Influence of Molten Salt on Luminescent Intensity and Particle Size of Y2O3 ：Eu^3＋ Phosphor

The Y-Eu oxalate precursor was prepared with a homogeneous precipitation method. And the additives, Na2CO3, S, NaCl or their combination, were introduced into the precursor to prepare Y2O3 ：Eu^3＋ red phosphors at 1000 1300 ℃ for 2 h. The effect of molten salts on particle size and luminescent intensity was studied. The experimental results showed that the complex molten salt （Na：CO3 ＋ S ＋ NaCl） was conductive to enhance the luminescent intensity of Y2O3 ：Eu^3＋. The emission intensity of the phosphor prepared with these additives at 1300 ℃ was about 45% higher than that of the one prepared without molten salt, and about 11% higher than that of the corresponding commercial phosphor. Meanwhile, the particle size of Y2O3 ：Eu^3＋ phosphor was controlled effectively with the molten salt.     

Luminescent Properties of SrGa2S4 :Eu and Its Application in Green-LEDs

Phosphor SrGa2S4Eu2 was synthesized with a high temperature solid state reaction.Its absorption spectrum, photoluminescence spectra, and fluorescence lifetime were studied in details.The excitation spectrum extended from UV to visible light region, and matched the emission of GaN chip.(Sr1-xEux)Ga2S4 emits strong green light and the concentration quenching did not occur; while the thermal quenching was evident.The emission peak shifted to long wavelength with increasing Eu2 concentration because of the changing of the crystal field strength.The lifetime of Eu2 ion was in the order of microsecond, which was reasonable for d→f transition.The electroluminescence spectrum of as-fabricated PC-LED at IF=20 mA was measured and most of the blue light of blue-LED chip at 460 nm was absorbed by the phosphor and simultaneously down-converted into an intensive green light at 540 nm.The color coordinate was (0.32, 0.63).SrGa2S4Eu2 was a promising phosphor for GaN-based green LEDs.     

Synthesis of Spherical （Y, Gd） BO3 ： Eu^3＋ Phosphor Using W/O Emulsion System

Spherical （Y, Gd）BO3：Eu^3＋ phosphor particles with a narrow size distribution（2 -4 μm） was obtained by firing the Y-Gd-Eu-BO3 precursor prepared in a W/O style emulsion system. In the W/O emulsion system, kerosene, used as oil phase, was mixed with Span 80 and Tween 80 compounds which were employed as the emulsifier with an HLB （hydrophile-lipophile balance） value of 5.2- 5.3. Both rare earths （Y, Gd and Eu） nitrate and boric acid solution or ammonia solution were used as aqueous phase. The synthesis conditions, such as emulsion composition, emulsifying style, precipitation reaction process, reaction temperature, morphology control, and so on, were investigated, and the optimum synthesis conditions for preparing spherical （Y, Gd）BO3：Eu^3＋ phosphor was obtained. The phosphor was characterized by XRD, SEM, laser particle size analysis, emission and excitation spectrum under vacuum ultraviolet （VUV）, and so on. The phosphor synthesized using the water-in-oil emulsion method with median diameter （D50） of 2 - 4 μm shows agreeable photoluminescence （PL） property and sphericity. The main emission peak appears at about 593 nm, which corresponds to ^5D0→^7F1 transition （magnetic-dipole transition） of the Eu^3＋ ion. The cell parameters and powder diffraction data were indexed. The structure of the phosphor belongs to the hexagonal system with space group P63/m.     

