Bi系高温超导氧化物相图研究进展

回顾了Bi系氧化物超导材料发现以来Bi系相图研究进展,着重讨论了Bi_2Sr_2CaCu_2O_8(2212),Bi_2Sr_2Ca_2Cu_3O_(10)(2223)两超导相周围固相面以下的四相区,高温分解反应,及对应固态四相区的固液五相零度量反应。指出为了指导超导材料的制备有必要对2212,2223两相周围的相图进行进一步的研究。对2212关键在于研究Bi_2Sr_2CuO_6(2201)非超导相、CaO、2223与2212及其相邻相是否平衡,形成哪些固态四相区及对应的固液五相零变量反应是什么?对2223关键在于研究2223及其相邻相与BiO_(1.5)-SrO-CaO与BiO_(1.5)-CaO-CuO两边际三元截面上的相是否平衡,构成哪些固相四相区,对应的零变量反应是什么?寻找2223,2212的初晶区仍是Bi系相图研究重点。     

碘量法测量氧化物超导体的氧含量

本文报道一种改进的碘量法测定氧化物超导体氧含量的方法,其相对误差可控制在0.5%以内,分析了该方法的误差来源及其消除的途径,并以YBa_2Cu_3O_(7-δ)为例,测定了在不同热处理条件下的氧含量与其结构的关系。此外还用本方法测定了Bi_2Sr_2Ca_(?)-_xY _xCu_2O_(5+δ)系列样品的氧含量。     

Ba_2CeCu_3O_(7.4)复合氧化物的物相、晶体结构及电性

本文报道了Ba-Ce-Cu-O的一种新相,它是立方BaCeO_3的一种超格子a=6.208 b=6.232(a、b～2~1/2ap)c=8.759(c～2ap)其空间群为PMMM。化学分析、热天平和结构分析表明其结构化学式为(Ba_(2.650)Ce_(0.175))(Cu_3Ce_(1.237)O_(10.452),在单相时,它是一个绝缘体。     

Bi_(4=x)Pb_xSr_3Ca_3Cu_4O_y超导体中高温相的形成条件

本文利用x-衍射、EDX、SEM、DTA等方法,对Bi_(4-x)Pb_xSr_3Ca_3Cu_4O_y超导体中的最佳含Pb量、高温相的形成条件、以及Pb在形成高温相中的作用等进行了研究。结果表明,Pb的加入可降低高温相的形成温度,能促进高温相的形成速率。当x=1.0时,超导起始转变温度为110K,而零电阻温度可达106K。在860℃下,经72小时烧结,可获得基本上都为高温相的超导体。     

γ射线辐照对铋系超导体的影响

日本原子能研究所等单位合作研究了γ射线对Bi_(1.3)Pb_(0.5)sr_2Co_2Cu_3O_10超导体的辐照,考察了辐照对超导电学性能的影响。在室温下将该材料以Co~(60)γ射线辐照,辐照剂量从1.5MR/h逐渐升至50MR/h,测量电阻率与转变温度的变化。实验结果表明,样品在25.25MR/h辐照时,临界转变温度由103.4K升至104.1K,且随着辐照量的增加,     

Co替代Mn对Pr_(0.6)Ca_(0.4)MnO_3磁性质及电荷有序的影响

用固相反应法制备Pr_(0.6)Ca_(0.4)Mn_(1-x)CoxO_3(x=0,0.02,0.04,0.06)系列多晶样品。通过X射线衍射(XRD)图谱检测样品的结构,通过零场冷(ZFC)和加场冷(FC)的磁化强度-温度(M-T)曲线,电子自旋共振(ESR)图谱,研究Co替代Mn对Pr_(0.6)Ca_(0.4)Mn O_3磁性质及电荷有序相的影响。结果表明:母体样品的宏观磁性质随温度的变化而发生多重变化,在238 K出现电荷有序相,TCO=238 K,200~173 K温区的ZFC曲线出现一个平台,173 K为Neel温度,即T_N=173 K,在40 K附近ZFC曲线出现一个尖峰,样品出现自旋玻璃态,自旋玻璃态转变温度T_f=40 K。Co替代Mn对Pr_(0.6)Ca_(0.4)Mn O_3的磁性质及电荷有序相影响明显,所有掺Co样品都没有表现出电荷有序特征,随温度降低从顺磁向铁磁/反铁磁混合相转变。Co替代Mn对电荷有序的破坏非常容易,当Co替代量x=0.02时电荷有序相被完全融化。Co替代Mn对电荷有序相的破坏之所以容易,是因为用非Jahn-Teller(JT)离子Co~(3+)替代JT离子Mn~(3+),削弱了Jahn-Teller畸变,间接证明Jahn-Teller电-声子相互作用是产生电荷有序的主要原因。     

