BaM_2ZnO_5∶Eu~(3+)(M=La,Gd)荧光粉的合成及其光谱研究

为了探索Eu3+在晶格位置中占据不同对称中心时的发光性质,采用高温固相法制备了BaM2ZnO5∶Eu3+(M=La,Gd)系列红色荧光粉,分别用X射线衍射(XRD)、扫描电镜(SEM)、荧光光谱(PL)对其晶体结构、形貌和发光性质进行了表征。结果表明,经1000℃烧结后可得到BaM2ZnO5(M=La,Gd)纯相,荧光粉的颗粒大小分布较均匀,粒径大约为3μm~5μm;BaM2ZnO5∶Eu3+(M=La,Gd)荧光粉可以被395 nm的近紫外光有效激发,BaLa2ZnO5∶Eu3+在595 nm处的发射峰为最强峰,对应于Eu3+的5D0→7F1(595 nm)磁偶极跃迁。Ba Gd2ZnO5∶Eu3+在627 nm处的发射峰为最强峰,对应于Eu3+的5D0→7F2(615 nm,627 nm)电偶极跃迁。     

掺杂离子对红色荧光粉NaLn_4(SiO_4)_3F∶Eu~(3+)(Ln=La,Gd,Y)发光性能的影响

利用高温固相法合成系列Na Ln4(Si O4)3F∶Eu3+(Ln=La,Gd,Y)红色荧光粉,用X射线粉末衍射仪和荧光分光光度计对荧光粉进行结构和性能表征,研究Eu3+浓度以及基质组成的变化对Na Ln4(Si O4)3F∶Eu3+(Ln=La,Gd,Y)发光性能的影响。在394 nm激发下,荧光粉Na La4-x(Si O4)3F∶x Eu3+中的Eu3+主要体现5D0→7F2(616 nm)和5D0→7F1(590 nm)跃迁发射,而且5D0→7F2和5D0→7F1跃迁发射强度比例随Eu3+浓度的增大而变化,较低浓度时5D0→7F1发射比5D0→7F2强,较高浓度时则刚好相反。在273 nm激发下,荧光粉Na La3.9-yGdy(Si O4)3F∶0.1Eu3+或Na La3.9-zYz(Si O4)3F∶0.1Eu3+中Eu3+的5D0→7F2(616 nm)发射随掺杂离子浓度增加而增强,而5D0→7F1发射强度变化不大。因此可以通过改变Eu3+浓度以及基质组成离子Gd3+或Y3+浓度对5D0→7F2和5D0→7F1发射强度加以调整,进而调整荧光粉的红光色度。     

白光LED用LaPO4:Eu3+红色荧光粉的合成与表征

利用水热法制备了性能稳定的红色荧光粉LaPO4:Eu3+,同时研究了不同的Eu3+浓度、煅烧温度对荧光粉发光性能的影响.通过X射线粉末衍射(XRD)和扫描电子显微镜(SEM)来表征荧光粉的晶体结构和颗粒大小及形貌;用激发光谱和发射光谱以及荧光衰减曲线来表征荧光粉的荧光性能.结果表明:未煅烧时前躯体主要是六方晶相LaPO4·0.5H2O,煅烧温度在900℃时,所制备样品为单斜相LaPO4:Eu3+;SEM图像显示5 at.%Eu3+掺杂LaPO4呈椭球形,颗粒长约为500 nm,宽约为300 nm.最大发射波长和激发波长分别为592 nm和393 nm,发射光谱中592 nm和612 nm的发射峰对应的是Eu3+离子的5D0→7F1和5D0→7F2跃迁.其荧光寿命为3.32 ms.     

Ho3+对二苯亚砜高氯酸铕配合物发光的影响

合成了高氯酸铕二苯亚砜和不同物质量比的高氯酸(Ⅲ)、钬(Ⅲ)二苯亚砜异核配合物(EuxHo1-x)(DPSO)7(ClO4)3.测定了配合物的组成、IR、粉晶荧光激发和发射光谱.荧光光谱表明虽然Ho3+的发射几率较高的5S2激发态能级高于Eu3+,但并未对Eu3+的发光产生敏化作用,相反当掺入0.002mol的Ho3+时即对Eu3+的发光产生猝灭作用.另外从Eu3+的荧光光谱知5D0→7F2的电偶极跃迁强度大大高于5D0→7F1的磁偶极跃迁,这表明铕(Ⅲ)在配合物晶体中处于非对称中心的位置.     