钠离子对KNa4B2P3O13: Sm荧光粉发光性能的增强作用研究

通过高温固相法在硼磷酸盐KNa₄B₂P₃O₁₃基质中掺杂稀土Sm3+离子获得橘红色发光性能,研究了电荷补偿剂Na+对该荧光粉发光性能的影响,开展了粉末X射线衍射、红外光谱、紫外可见漫反射、荧光光谱、荧光寿命及量子效率等测试对材料的物相、形貌和发光性能进行了表征。研究结果表明,该荧光粉的荧光发射源于Sm3+的4G_5/2→6H_5/2（562 nm）、4G_5/2→6H_7/2（598 nm）和4G_5/2→6H_9/2（645 nm）跃迁,Na+的掺杂没有改变Sm3+特征发射峰的形状和位置,增强了其发光强度。Na+浓度为1%时,可使发光积分强度提高48%。此外,掺杂Na+对荧光粉的寿命和色坐标无明显影响,其色坐标均位于橘红色区域。      

Investigations on Valence-Change Behaviors of Europium Ions in Eu-Doped Aluminate and Silicate Phosphors

Compounds of Sr3Al2O6∶Eu, Sr4Al14O25∶Eu, and BaZnSiO4∶Eu were synthesized by high-temperature solid state reactions. The doping Eu3 ions were partially reduced to Eu2 in Sr4Al14O25∶Eu and BaZnSiO4∶Eu prepared in an oxidizing atmosphere, N2 O2. However, such an abnormal reduction process could not be performed in Sr3Al2O6∶Eu, which was also prepared in an atmosphere of N2 O2. Moreover, even though Sr3Al2O6∶Eu was synthesized in a reducing condition CO, only part of the Eu3 ions was reduced to Eu2 . The existence of trivalent and divalent europium ions was confirmed by photoluminescent spectra. The different valence-change behaviors of europium ions in the hosts were attributed to the difference in host crystal structures. The higher the crystal structure stiffness, the easier the reduction process from Eu3 to Eu2 .     

作为白光LED用铕掺杂氟化镧红色荧光粉的制备与光谱性能研究

采用水热法制备具有单一相六方晶系的LaF₃:Eu3+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LaF₃:Eu3+纳米荧光粉进行表征.LaF₃:Eu3+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D_4h降至到C_2v,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LaF₃:Eu3+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,LaF₃:Eu3+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.      

Sol-Gel Preparation and Luminescence Properties of BaMgAl10O17 ： Eu^2＋ Phosphors

The synthesis of BaMgAl10O17： Eu^2＋ （BAM） phosphors using the sol-gel method and their luminescence properties were reported. The blue-light emitting BAM was synthesized using citric acid and ethylene glycol as chelating materials. Emission of blue-light was obtained from these phosphors. The luminescent intensity increases as the temperature of heat treatment is increased, This study investigated the effects of the molar ratio of ethylene glycol to citric acid （Ф value）, with respect to the phase formation and luminescence properties of BAM. The variation of the Фvalue resulted in the change of the sol-gel reaction mechanism and the microstructures of the resultant powders. An increase in Фvalue leads to an increase in the rate of BAM phase formation. The photoluminescent intensity of the prepared phosphors increases with heating temperatures because of enhanced crystallization.     

熔盐法制备(La,Ce,Tb) PO4的工艺研究(

以NaCl和KCl为熔盐,采用熔盐法合成了(La,Ce,Tb)PO₄绿色荧光粉.利用XRD、SEM、激光粒度仪、光谱分析仪等测试和分析荧光粉物相、粒径、形貌及发光性能,主要考察了复合熔盐用量、合成时间及合成温度对荧光粉性能的影响,并对反应机理进行探讨.结果表明,复合熔盐与前驱体的摩尔比为2.5~3.5,在900 ℃保温3 h,可以得到性能良好的(La,Ce,Tb) PO₄绿色荧光粉,其发光亮度优于高温固相法.      