稀土锰氧化物Nd_(0.5)Sr_(0.4)Ca_(0.1)MnO_3的磁性研究

通过XRD和SQUID研究了Nd_(0.5)Sr_(0.4)Ca_(0.1)MnO_3多晶样品的结构和磁性.研究结果表明,该样品单相性好,空间群为Pbnm,在高温区呈现顺磁性,随着温度降低出现了顺磁-反铁磁的转变,相变温度点-奈尔温度(T_N=200K),当温度低于200K时,铁磁与反铁磁两相共存,温度低于150K时铁磁逐渐消失,直到完全变为反铁磁.     

In-Sb-Sn和Bi-Pb-Sn三元系相图

采用室温和高温X射线衍射测定了In-Sb-Sn和Bi-Pb-Sn两个三元系25℃的等温截面图。用高温衍射确定了在Bi-Pb-Sn三元系中X相的结构,该相属六角晶系,在100℃对于成分为Bi_(?)Pb_(55)Sn_5的X相,属六角晶系,a=0.3518(1)nm, c=0.5819(1)nm, Mg型结构。     

铅取代BiSrCaCuO超导系中部分铋的研究

铅在Bi_(2-x)Pb_xSr_2Ca_2Cu_3O_y超导系中的最大固溶度在x=0.30～0.45范围内。但是,只有添加适量的铅才能促进高T_c相的形成,和改善其热稳定性。x=0.2的样品具有最佳超导性。当铅含量增加到x>O04时,超导性降低。冷轧加工在带材中形成〔001〕织构是带材J_c提高的主要原因     

Blue-emitting Sr_(1-x)Ca_xLu_2O_4:Ce~(3+) phosphors for high CRI white LEDs

A broadband blue-emitting Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+)(x=0-0.2) phospho rs were synthesized,which can be used for near-UV pumped white light-emitting diodes(w-LEDs).The crystal structures,photoluminescence pro perties,external quantum efficiency,the rmal stability and application perfo rmance of Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+),by partially substituting Sr~(2+) with Ca~(2+)(x=0-0.2),were studied by various analytical techniques.When the Ca/Sr ratio of Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+) gradually increases,the emission peak of Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+) red-shiftes from 459 to 465 nm,corrected external quantum efficiency increases from 31.8% to 42.9%,and the thermal stability is also improved.The mechanism of the changes of the photoluminescence emission and excitation spectra,external quantum efficiency and thermal stability properties was also investigated in detail.In addition,a w-LED was fabricated by using SrLu_2 O_4:Ce~(3+)(blue),β-sialon:Eu~(2+)(green) and(Sr,Ca)AlSiN_3:Eu~(2+)(red) phosphors combined with a 405 nm near-UV LED chip,and its color rendering index(CRI) reaches 96.0.When Sr_(0.8)Ca_(0.2)Lu_2 O_4:Ce~(3+)is applied as blue phosphor to substitute SrLu_2 O_4:Ce~(3+),the obtained w-LED devices have high luminous efficiency,and CRI greater than 95.0.These re sults show that the Sr_(1-x)Ca_xLu_2 O_4:Ce~(3+) can be potential blue phosphors for n-UV pumped high CRI w-LEDs application.     

