,x≤5.6时,DTA曲线在1000℃以下显示了两个吸热峰,DTA曲线可分成三个阶段,分别对应于合成单相Sr14-xCaxCu24O41的固相反应过程;x≥8.4时,DTA曲线在1000℃以下显示了三个吸热峰,800℃附近的第一个吸热峰反映系统中CaCO3的含量,第三个吸热峰的有无是能否合成单相化合物的决定性标志.     

原位法MgB2-B4C复相超导体的成相与特性

以B4C粉末与Mg粉为原料,采用真空同相反应法成功制备了复相MgB2超导块材,研究了不同制备工艺下MgB2的成相,测量分析了材料的X射线衍射谱、扫描电镜图像、低温电输运特性等.结果显示,合成的复相超导材料含MgB2超导相、B4C绝缘相和少量MgB2C2杂相,MgB2超导相含量与B4C粒径、合成温度、反应时间等有关,并在...     

Sb2O3的丰度对（1-x）La0.6Dy0.1Sr0.3MnO3/（x/2）（Sb2O3）电输运性质的影响

用固相反应法制备(1-x)La0.6Dy0.1Sr0.3MnO3/x/2(Sb2O3)(x=0.00,0.02,0.15)样品,通过X射线衍射(XRD)图谱,扫描电子显微镜(SEM)照片及SEM能谱(EDS),ρ～T曲线研究样品的结构及电输运性质.结果表明:Sb离子没有进入Mn位,Sb2O3包覆在La0.6Dy0.1Sr0.3MnO3颗粒表面,Sb2O3起助熔剂作用,使得复合样品的颗粒变大且大小相对均匀;复合样品的绝缘体-金属转变温度TP较纯的La0.6Dy0.1Sr0.3MnO3的TP提高20K左右,对x=0.15的样品电阻高峰值比纯的La0.6Dy0.1Sr0.3MnO3的峰值电阻率增大两个数量级,用自旋极化隧穿理论予以解释.     

New Members of the RuSr 2 RECu 2 O 8 Family of Phases (RE=Rare Earth) Obtained at High Pressure and Temperature

At room pressure, Sm, Eu and Gd seem to be the only RE elements that accept to enter into the structure of RuSr 2 GdCu 2 O 8 . However high pressure and high temperatures allow one to replace gadolinium by other lanthanide cations. We have been successful in replacing Gd by Y, La, Pr, Nd, Tb, Dy, Ho and Er. X-ray diffraction patterns fitted by the Rietveld method show that the average crystal structure of RuSr 2 RECu 2 O 8 is tetragonal with P 4/ mmm space group symmetry. Micro-Raman experiments have been performed on RuSr 2 GdCu 2 O 8 samples synthesized at both high and room pressure; the resulting spectra are consistent with the same structure, since there are no major changes in the low-frequency range.     

Cr掺杂对BaxSr1-xRuO3体系磁性和输运性质的影响

本文采用固相反应法制备了BaxSr1-xRuO3和BaxSr1-xRu0.9Cr0.1O3两组样品,对比研究了它们磁性和电输运性质.当掺杂量少于0.2时,体系处于有少许畸变的钙钛矿的3C结构,Cr的掺入很大幅度提高了体系的铁磁转变温度Tc,电输运性质上也由坏金属行为转变为Mott绝缘体的行为,并且在铁磁相变附近出现电阻拐点.当掺杂量大于等于0.2时,体系发生结构相变,由畸变钙钛矿3C结构变为6 M的单斜结构.这时,Cr的掺入对体系的影响并不明显.这些结果表明引起SrRuO3铁磁转变温度升高的Ru+5-O-Cr+3相互作用对晶格结构有强烈的依赖关系.     

Sensitivity to disorder of the metallic state in the ruthenates

We report the results of transport measurements on SrRuO3, Sr3Ru2O7, and CaRuO3. In SrRuO3 and Sr3Ru2O7, our findings are consistent with the predictions of Fermi liquid theory, in contrast to previous reports based on samples with much shorter mean free paths. In CaRuO3, however, a T1.5 power law is seen in the resistivity in the high purity samples studied here. Our work gives concrete evidence that even the metallic state of the ruthenates is highly sensitive to disorder.     