溶胶-凝胶法制备La2Ce2O7:Eu3+及其发光性能

采用溶胶-凝胶法（Sol-gel）合成La₂Ce₂O₇:Eu3+系列红色荧光粉,并研究煅烧温度、Eu3+掺杂浓度以及不同种类电荷补偿剂对样品发光性能的影响.通过XRD、SEM、荧光光谱对样品的晶体结构、形貌以及发光性能进行测量和表征.结果表明:实验所得样品主晶相为La₂Ce₂O₇,属于萤石结构. Eu3+及电荷补偿剂的掺杂没有改变其晶体结构.合成的样品在467 nm蓝光激发下发出612 nm的红光.样品的发光强度随煅烧温度以及Eu3+掺杂浓度的提高先增强后减弱,样品的较优的煅烧温度为1 100 ℃,Eu3+较优的掺杂浓度为10 %（摩尔百分比）.掺入电荷补偿剂可以有效增强样品的发光强度,其中掺入Li+后发光增强的效果最显著.      

阳离子引入对CsPF6:Mn4+红色荧光粉发光性能的影响

采用共沉淀法在室温条件下合成了CsPF₆:Mn4+荧光粉,研究了Li+、Na+、K+阳离子的引入对CsPF₆:Mn4+荧光粉发光强度的影响。所制备的系列荧光粉样品均为立方结构纯相。在蓝光激发下,呈现最强峰位于634 nm处的一系列窄带红色发射。加入K+和Li+后,发光强度增强,加入Na+后发光强度有所减弱,其中加入K+的CsPF₆:Mn4+荧光粉发光强度最强。CsPF₆:Mn4+, K+荧光粉的发射强度随着温度的上升先增强然后由于非辐射跃迁的增加而降低,在423 K时达到最大值,发射强度相较于未引入阳离子的荧光粉发射强度亦增强。阳离子的引入可以有效提升CsPF₆:Mn4+荧光粉的发光性能。      

微波辅助液相沉淀法合成Ca(MoO4)1-x(WO4)x:Eu3+红色荧光粉

以尿素为沉淀剂，采用微波辅助液相沉淀法合成了类球状双基质Ca(MoO₄)_1-x(WO₄)_x:Eu3+红色荧光粉，通过采用XRD、SEM、荧光光谱(PL)等现代分析技术对荧光粉的结构、形貌及发光性能进行了表征.结果表明，制备的Ca(MoO₄)_1-x(WO₄)_x:Eu3+红色荧光粉晶型完整，纯度高，为白钨矿结构；掺杂WO₄2-离子后，CaMoO₄:Eu3+红色荧光粉的发光性能明显增强，当WO₄2-离子的掺杂量x=0.4时，在395 nm激发下，在616 nm处的主发射峰的发光强度达到最大，掺杂浓度过高时会出现浓度淬灭现象.其较优的煅烧温度为1 000 ℃，煅烧时间为4 h.      

Preparation of BaMgAl10O17 ：Eu^2＋ and Its Phase Behavior in Microemulsion System

BaMgAl10O17 ： Eu^2＋ （BAM） was prepared in the microemulsion system and its phase behavior was studied. There exists a small region in the reverse microemulsion system where the dispersed particles are of spherical form. In this way, BAM blue phosphor with good dispersion can be synthesized. The microemulsion phase diagrams of the pseudo-ternary system （Triton X-100/cosuffactant-oil-BAM brine） were first established intuitively by the dilution method. The microstructure of microemulsions was determined through eyeballing, conductance technique, and polar optical microscopy. Its phase behavior is affected by various factors, such as temperature （room temperature, 30, 40 ℃）, oil, surfactants, and cosurfactants in microemulsions. According to the phase diagrams, the microemulsion system of Triton X-100/1-hexanol-hexane-BAM brine was chosen to prepare the precursor. The BAM phosphor can be obtained via sintering the precursor at a comparatively low temperature. The phosphors were characterized by XRD and vacuum ultraviolet （VUV） spectra.     