三位置掺杂对BiCuSeO功能陶瓷热电性能的影响

对BiCuSeO功能陶瓷进行Bi/Cu/Se三位置掺杂,采用机械合金化和放电等离子烧结工艺制备Bi_(1-x)Ba_(x/2)-Pb_(x/2)Cu_(1-x)Ni_xSe_(1-x)Te_xO (x=0,0.02,0.04,0.06,0.08,0.10,摩尔分数)陶瓷,通过掺杂前后的物相组成、组织结构、电传输参数、热传输参数等表征,研究三位置掺杂对Bi Cu Se O功能陶瓷热电性能的影响和强化机理。结果表明,三位置掺杂可杂糅几种元素的增益效果,使Bi Cu Se O功能陶瓷保持较高Seebeck系数的前提下,电导率和功率因子显著提高。最佳掺杂量x为0.10,所得Bi_(0.90)Ba_(0.05)Pb_(0.05)Cu_(0.90)Ni_(0.10)Se_(0.90)Te_(0.10)O陶瓷在873 K温度下获得最高功率因子0.71 m W/(m·K~2)和最大热电优值1.06,分别约为未掺杂陶瓷的2.5倍和2倍。     

锂离子电池正极材料LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2的制备与性能研究

以自制Ni0.4Co0.2Mn0.4(OH)2前驱体和Li_2CO_3为原料,在空气气氛下采用固相烧结工艺制备了LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2锂离子电池正极材料。通过SEM和XRD等手段对材料烧结前后形貌与结构进行表征,并测试了烧结后锂离子电池正极材料的电化学性能。结果表明,Ni0.4Co0.2Mn0.4(OH)2前驱体具有良好的片状嵌入结构,且烧结制备的LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2正极材料混排因子c/a=4.967 3,阳离子混排因子I(003)/I(104)=1.25、I(006+102)/I(101)=0.333、I(018)/I(110)=0.87,表明LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2具有良好的层状结构。在2.5~4.6V、0.2C和0.5C下,LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2正极材料的首次放电比容量分别为166和154mAh/g,循环80次后容量分别保持为111和100mAh/g,具有良好的电化学性能。     

原位溶胶-凝胶法制备CoFe_2O_4/Bi_(0.5)(Na_(0.8)K_(0.2))_(0.5)TiO_3复合材料的磁电性能

采用原位溶胶–凝胶法制备xCoFe_2O_4/(1-x)Bi_(0.5)(Na_(0.8)K_(0.2))_(0.5)TiO_3(x为Co Fe_2O_4的摩尔分数,x=0.2,0.3,0.4)复合材料,研究磁性相CoFe_2O_4的含量对Co Fe_2O_4/Bi_(0.5)(Na_(0.8)K_(0.2))_(0.5)TiO_3复合材料结构、形貌及铁电性、铁磁性和磁电耦合性能的影响。结果表明,该复合材料中只存在CoFe_2O_4和Bi_(0.5)(Na_(0.8)K_(0.2))_(0.5)TiO_3两相;材料的饱和磁化强度和剩余磁化强度随Co Fe_2O_4含量增加而增大,而饱和极化强度和剩余极化强度随CoFe_2O_4含量增加而减小;当偏置磁场强度为72 k A/m时,0.3Co Fe_2O_4/0.7Bi_(0.5)(Na_(0.8)K_(0.2))_(0.5)TiO_3复合材料的磁电电压系数达11.8 m V/A。     

Fine controllable blue emission and its mechanism in Ce3+-doped orthosilicate solid solution phosphors for different plant growths

