掺杂Y2O3和BaCeO3提高MOD-YBCO超导性能的研究

本文通过在前驱液中添加过量钇盐和铈的有机盐,采用三氟乙酸盐-金属有机沉积法(TFA-MOD) 在铝酸镧单晶基体上制备了含有纳米氧化钇和纳米铈酸钡的YBCO薄膜. 与纯YBCO薄膜相比,掺杂Y₂O₃/BaCeO₃的YBCO膜的临界转变温度几乎保持不变,为91 K左右. 而掺杂Y₂O₃/BaCeO₃的YBCO膜的临界电流密度达到5.0 MA/cm² (77 K, 0T), 是纯YBCO膜临界电流密度的1.5倍.薄膜中的Y₂O₃和BaCeO₃可能在YBCO内部起到了 有效的钉扎磁通作用. 关键词： 钇钡铜氧薄膜 2O₃和纳米BaCeO₃')" href="#">纳米Y₂O₃和纳米BaCeO₃ 磁通钉扎 三氟乙酸盐-金属有机沉积     

掺Ca-(RPr)-123系列超导体的高压合成

利用高温高压方法成功地合成出(R_0.4Pr_0.6)_0.5Ca_0.5Ba₂Cu₃O_7-δ(其中R=La,Pr,Nd,Sm,Eu,Gd,Y)单相123相超导体.其结果表明,在Pr系的R-123相化合物中掺Ca都能够获得高T_c的超导体,其超导转变温度都在100K左右. 关键词： 超导体 Pr-123相化合物 高压合成 稀土     

新块材超导体Pr1-xCaxBa2Cu3O7-δ(0.4≤x≤0.6)的高压合成与超导电性

采用高温高压合成方法，合成出了Pr_1-xCa_xBa₂Cu₃O_7-δ(0.4≤x≤0.6) 系列块材超导体，在缺氧的Pr_0.5Ca_0.5Ba₂Cu₃O_7-δ四方123结构样品中得到了T_c为98K.实验结果表明Pr在123结构中的价态为大于3+的混合价态，因而空穴填充和杂化导致的载流子局域化是Pr抑制123相超导电性的关键因素. 关键词：     

粉末熔化法(YHo)Ba2Cu3O7-y超导体的性能与微结构

采用粉末熔化工艺(PMP)制备了高J_c的(YHo)Ba₂Cu₃O_7-y差热分析结果表明,添加Ho可以改变Y系超导体的熔化温度。在YBa₂Cu₃O_7-y中加部分Ho替代Y可以提高体系的J_c,减小样品中211相的平均直径,并且微结构得到改善,在211粒子周围存在大量的晶体缺陷,这些晶体缺陷可能是有效的钉扎中心。 关键词：     

ScF3，NaScF4，(NH4)2NaScF6的可控合成与上转换发光性能的研究

钪基氟化物化学性质稳定、声子能量低、无辐射弛豫概率较低,是一种新型高效的基质材料,并且Sc3+半径较小,能与多种氨羧络合剂形成稳定的螯合物,因而具有更加奇特的物理和化学性质,近年来,成为许多科学家研究的热点。以聚乙烯二胺(PEI)作为表面活性剂,采用水热法在反应温度为200 ℃时成功制备了ScF₃∶Yb3+/Er3+,NaScF₄∶Yb3+/Er3+,(NH₄)₂NaScF₆∶Yb3+/Er3+纳米上转换发光材料。通过X射线衍射仪(XRD)、透射电镜(TEM)、扫描电镜(SEM)和荧光光谱仪对所制备样品的晶相、形貌和发光特性进行了研究,结果显示：通过改变反应物NH₄F和Ln3+的比例(NH₄F/Ln3+=1∶1,2∶1,2.5∶1,3∶1,4∶1,6∶1,10∶1,20∶1,30∶1,40∶1,50∶1)实现了对样品产物、晶相、形貌的控制。当NH₄F/Ln3+为2.5∶1时,生成了纯立方相的ScF₃;在NH₄F/Ln3+为4∶1时,生成了六角相的NaScF₄;在NH₄F/Ln3+为40∶1时,生成了一种纯立方相的新型基质材料(NH₄)₂NaScF₆,样品结晶度高,形貌均一,有正方形片状和足球状多面体;在980 nm红外激光的激发下,不同NH₄F/Ln3+比例生成的样品发光呈现桔黄→桔红→绿→黄绿等多种颜色的变化。实验表明仅改变NH₄F一种原料的用量,就可以生成ScF₃∶Yb3+/Er3+,NaScF₄∶Yb3+/Er3+和(NH₄)₂NaScF₆∶Yb3+/Er3+ 三种不同的产物,说明NH₄F的用量对产物的生成有决定性的作用,对晶相的转换、颜色的调控亦有重要影响。     