溶胶-凝胶法制备Sr2SiO4:Tb3+绿色荧光粉及其发光性能

采用溶胶-凝胶法合成了一系列适合紫外-近紫外激发的(1-X)Sr₂SiO₄:XTb3+(X=0,0.01,0.02,0.03,0.04,0.05,0.06)绿色荧光粉,并采用X射线衍射(XRD)、扫描电子显微镜(SEM)和荧光光谱(PL)研究了样品的结构及发光性能.由XRD的检测结果可知,合成样品属于单斜晶系的β-Sr₂SiO₄相.由SEM图可知,所有样品都呈无规则块状结构.当监测波长为546 nm,样品的激发光谱的主峰位于370 nm处,属于Tb3+的4f-4f特征跃迁吸收.当激发波长分别为285 nm和250 nm,所有样品在488 nm,547 nm,586 nm,623 nm处都出现了1个强发射峰,分别对应Tb3+的5D₄→7F₆、5D₄→7F₅、5D₄→7F₄和5D₄→7F₃电子跃迁.最强发射峰位于547 nm处,呈现特征为绿光发射.随Tb3+掺杂量增大,发射强度呈现出先增大后减小的变化趋势,即存在浓度猝灭效应.当Tb3+掺杂量为X=0.03时,样品的发光强度最大.      

助熔剂对Y3Al5O12:Ce荧光粉的影响

采用高温固相反应法合成了黄色荧光粉Y₃Al₅O₁₂:Ce,研究了助熔剂对Y₃Al₅O₁₂:Ce荧光粉发光特性的影响.XRD的测量结果表明加入合适的助熔剂有利于荧光粉的晶化,并且不引入杂相.选择H₃BO₄和SBL同时使用效果要好于单独使用一种助熔剂.助熔剂的加入可增大荧光粉的激发和发射光谱强度,并能有效降低荧光粉的中心粒径.      

酶催化分光光度法测定环境水中痕量钒

钒对牛血红蛋白模拟酶催化过氧化氢氧化罗丹明B体系有强烈的抑制作用, 据此建立了酶催化分光光度法测定痕量钒的新方法。试验从pH值、罗丹明B浓度、过氧化氢浓度、牛血红蛋白浓度和反应时间等方面探讨了体系的实验条件。在pH 9.8的NH₃·H₂O-NH₄Cl缓冲溶液中, 当罗丹明B、H₂O₂和血红蛋白的浓度分别为1.5×10^-5 mol/L、1.5×10^-4 mol/L和 2.0×10^-6 mol/L时, 测定钒的线性范围为3.1×10^-4 ~6.2×10^-3 g/L, 方法的检出限为2.1×10^-6 g/L。1 000倍Na⁺、K⁺、Cl^- 、NO₃^-、NH₄⁺ 、F^-、BrO₃^-, 500倍Ca²⁺、Fe³⁺ 、Al³⁺、 Mn²⁺、Ba²⁺、CO₃^2-, 100倍C₂O₄^2-, 5倍Cu²⁺对钒的测定没有干扰。对环境水样中痕量钒进行测定, 结果的相对标准偏差(n=7)为3.7%, 与萃取分光光度法的结果基本一致, t检验结果表明两种方法没有显著性差异。     

沉金后液中金、铂、钯、碲的组态特征及其碲捕集稀贵金属机制

铜阳极泥沉金后液是回收铂族金属铂、钯的重要原料来源.根据铜阳极泥氯化浸出过程稀贵金属可能发生的电极反应,分析了沉金后液中金、铂、钯、碲的存在价态,通过热力学计算绘制了金、铂、钯、碲的多形态组分图,并研究了单一金、铂、钯体系碲捕贵金属机制.沉金后液中稀贵金属金、铂、钯和碲的价态分别为Au3+,Pt2+,Pt4+,Pd2+...     