蓝光激发锡酸盐红色荧光粉的光谱性能

采用高温固相法合成了Sr2-xSnO4∶Eu3+x系列红色发光粉,该荧光粉属于四方晶系结构。以465 nm的蓝光激发样品,Sr2-xSnO4∶Eu3+x荧光粉发射红光,以Eu3+的5D0-7F2电偶极跃迁发光最强。该材料能非常好地吸收465 nm波长的光。研究了激活剂Eu3+的浓度对Sr2-xSnO4∶Eu3+x样品发光性能的影响。结果表明,Eu3+的最佳掺杂浓度为5%。     

Eu3+掺杂Sr2CeO4荧光体的制备、发光性能及能量传递

采用柠檬酸-凝胶法成功地制备了Eu3+掺杂的Sr2CeO4荧光体.用X射线粉末衍射、拉曼光谱、紫外可见吸收光谱和荧光光谱等分析手段研究了荧光体的结构、光致发光性能及能量传递.结果表明,Sr2CeO4∶ Eu荧光体的激发光谱由两部分组成一个宽的激发带和属于Eu3+的f - f跃迁的锐线谱(峰位是395nm、466nm、532nm),它的发射光谱中除了出现常见的发射峰如585nm(5D0→7F1) 、616nm(5D0→7F2)、655nm(5D0→7F3)和704nm(5D0→7F4)外,还包含有来自较高能级激发态5D1的跃迁的发射,即509nm(5D1→7F0)、534nm(5D1→7F1)、554nm(5D1→7F2).这些发射峰在其它基质材料中难以观察到.发射主峰位于616nm附近,没有出现5D0→7F0的跃迁发射,这表明Eu3+在Sr2CeO4基质中处于无反演中心或偏离反演中心的格位上.Sr2CeO4∶Eu荧光体中存在着从基质Sr2CeO4到Eu3+的能量传递.     

红色Sr1-2xNaxWO4∶Eux3+荧光体的制备与发光性能

采用传统高温固相法,以钨酸锶为基质材料,掺杂稀土Eu3+制备了可被紫色光有效激发的红色荧光粉Sr1-2xNaxWO4∶Eu3x+。通过测定与分析样品Sr1-2xNaxWO4∶Eu3x+的激发和发射光谱,发现激发光谱在395nm处吸收值最大,发射光谱的发射主峰位于613nm处,属于Eu3+的5D0→7F2特征跃迁。不同的Eu3+掺杂浓度下样品发光强度不同,当x=0.07时发光强度最佳。电荷补偿剂Na+对样品发光强度的影响很大,主要原因是Na+的加入会影响基质的晶体结构,当Na+的含量与Eu3+含量相同时样品发光强度最好,Na+含量增加到一定程度后基质结晶不完善,荧光体的发光强度急剧下降。     

微波辅助液相法制备CaMoO4∶Eu3+荧光粉

采用微波辅助液相沉淀法制备了Ca1-xMoO4∶ Eu3+(0.05≤x≤0.09)系列红色荧光粉.通过荧光光谱仪、SEM、XRD测试和表征了该荧光粉的荧光性能、形貌、结构.结果表明,当Eu3+掺杂量为0.07,烧结温度为900℃,保温时间为3h时,可获得性能最佳的荧光粉,在395 nm和465 nm波长激发下,在616 nm处出现了很强的发射峰,对应于Eu3+的5D0→7F2的跃迁.采用微波辅助液相沉淀法制备的荧光粉发光强度高于高温固相法所制备的荧光粉,适合白光LED用红色荧光粉.     

SrY2O4:Eu3+超细荧光粉的制备及光致发光性能研究

采用OP-10(表面活性剂)/异戊醇(助表面活性剂)/水/环已烷(油)W/O微乳液为反应器,以草酸盐沉淀为前驱物制备了SrY2O4:Eu3 超细荧光粉.通过热重及差热分析(TG-ETA)、X射线衍射(XRD)、扫描电镜(SEM)和荧光光谱观测,研究了SrY2O4:Eu3 超细荧光粉的制备条件、形貌以及光致发光性能.XRD结果表明,1000℃烧结2h可得到SrY2O4纯相.扫描电镜照片显示颗粒基本为橄榄球形,粒径约为70nm～100nm.分别以250nm和260nm的近紫外光激发样品,SrY2(1-x)O4:Eu2x3 超细荧光粉发出明亮的红光,对应于Eu3 的4f-4f跃迁,当Eu3 的掺杂浓度为9%(摩尔分数,下同)时,在610nm和615nm处的发光强度最大,而5D0→7F0和5D0→7F1跃迁的分裂表明Eu3 在SrY2O4晶格中占据了Y3 的两种不同格位.     