T*相超导体(Bi,Sr)2(Y,Ce)2Cu2Oy的性质研究

研究了T^*相超导体（Bi，Sr）₂（Y，Ce）₂Cu₂O_y的成相规律，发现缓冷对T^*相单相样品的制备是有利的．淬火样品的主相物质为Ce₂Y₂O₇，完全不含T^*相结构．在室温到熔化温度的范围，热分析未观察到结构相变．在240—460℃，相对每个Cu原子超导体失氧约0.1个氧．氧气中烧结并缓冷到室温的样品在30K出现零电阻现象 关键词：     

CoxTi1－xO2－δ体材中氢退火引起的铁磁性及结构相变

利用固相反应法在700℃—1000℃不同的温度下、空气中烧结Co₃O₄ 和TiO₂混合物，制备了(Co₃O₄)_x/3(TiO2)_1-x(03，说明Co₃O₄与TiO₂反应形成了CoT iO₃；同时，在700 ℃低温和900 ℃以上的高温烧结样品中分别观察到了单相的 锐钛矿和金红石相结构.经高低温烧结的样品在500 ℃氢退火后，CoTiO₃相消失 ，锐钛矿相的Co_xTi_1-xO_2-δ形成.X射线光电子能谱(X PS)分析显示，氢退火样品中的Co以+2氧化价态存在，同时没有观察到金属态的Co，这说明 氢退火样品中的室温铁磁性不是源于金属Co颗粒的形成，而是与钙钛矿结构的CoTiO_{3< /sub>相的消失和锐钛矿型的CoxTi1-xO2-δ相的形成 有关.(Co3O4)x/3(TiO2)1-x( 0x}Ti_1-xO_2-δ相的本征铁磁性，伴随着结构相变而产生的Co离子之间的铁磁交换相互作用或 许是样品室温铁磁性产生的根本原因. 关键词： 室温铁磁性 结构相变 锐钛矿 氢退火     

蓝光激发的Y2.93Al5O12∶0.07Ce3+黄色荧光粉的制备及光致发光

以Al₂(SO₄)₃·18H₂O、尿素为原料,采用水热-热解法制备了球形α-Al₂O₃粉体。以自制α-Al₂O₃、Y₂O₃及CeO₂为原料,固相法制备了白光LED用Y_2.93Al₅O₁₂∶0.07Ce3+黄色荧光粉,通过X射线衍射（XRD）、扫描电镜（SEM）、X射线能谱（EDS）及荧光光谱（PL）等对产物的物相、形貌及光致发光性能进行了表征。结果表明：水热-热解法制备出了物相纯净、分散性良好的球形α-Al₂O₃粉体,以该α-Al₂O₃为原料,合成出可被460 nm蓝光有效激发,发射光谱为峰值在550 nm宽带的Y_2.93Al₅O₁₂∶0.07Ce3+荧光粉,色坐标为（0.453,0.531 9）,采用GSAS软件对Y_2.93Al₅O₁₂∶0.07Ce3+荧光粉的XRD图进行了Rietveld结构精修,精修图与XRD测试图完全吻合,Y,Al,Ce,O四元素均匀地分布在黄色荧光粉产物中,Y_2.93Al₅O₁₂∶0.07Ce3+黄色荧光粉的激发光谱由两个部分组成,在340和460 nm处有两个非常明显的吸收峰,Ce3+的4f能级由于自旋-耦合而劈裂为两个光谱支项2F_7/2和2F_5/2,其中2F_5/2为基谱项。340 nm的激发峰对应于2F_5/2→5D_5/2的跃迁,460 nm的激发峰属于2F_7/2→5D_3/2的跃迁,并且460 nm处的激发强度强于340 nm处激发强度。以460 nm为监测波长得到的发射光谱,最强发射峰位于550 nm,Y_2.93Al₅O₁₂∶0.07Ce3+荧光粉是一种适用于白光LED的高性能黄色荧光粉。     

赝能隙导致的YBa2(Cu1－xMx)3O7-δ(M=Co,Zn)薄膜的输运性质异常

报道了两类典型元素替代的超导Y123相体系-YBa2(Cu1-xCox)3O7-δ(x=001,002)和YBa2(Cu1-yZny)3O7-δ(y=0005,0010)薄膜的电阻率温度特性(ρ(T))和Hall效应(RH(T)).研究表明,Co掺杂的Y123相体系十分类似于氧欠掺杂的情况,对Co掺杂的薄膜样品,由电阻率温度特性定义的赝能隙打开的温度T分别为193和225K.而Zn掺杂的样品没有观察到赝能隙打开对电阻率温度特性的影响.由Hall效应的测量和Hall角(cotθH)定义了另一个特征温度T0, 关键词： 赝能隙 Y123相 Hall效应     