通过改变基质阳离子半径使O~(2-)→Eu~(3+)电荷迁移带红移

采用高温固相法在1 300℃合成了A_(0.98)Nb_2O_6∶Eu_(0.02)(A=Ca,Sr,Ba)荧光粉。X射线衍射(XRD)的结果表明烧结后得到的产物为纯相。利用稳态荧光光谱(PL)和漫反射光谱(DRS)对A_(0.98)Nb_2O_6∶Eu_(0.02)(A=Ca,Sr,Ba)的发光性质进行了研究。结果表明A_(0.98)Nb_2O_6∶Eu_(0.02)(A=Ca,Sr,Ba)荧光粉可以发射Eu~(3+)的特征红光,光强度按Ca Nb_2O_6Sr Nb_2O_6Ba Nb_2O_6从大到小排列。激发光谱中可以观察到Eu~(3+)离子的电荷转移跃迁(CT)和f-f跃迁吸收。其中CT吸收峰因基质阳离子半径的增大而发生了较大程度的红移,从270 nm红移到了330 nm。     

Phase separation in A-site-ordered perovskite manganite LaBaMn2O6 probed by 139La and 55Mn NMR

139La- and 55Mn-NMR spectra demonstrate that the ground state of the A-site-ordered perovskite manganite LaBaMn2O6 is a spatial mixture of the ferromagnetic and antiferromagnetic regions, which are assigned to the metallic and the insulating charge ordered state, respectively. This exotic coexisting state appears below 200 K via a first-order-like formation of the antiferromagnetic charge ordered state inside the ferromagnetic metal one. The Mn spin-spin relaxation rate indicates that the ferromagnetic region coexisting with the antiferromagnetic one in LaBaMn2O6 is identical to the bulk ferromagnetic metal phase of the disordered form La0.5Ba0.5MnO3 in spite of the absence of A-site disorder. This suggests a mesoscopic rather than nanoscopic nature of the ferromagnetic region in LaBaMn2O6.     

Molecular Structure and Dimerization of d-Cycloserine in the Solid State

d-cycloserine (CS) is transformed into cis-3, 6-bis(aminooxymethyl)-2, 5-piperazinedione (CS-dimer) in the solid state under a humid atmosphere. This dimerization process was followed by measuring the IR bands characteristic of CS and CS-dimer. The reaction was accelerated by the presence of increased water vapor. The X-ray analysis of CS monohydrate (CS · H₂O) revealed that the CS molecules exist as a zwitter ion where the α-amino N atom is protonated and the amide N atom is deprotonated in the crystal. Participation of water molecules was suggested in the dimerization of CS.     

Synthesis and physical properties of alkaline earth metal graphite compounds

We report synthesis and search for superconductivity of Ba, Sr, Ca and Mg-GIC. We adopted conventional vapor phase reaction in order to prepare high quality GICs. No superconducting transition was found for Ba and Mg-GIC. As for Sr, Sr-GIC showed a sharp superconducting transition at T_c=1.65 K. Sr graphite compound SrC_x prepared from powder graphite by thermal treatment at higher temperature showed ferromagnetic character.     

不同激发波长对Sr3Al2O6∶Eu2+,Dy3+红色长余辉发光材料发射光谱的影响

采用高温固相法合成了Sr3Al2O6∶Eu2+,Dy3+长余辉发光材料。用X射线衍射仪及荧光分光光度计对材料物相及光谱性能进行了分析。结果表明:所得样品为Sr3Al2O6的纯相,在360nm波长的激发下,得到波峰为537nm的宽带发射光谱;在468nm波长的激发下,得到波峰为590nm的宽带发射光谱;在波长为394nm的激发下,537和590nm的峰同时出现。根据晶格场效应和电子云膨胀效应,对不同激发波长对Sr3Al2O6∶Eu2+,Dy3+发射光谱的影响进行了解释。结果表明:在Sr3Al2O6∶Eu2+,Dy3+中发光中心因其5d能级劈裂幅度不同及4f65d1能带重心不同而导致发光颜色的不同。     

Fabrication of high performance Gd–Ba–Cu–O single grains in air using a practical melt processing technique

A practical processing route for the fabrication of LRE-Ba–Cu–O single grain superconductors has been developed at the University of Cambridge based on a generic, Mg-doped Nd-123 melt textured seed and suppression of the formation of the solid solution phase in air by enriching the precursors with higher Ba concentration. The processing of high performance Gd–Ba–Cu–O single grains using this processing route is described. The Mg-doped generic seed crystal has been used effectively to promote heterogeneous nucleation via a cold-seeding process. The Gd/Ba solid solution has been suppressed by enriching Gd–Ba–Cu–O precursor powders with two different Ba-rich compositions. This involved adding BaO₂ and GdBa₆Cu₃O_y (Gd-163) (a novel Ba-rich second phase) to the precursor powders, respectively. The Gd-163 phase has been observed not only to suppress formation of the solid solution phase, but also to promote increased heterogeneous grain size. A detailed further study has been carried out with an initial aim of optimizing the BaO₂ and Gd-163 phase content of the precursor composition to produce a single grain almost free of solid solution. Based on the optimized parameters, large single grain Gd–Ba–Cu–O superconductors have been fabricated in an air atmosphere and demonstrated to exhibit record trapped magnetic fields for this material melt processed in air in relatively small single grain samples. The trapped fields of samples produced in air atmosphere are at least comparable to those processed under reduced oxygen partial pressure.