The designed Ce~(3+)-doped alkaline-earth silicate phosphors Ca_mSr_(2-m-n)Ba_nSiO_4:Ce~(3+),Li~+(CSBS:Ce~(3+))were synthesized by a high temperature solid-state reaction. The crystal field splitting and the centroid shift from the free ion energy of 5 d configuration were approximated from the spectrum for Ca_2SiO_4,Sr_2SiO_4 and Ba_2SiO_4 phosphors. The single-phase purity was checked by means of X-ray diffraction. Here,when the doped concentration of Ca~(2+) is less than 80%(m ≤1.6), we report the structural phase transformation from monoclinic system β-Ca_2SiO_4 to orthorhombic system α-Ca_2SiO_4. The phosphors excited by near-ultraviolet(NUV) light at wavelengths ranging from 200 to 400 nm demonstrate a broad asymmetric blue emission band. The emission peak wavelength redshifts firstly from 417 nm of Ca_2SiO_4 to 438 nm of Sr_(0.3)Ca_(1.6)SiO_4, and then blueshifts to 411 nm of Sr_2SiO_4, and the end of 401 nm of Ba_2SiO_4.These results indicate that the tunable blue-emission of the phosphors can be realized through changing the solid solution components, which has a potential use as a blue component for fabricated precision modulation LEDs light sources and auxiliaries of SSC plastics films for different plant growths.We discuss in detail the possible mechanism and energy diagram of the tunable blue luminescence in Ca_mSr_(2-m-n)Ba_nSiO_4:Ce~(3+),Li~+ phosphors.     

在还原条件下ti—Si—Ca—O系中的相关系和钛氧化物的硅热还原

研究了1300—1600℃温度间 Ti-Si-Ca-O 系的相关系。1300℃时 Ti-Si-O 亚系中 Ti_2O_3与 Ti_5Si_3和 SiO_2共存。硅化物Ti_5Si_4、TiSi、TiSi_2除了与金属硅之外,也和 SiO_2共存。1600℃时 Ti_5Si_3与 TiO+Ti_2O_3,Ti_2O_3+SiO_2,以及 SiO_2+Ti_5Si_4共存。具有40%(原子)Ti 的液态 Si-Ti 合金与 SiO_2共存。在 CaO-Ti_2O_3-SiO_2 亚系中有一种石榴石结构a=12.165±0.001的三元相 Ca_3Ti_2Si_3O_(12),还有二元化合物 Ca_2Ti_2O_5与 Ca_8Ti_6O_(17),发现后面这两种化合物是CaTiO_(1+x)和 Ca_4Ti_3O_(4+3x)固溶系组成部分,其中前者具有钙钛矿结构。发现在 CaO-Ti_2O_3—SiO_2系中能与所有三相组合物平衡的金属相是 Si 含量仅小量变化的化合物 Ti_5Si_3(熔点=2125℃).为了在1600℃时由硅热还原钛的氧化物得到液态金属和渣,必须用过量的 Si 来获得40%原子(52重量%)Ti(或低于此)的硅钛合金。     

新型蓝色长余辉荧光粉SrAl_2O_(4-y)N_y∶Eu~(2+),Dy~(3+)发光性能研究

采用高温固相反应合成了SrAl_2O_(4-y)N_y∶Eu~(2+),Dy~(3+)系列长余辉荧光粉,并研究了SrAl_2O_(3.75)N_(0.25)∶Eu~(2+),Dy~(3+)体系的晶体结构、光谱特性、余辉衰减曲线及热释发光曲线。X射线衍射分析结果表明,SrAl_2O_(3.75)N_(0.25)∶Eu~(2+)荧光材料属六方晶系,P6322空间群,晶胞参数a=b=5.14,c=8.462,γ=120°。荧光光谱测试结果表明,SrAl_2O_(3.75)N_(0.25)∶Eu~(2+)的激发光谱和发射光谱均为宽带谱,激发光谱位于283 nm~450 nm,发射光谱的峰值位于487 nm,属于Eu~(2+)的4f65d1→4f7跃迁发射。Eu~(2+)的掺杂量并不改变SrAl_2O_(3.75)N_(0.25)∶Eu~(2+)发射光谱的形状和峰值位置,但对相对发光强度有较大影响,Eu~(2+)的摩尔浓度为2%时相对发光强度最高。余辉衰减曲线表明,Sr_(0.97)Al_2O_(3.75)N_(0.25)∶Eu_(0.02),Dy_(0.01)的余辉衰减符合指数衰减规律,由初始的快衰减和之后的慢衰减两个过程组成。通过热释发光曲线对荧光材料中的陷阱能级进行计算,得出Sr_(0.97)Al_2O_(3.75)N_(0.25)∶Eu_(0.02),Dy_(0.01)的能级陷阱为0.42 V,掺Dy~(3+)有利于提高该荧光材料的初始发光亮度和余辉时间。     