YAG：Ce发光材料合成的助熔剂研究

采用高温固相法合成YAG:Ce荧光粉时,传统的以硼酸为助熔剂的产物硬度很大,处理过程中容易破坏晶体形貌,影响发光性能.采用氟化物助熔剂(MgF₂、CaF₂、SrF₂、BaF₂、AlF₃)及它们与H₃BO₃混合助熔剂来制备YAG:Ce,研究了助熔剂种类及其浓度对制得的粉体发光性能的影响,比较了它们的晶体形貌与物相组成.结果表明,采用不同助熔剂合成的YAG:Ce的激发光谱及发射光谱基本相同,而BaF₂、AlF₃、SrF₂及它们与H₃BO₃的混合助熔剂系列,可在一定程度上降低产品硬度、提高产品发光亮度;其中H₃BO₃~SrF₂系列、H₃BO₃~BaF₂系列的晶化程度与粒度分布均有改善;H₃BO₃~BaF₂系列的物相组成比较纯,除Y₃Al₅O₁₂主相外基本无杂相.     

掺Ce的Y－Ba－Cu－O体系成相的拉曼光谱分析

掺Ｃｅ的Ｙ－Ｂａ－Ｃｕ－Ｏ体系成相的拉曼光谱分析许存义，左健，王跃（中国科学技术大学结构分析开放研究实验室合肥２３００２６）ＳｔｕｄｙｏｎＴｈｅＲａｍａｎＳｐｅｃｔｒｕｍｏｆＣｅ－ｄｏｐｅｄＹ－Ｂａ－Ｃｕ－ＯＳｙｓｔｅｍ￥ＣｕｎｙｉＸｕ；ＪｉａｎＺｕ...     

Improvement of the superconducting properties of an infiltrated YBCO bulk superconductor by a BaCeO3 addition

Single grain YBa₂Cu₃O_7−x (Y123) bulk superconductors with Y₂BaCuO₅ (Y211) and various amounts of BaCeO₃ (5–45 wt.% by an increment of 10 wt.%) were fabricated by a seeded infiltration process. The addition of BaCeO₃ was found to be effective for a modification of the microstructure and an improvement of the superconducting properties. The refinement effect for Y211 particles within an entire superconducting YBa₂Cu₃O_7−x (Y123) matrix was achieved by BaCeO₃ additions. The critical current density (J_c) values were increased as the BaCeO₃ contents were increased (maximum J_c at 35 wt.% BaCeO₃ addition). The J_c improvement by BaCeO₃ additions might be due to the microstructure modifications associated with the finely distributed Y211 and BaCeO₃ particles. With the addition of BaCeO₃ the onset T_c values decreased slightly, indicating highly limited Ce substitution for Y site. It can be concluded that the BaCeO₃ addition has a beneficial effect on the morphology, the size and the distribution of the Y211 inclusions and the microstructure regarding pinning improvement.     

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}     

Compounds in mixed phase CeBa2Cu3Oy and TbBa2Cu3Oy systems

An analysis of the composition of Ce and Tb barium copper oxide samples with the nominal composition CeBa₂Cu₃O_y and TbBa₂Cu₃O_y, prepared with the same solid state reaction method used for the other superconducting rare earth (R) barium copper oxide RBa₂Cu₃O_7- compounds, is described. The analysis indicates that these samples are multiphase and consist mostly of 1) the perovskite phases BaCeO₃ or BaTbO₃, 2) CuO, and 3) BaCuO₂. No trace of the oxygen deficient orthorhombic perovskite type structure of YBa₂Cu₃O_7- could be found in the X-ray diffraction patterns. Consequently, the compounds do not display superconductivity. The magnetization measurements indicate that BaCeO₃ is weakly paramagnetic which is consistent with tetravalent Ce. The BaTbO₃ compound exhibits an antiferromagnetic transition at a Néel temperature T_N-35 K, and its magnetic susceptibility above T_N can be described by a Curie-Weiss law with an effective moment that corresponds to tetravalent Tb.     