磷酸镧除氟的H+,Zn2+,La3+∥SO2-4,PO3-4-H2O体系中Zn2+的间接络合滴定

采用镧盐除氟剂LaPO₄对锌电解液除F时,由于La³⁺和PO^3-₄的存在,H⁺,Zn²⁺,La³⁺∥SO^2-₄,PO^3-₄-H₂O体系中Zn²⁺不能直接用传统的滴定法测定。通过向待测液中加入适量NH₃·H₂O-NH₄Cl缓冲溶液络合Zn²⁺(Zn₃(PO₄)₂溶于氨性溶液),使La³⁺进入固相,抽滤、洗涤沉淀以分离Zn²⁺和La³⁺,收集滤液用EDTA(铬黑T作指示剂)滴定Zn²⁺,建立了间接络合滴定该体系中Zn²⁺的方法。实验结果表明:缓冲溶液采取较高的浓度配方、冲洗液采用稀释的缓冲溶液为宜。对于含0.1~1.0mmol Zn²⁺的样液,确定缓冲溶液为54g NH₄Cl溶于水,再加入350mL NH₃·H₂O,定容至1L,用量为20mL;冲洗液为缓冲溶液(1+2);为便于沉淀转移,加入沉淀La³⁺理论量1.1倍的F^-(La³⁺物质的量的3.3倍),可使沉淀转为不易于粘附玻璃的LaF₃。方法的定量限为0.01mol/kg。吸取含Zn²⁺在0.1~1.0mmol的H⁺,Zn²⁺,La³⁺∥SO^2-₄,PO^3-₄-H₂O体系平衡液,按照实验方法测定Zn²⁺,结果的相对标准偏差(RSD,n=6)小于0.1%,加标回收率为99%~100%。     

聚L-苏氨酸修饰电极方波溶出伏安法测定铅

在pH 3.5的NaAc-HAc缓冲液中,用循环伏安法制备聚L-苏氨酸修饰玻碳电极,探讨了Pb²⁺在修饰电极上的方波阳极溶出伏安特性,建立了方波阳极溶出伏安法测定Pb²⁺的方法。在最佳实验条件下,铅离子浓度在5.00×10^-8～7.50×10^-6 mol/L范围内与峰电流呈良好的线性关系,检出限为5.0×10^-9 mol/L。测定2.50×10^-6 mol/L Pb²⁺,当相对误差在±5%时,至少1 000倍K⁺、Na⁺、SO₄^2-、PO₄^3-、NO₃^-、Cl^-、Ca²⁺、Ba²⁺、Mn²⁺、Mg²⁺、Al³⁺、Zn²⁺、Fe³⁺、Cr³⁺、Co²⁺、Cd²⁺,200倍Cu²⁺不干扰Pb²⁺的测定。按照实验方法测定2个污水样中痕量铅,结果的相对标准偏差(RSD,n=6)分别为1.4%和2.4%,加标回收率分别为99%和103%。     

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.     

纳米TiO_2修饰的涂碳型PVC膜汞离子选择电极的研制与应用

制备了以纳米TiO2为修饰剂的涂碳型PVC膜汞离子选择电极,并用于汞离子的测定。对比裸碳电极、普通涂碳型汞离子选择电极和纳米TiO2修饰的涂碳型PVC膜汞离子选择电极在1.0×10-3 mol/L铁氰化钾溶液中的循环伏安图,发现纳米TiO2修饰的涂碳电极的氧化还原峰电流明显增加,且可逆性良好。对比普通涂碳电极和纳米TiO2修饰涂碳电极的响应曲线,发现纳米TiO2修饰涂碳型汞离子选择电极的Nernst响应范围更广,为1.0×10-2~1.0×10-6 mol/L,级差为30mV/pC。而且,纳米TiO2修饰涂碳型汞离子选择电极比普通涂碳电极的pH值范围更广。此外,与普通电极相比,修饰电极的检测下限更低,为4.5×10-7mol/L。常见的离子如Cu2+、Cd2+、NH4+、Zn2+、Cl-、Ca2+、Fe3+、K+、Na+、I-、Fe2+、Mg2+、Al 3+、SO42-、CH3COO-、NO3-等的选择性系数均小于0.01,在室温下电极的使用寿命约为3个月。电极用于电位分析法测定实际污水样品中汞离子,测定结果与原子吸收光谱法结果相一致,相对标准偏差为1.9%~2.4%。