白光LED用LaF_3:Eu~(3+)红色荧光粉的制备与表征

采用水热法制备具有单一相六方晶系的LaF_3:Eu~(3+)纳米荧光粉.通过X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、光致发光光谱(PL)和荧光衰减曲线对LaF_3:Eu~(3+)纳米荧光粉进行表征. LaF_3:Eu~(3+)荧光粉的激发光谱主要由250 nm处的宽带(O2-→Eu3+的电荷转移跃迁)和一些尖峰(Eu3+f-f跃迁)构成,其中位于近紫外区396 nm处有一较强的激发峰.通过发射光谱探测Eu3+在LaF3晶体中的局部晶场环境.在298 K下激发光谱和发射光谱可知,在六方晶系的LaF3纳米晶体中的Eu3+晶格位置从D4h降至到C2v,这是由于晶格变化所造成的.在396 nm激发下,观测到较优掺杂浓度为10%的LaF_3:Eu~(3+)荧光粉在591 nm(5D0→7F1跃迁)处有强烈的红色发射峰.其发光性能表明,LaF_3:Eu~(3+)红色荧光粉在近紫外发光二极管领域具有潜在的应用价值.     

Superconducting Transition Temperature in YBa2Cu4O8/La2/3 Ca1/3 MnO3 / YBa2 Cu4O8 Heterostructure

YBa2Cu4O8/La2/3 Ca1/3 MnO3/YBa2Cu4O8 （ Y-124/LCMO/Y- 124） heterostructure was prepared by facing-target sputtering technique. The oscillatory superconducting transition temperature was observed when the thickness of LCMO d L is larger than critical thickness d L^CR. The metal-insulator transition temperature can only be detected at d L 〉 d L^CR. The dependence on the spacer layer in LCMO/Y-124 systems suggests strongly the interplay of ferromagnetic and superconducting couplings.     

Visible luminescence of lanthanide ions in Ca3Sc2Si3O12 and Ca3Y2Si3O12

The crystalline materials Ca₃Sc₂Si₃O₁₂ and Ca₃Y₂Si₃O₁₂ were characterized by different crystal structures, as the former is a cubic garnet, while the latter is an orthorhombic compound. We investigated the optical spectroscopy of these materials doped with several trivalent lanthanide ions and compared the results for the two hosts. Polycrystalline samples were prepared by solid state reaction, both undoped and doped with the trivalent lanthanide ions Eu³⁺, Tb³⁺ and Sm³⁺. Emission, excitation and Raman spectra of these materials were measured at temperatures ranging from 300 to 10 K. The optical spectra were assigned and discussed, and the effects of the crystal structure of the host on the spectroscopic behaviour were addressed. The technological potential of these compounds in the field of optical materials and devices was discussed.     

Al2O3La2O3Y2O3/Cu复合材料的电弧侵蚀特性研究

采用喷射沉积和内氧化法制备出Al₂O₃La₂O₃Y₂O₃/Cu复合材料,研究该材料在直流20 V/20 A的工作条件下触点的电弧侵蚀特性,并与Al₂O₃/Cu材料进行了对比分析.利用电子天平、扫描电镜等方法分析电弧侵蚀后触点的质量变化和表面微观结构.结果表明,通过添加Y₂O₃、La₂O₃稀土氧化物颗粒,可有效降低触头材料的材料转移量.Al₂O₃La₂O₃Y₂O₃/Cu材料的抗熔焊性和抗烧损性优于Al₂O₃/Cu材料的性能.在直流阻性负载条件下Al₂O₃La₂O₃Y₂O₃/Cu阳极触头表面形成凹坑,阴极触头表面形成凸起,触点表面显示出浆糊状凝固物和喷发坑等电弧侵蚀形貌特征.      

CaO—SiO2—Na2O—CaF2—Al2O3—MgO保护渣系的Al2O3吸收速率和粘度

采用CaO-SiO2-Na2O-CaF2-Al2O3-MgO渣系,通过测定熔渣的粘度和Al2O3吸收速率,研究连铸保护渣的Al2O3吸收速率与粘度及化学成分之间的关系。在一定条件下,当CaO/SiO2为1.2左右时,粘度达到最小值,Al2O3吸收速率达到最大值,分别为0.10?Pa*s、8.403×10-4?kg*m-2*s-1。随着渣中Na2CO3含量、CaF2含量和MgO含量的增加,粘度减小,Al2O3吸收速率增大。随着渣中Al2O3含量的增加,粘度增大,Al2O3吸收速率减小。粘度为Al2O3吸收速率的主要控制因素。随着熔渣粘度的增加,连铸保护渣的Al2O3吸收速率逐渐减小。     

CaO-La2O3-B2O3-Eu2O3转光玻璃的合成及荧光性质

X射线衍射研究表明CaO-La2O3-B2O3-Eu2O3体系的玻璃化温度在1025℃附近.荧光光谱和ESR谱研究表明,在CaO-La2O3-B2O3-Eu2O3玻璃体系中存在着Eu2+和Eu3+两种价态离子. 316, 360, 379, 394, 413, 462和532nm锐线激发峰和592,616和650红区发射峰分别对应Eu3+的f-f激发跃迁和5D0-7FJ (J=1,2,3)跃迁发射;351nm和427nm宽带激发峰和蓝区发射分别对应Eu2+的5d-4f激发跃迁和发射.     