Calorimetric study of phase transitions in the perovskite BaCeO3

Differential scanning calorimetry was used to study phase transitions (PT) in the perovskite BaCeO₃. It is shown that its phase state is determined by a second-order λ transition at T _tr=520–540 K and a first-order δ transition at T _tr=600–670 K. Differences in PT parameters between ceramic and fused BaCeO₃ have been established. Fiz. Tverd. Tela (St. Petersburg) 40, 2109–2112 (November 1998)     

Phase evolution and morphology of nanocrystalline BaCe0.9Er0.1O3−δ proton conducting oxide synthesised by a novel modified solution combustion route

Pure BaCeO₃ and 10 mol% Er₂O₃ doped BaCeO₃ (BCE) was synthesised by a novel modified solution combustion synthesis (MCS) route wherein the pH of the precursor solution was varied and the phase formation and morphology were compared with those obtained in conventional solution combustion synthesis (SCS). X-ray diffraction (XRD) studies confirmed the presence of the undesirable BaCO₃ phase in the calcined powders prepared using SCS route whereas the powders synthesised with the modified (MCS) route exhibited a single perovskite phase after calcination. Variation in the pH of the precursor solution resulted in a morphology change from a mix of irregular and globular at pH 4 to more spherical at pH 6 and 8. Fourier transform infrared spectroscopy (FT-IR) studies revealed that calcination time has more pronounced effect on phase formation than calcination temperature. A calcination time of 10 h at 1000 °C resulted in negligible amount of BaCO₃. Such prolonged calcination treatment resulted in substantial grain growth in the SCS sample while the MCS samples were still in the nanocrystalline form. Absence of the ceria peak (464 cm^–1) in the Raman spectra confirmed the presence of a single perovskite BaCeO₃ phase in the sintered pellets as well.     

A M?ssbauer spectroscopic study on the action of Ce in the catalyst for dehydrogenation of etylbenzene to styrene

Two series of Fe-K catalysts for dehydrogenation of ethylbenzene to styrene were prepared with different amounts and different compounds of the additional element Ce. M?ssbauer spectroscopy has been used to determine the Fe compound in the catalyst and to investigate the effect of Ce. The catalytic properties of the catalysts have also been measured. The results show that the element Ce in the catalyst is favorable to form the predecessor of the catalytic active phase, the compound KFe₁₁O₁₇ and that the optimal percentage of CeO₂ is 8%～15% in the catalyst which is favorable to the formation of KFe₁₁O₁₇ and to get better catalytic properties.     

Preparation and characterization of cerium oxide doped TiO2 nanoparticles

A mixed oxide consisting of TiO₂ as the major phase and CeO_2−y (0<y<0.5) as the dopant phase was prepared via the sol-gel reaction of Ti(i-OC₃H₇)₃ in an aqueous solution of Ce(NO₃)₃. The resulting oxide powders with different CeO_2−y contents were all composed of nano-sized spheres. The CeO_2−y phase was identified to have retarding effect on the phase transition from anatase TiO₂ to rutile TiO₂ at calcinations temperature as high as 800 °C, which would otherwise be a thorough conversion. The CeO_2−y-TiO₂ powders could apparently shift the UV-absorption band of TiO₂ toward visible range, and there was an optimal CeO_2−y content in association with the maximum absorbance. This effect is interpreted as the existence of an n-type impurity band, due to the substitution of Ti⁴⁺ for Ce^3+/4+ at the interface between the two oxides, in the gap of TiO₂. According to X-ray photoelectron spectroscopy (XPS) investigation, the Ti element mainly existed as the chemical state of Ti⁴⁺ and the Ce oxide doping did not affect the peak position of Ti 2p. The Ce 3d spectrum of CeO_2−y-doped TiO₂ sample basically denotes a mixture of Ce^3+/4+ oxidation states giving rise to a myriad of peaks.     

Studies of impurity levels in Rh-doped and Ce-doped photorefractive BaTiO3

Impurity levels, light-induced and thermo-induced charge transfer processes in Rh-doped and Ce-doped photorefractive BaTiO₃ were studied. The thermal depths and optical transitions of these impurity levels in the crystals were determined by using such methods as light-induced absorption, thermo-induced absorption, and grating dark decay. The origins of these impurity levels were discussed. We demonstrated, for the first time to our knowledge, that thermo-induced absorption spectroscopy is a useful and complementary technique for investigating the impurity levels in photorefractive crystals. With this technique, the deep impurity level generated by Ce in BaTiO₃:Ce was revealed and identified. Received: 7 July 1999 / Revised version: 24 September 19999 / Published online: 2 February 2000     

Superconducting—normal phase boundaries of (La,Th)Ce systems

The dependence of the superconducting transition temperature T_c on Ce impurity concentration n is reported for various ($\text{La, Th}$)Ce systems. These results document for the first time the evolution of the superconducting— normal phase boundary (T_c vs n curve) as an impurity undergoes magnetic- nonmagnetic transition which for Ce impurities in ($\text{La, Th}$)Ce systems proceeds with increasing Th concentration. Observed for only the second time, re-entrant T_c vs n curves are reported for two La-rich La, Th host compositions.