La0.6Pr0.4Fe11.4Si1.6B0.2合金及其氢化物的磁热效应

研究了La0.6Pr0.4Fe11.4Si1.6B0.2合金及其氢化物La0.6Pr0.4Fe11.4Si1.6B0.2Hy的制备工艺与磁热效应。室温XRD分析与SEM成分分析表明La0.6Pr0.4Fe11.4Si1.6B0.2合金主相为NaZn13型立方结构(空间群为Fm-3c),存在富La相(空间群为P4/nmm)与富Fe相。氢化物La0.6Pr0.4Fe11.4Si1.6B0.2Hy的晶格常数a由合金的1.2295 nm增大到1.2491 nm。DSC测定氢化物的氢含量y约为1.7。磁性测量结果表明:氢化物La0.6Pr0.4Fe11.4Si1.6B0.2Hy的居里温度TC由合金的198 K增至325 K,提高了127 K。在0～1.5 T外磁场下合金与氢化物最大磁熵变-ΔSmMax均为9.1 J.kg-.1K-1。氢化物La0.6Pr0.4Fe11.4Si1.6B0.2Hy在室温下搁置190 d后物相与磁热效应基本保持不变。     

超导化合物YBa_2 Cu_3 O_x定向反应合成过程的动力学初探

借助测量Y_2Cu_2O_5-BaCuO_2混合物样品电阻的变化,研究了定向反应合成YBa_2Cu_3O_x超导化合物固相反应的动力学。反应遵循 其中α_t——t时刻的反应分数; k——反应速度常数。 研究确定反应过程是化学反应控制,反应激活能为893 kJ/(mol·K)_0Y_2Cu_2O_5-BaCuO_2二元系反应完成时间可表示如下: 1nt_1=-89.25+108781/T 对定向反应合成过程和由Y_2O_3-BaCO_3-CuO三元系混合物的合成过程的反应完成时间进行了比较。     

Bi_2(Sr,Ca)_3Cu_2O_(8+δ)系超导体输运临界电流密度

用输运法研究了阳离子对磁通钉钆的影响。在20T、5T 磁场下,铋组分不饱和试样的临界电流密度比组分符合化学计量比试样高2～6倍。但在无磁场情况下,两者具有相同的 J_c 值,且其H_(c2)值大致相同。这些数据表明,在 Bi_2(Sr,Ca)_3Cu_2O_(8+δ)     

Hybridization between microstructure and magnetization improvement in lead and RE co-doped BiFeO_3

The crystal structure,magnetic and electrical properties of Bi_(0.96)Pb_(0.04) FeO_3 and Bi_(0.92)Pb_(0.04)RE_(0.04)FeO_3(RE=La,Sm,Dy and Yb)polycrystalline samples were prepared by the flash autocombustion technique.X-ray diffraction(XRD)measurements show that the rare-earth doped compositions crystallized in rhombohedral symmetry of space group R3 c.The undoped sample consisted needle shape particles while rare earth substitution preferred platelet like particles as clarified from high resolution transmission electron microscopy(HRTEM).Morphological features were examined using field emission scanning electron microscopy(FESEM).Magnetization measurements showed that Yb~(3+) samples possessed the highest room temperature saturation magnetization while when Bi~(3+) ions were substituted by La~(3+) ions,a smaller M_S(0.28 emu/g)was obtained.The coexistence of ferroelectric and magnetic transitions was detected using DSC and χM,indicating the multiferroic characteristics of Bi_(0.92)Pb_(0.04)RE_(0.04)FeO_3 crystallites.The Néel temperature shifted upwards with decreasing the ionic radius of rare earth ion.Nice correlation was established between microstructure,morphology and magnetic properties in view of the contribution of magnetocrystalline and shape anisotropy in the magnetic parameters values.