Fracture Behavior in Cu46.5Zr46.5Al7 and Cu46.5Zr41.5Al7Y5 Bulk Metallic Glasses

The interplay between chemical composition, plastic behavior, and fracture modes of Cu_46.5Zr_46.5Al₇ and Cu_46.5Zr_41.5Al₇Y₅ bulk metallic glasses (BMGs) was investigated by compression tests and fracture surfaces analyses. The aim was to explore the possibility of coupling physical, chemical, and hardness properties, with adequate macroscopic compressive plasticity. Cylindrical test samples, having a height-to-diameter ratio equal to 2, were machined and ground from as-cast bars and were tested in compression between lubricated plates, the displacement being measured by a clip-gage inserted between the plates. Y free BMG engineering stress-strain curves show a plastic behavior consisting of successive sudden stress drops and linear reloading segments. A detailed analysis of these features was performed to yield a correlation between the plastic deformation steps and the released elastic energy associated with each serration.     

CaO--TiO2--Fe2O3三元系中Ca3TiFe2O8的生成机理

钒钛磁铁矿是烧结矿重要的原料之一,Ca₃TiFe₂O₈作为钒钛烧结矿中矿物被发现之后,其生成机理尚不明确.本文采用X射线衍射分析、元素能谱分析和TG-DSC分析相结合的方法,研究了Ca₃TiFe₂O₈的生成机理以及不同温度、CaO与TiO₂含量下Ca₃TiFe₂O₈的生成规律.实验结果表明,Ca₃TiFe₂O₈由Ca₂ Fe₂O₅和CaTiO₃反应生成,即CaO和Fe₂O₃反应生成Ca₂ Fe₂O₅;其后,与CaTiO₃反应生成Ca₃TiFe₂O₈.反应时间越长,Ca₃TiFe₂O₈的生成量越大,但反应温度对Ca₃TiFe₂O₈生成的影响并不明显.另外,还发现CaO含量越高,Ca₃TiFe₂O₈越易于生成,而且等摩尔Fe₂O₃和CaO下只要存在TiO₂,就会有Ca₃TiFe₂O₈生成.      

Effect of Fe2O3 Loading Amount on Catalytic Properties of Monolithic Fe2O3/Ce0.67Zr0.33O2 -Al2O3 Catalyst for Methane Combustion

Ce0.67Zr0.33O2-Al2O3 solid solution was prepared by the co-precipitation method. Fe2O3-based catalysts supported on the solid solution were obtained by the impregnation method. The article revealed that the optimal loading amount of Fe2O3 on Ce0.67Zr0.33 O2-Al2O3 in our experimental condition for catalytic combustion of methane was 8% （ mass fraction）. The prepared catalysts were characterized by BET, TPR, XRD analyses, and their catalytic activity was investigated after being calcined at 873 K and after being aged in water gas at 1273 K. When the loading amount of Fe203 was 8% （ mass fraction）, the catalyst held the highest activity, and the best temperature speciality and thermal stability. The complete-conversion temperature of methane for fresh and aged sample was 788 and 838 K, respectively. The range between the light-off temperature and the complete-conversion temperature was only 15 K. The characterization results of XRD indicated that Fe2O3 was well dispersed on the Ce0.67Zr0.33O2-Al2O3 matrix. The results of BET and TPR were in good harmony with the catalytic activity results.     

Magnetocaloric Effect of Ni56Mn18.8Ga24.5 Gd0.7 Alloy

Inrecent years materials with high magnetocaloriceffect (MCE) have attracted considerable attention ow-ingto its potential application as a magnetic refriger-ant .Many material systemsthat underwentthefirst-or-der magnetic transition have been found to exhibit agiant MCE. Their typical representatives areGd5(SixGe1 -x)4[1 ,2]and La (FexSi1 -x)13[3 ,4]alloys .Ni MnGa is aferromagnetic shaped memory alloy whichundergoes a reversible first-order structural phase tran-sition (SPT) with the …     

Al2O3-V2O5体系的热力学优化

在对Al₂O₃-V₂O₅体系相图、热力学数据以及晶体结构数据进行综述与评估的基础上,采用相图计算方法对Al₂O₃-V₂O₅体系进行热力学优化.液相采用修正的似化学模型进行描述,利用对近似处理液相中存在的短程有序.将液相模型的最大短程有序设置在AlVO₄处,将VO₄3-当作液相中V₂O₅的基本组成单元.体系中AlVO₄相看作线性化合物.计算结果很好的重现了选定的实验数据,获得了一套合理、可靠、自洽的模型参数用来描述体系中各相的热力学性质,为Al₂O₃负载V₂O₅型催化剂催化性能的提高打下坚实的基础.