掺铕长余辉铝酸锌荧光粉合成条件研究

以ZnAc2、Al(NO3)3和Eu(NO3)3为原料,采用燃烧法制备掺杂Eu的ZnAl2O4:Eu2+长余辉荧光粉。探讨加入不同量的稀土Eu(NO3)3、不同燃烧温度和不同燃烧时间条件下,合成的ZnAl2O4:Eu2+长余辉荧光粉的发光效果。结果发现,当稀土加入量n(Eu)/n(Al)1/25,燃烧温度500～700℃,燃烧时间30 min时,制得的荧光粉发光效果最好。     

磷钒酸盐红色发光粉的制备及性能研究

采用燃烧法合成了一种近紫外激发的Ca3((P,V)O4)2:Eu3+发光材料,用X射线衍射谱、荧光光谱对样品进行了表征。结果表明,荧光粉基质Ca3((P,V)O4)2具有畸变的Ca3(VO4)2的结构,VO34-取代了部分的PO34-,但Ca2+的半径与Eu3+接近,因此Eu3+容易进入晶格,表现出良好的发光性能。荧光光谱分析发现荧光粉可被376 nm紫外光激发,主发射峰值位于620 nm(Eu3+离子的5D0→7F2跃迁)的红光,同时详细研究了Eu3+离子掺杂浓度、引发温度及尿素用量对荧光粉发光性能的影响。     

红色荧光粉YAl3(BO3)4:Eu3+的制备及发光性能研究

以稀土氧化物、硝酸铝和硼酸为原料,高温固相反应制备了单相红色荧光粉YAl3(BO3)4:Eu3+,用X射线衍射和发射光谱对荧光粉末的结构和发光性能进行了分析.研究了煅烧温度、Eu3+掺杂量对其发光性能的影响.结果表明,反应物在1 250 ℃下煅烧可制得单相YAl3(BO3)4:Eu3+晶体,在YAl3(BO3)4:Eu3+晶体中,Eu3+取代了YAl3(BO3)4晶体中Y3+,占据了非对称中心格位.在394 nm的紫外光激发下,YAl3(BO3)4:Eu3+荧光粉具有很强的发光性能,与(Y,Gd)BO3:Eu3+荧光粉相比,最强发射线波长由596 nm变为618 nm,由橙红色光变为红色光,色纯度有了很大提高.Eu3+的最佳掺杂量为8%(物质的量分数).     

YVO4:Eu3+,Bi3+荧光粉的制备及荧光性能研究

用溶胶凝胶法在较低温度下制备了YVO4:Eu3+,Bi3+荧光粉,采用X射线衍射仪(XRD),扫描电子显微镜(SEM)及荧光分光光度计测试,研究了合成产物的结构、表面形貌,分析了在Eu3+含量一定的情况下掺杂Bi3+的浓度的变化对发光性能的影响.结果表明,溶胶凝胶法合成的YVO4:Eu3+,Bi3荧光粉为单相结构、粒径在1 μm左右、无团聚现象;Bi3+对Eu3+离子有敏化作用,在一定浓度下使荧光粉的发射强度增加.     

白光LED用Ca_6Sr_4(Si_2O_7)_3Cl_2:Ce~(3+),Eu~(2+),Sm~(3+)荧光粉的合成及其发光性质

采用传统的高温固相法合成了Ce3+,Eu2+,Sm3+离子分别单激活和三种稀土离子共激活的Ca6Sr4(Si2O7)3Cl2荧光粉,并通过X射线粉末衍射、荧光光谱和CIE色坐标对其结构和发光性质进行了研究。荧光粉Ca5.91Sr3.96(Si2O7)3Cl2:0.02Ce3+,0.04Eu2+,0.04Sm3+在365 nm激发下能发射高强度白光,其色坐标为x=0.2183,y=0.2187,有望成为一种新型白光LED灯用荧光粉。     

新型Sr2V2O7:Eu3+荧光材料的制备及表征

以高纯度的SrCO3、NH4VO3、Eu2O3和Yb2O3等为主要原料,采用高温固相法合成荧光粉。X-粉末衍射及荧光光谱证实合成了一种在可见光范围内有广泛吸收的发黄光的钒酸盐体系荧光粉。其中Eu3+的最佳掺杂摩尔浓度比为0.09,最佳煅烧温度为1223K。     

LED用的Gd2(MoO4)3:Eu3+红色荧光粉的制备和性能研究

本文利用液相沉积法合成白光LED用的Gd2(MoO4)3:Eu3+红色荧光粉,利用X射线衍射、荧光光谱以及扫描电镜进行系列表征,系统研究掺杂离子浓度、退火温度等条件对Gd2(MoO4)3:Eu3+荧光粉的发光性能影响。结果表明:当pH=7,退火温度为1100℃,Gd:Eu摩尔比例为1.8:0.2时,所合成的荧光粉为正交晶系的类白钨矿结构Gd2(MoO4)3化合物(20-0408),荧光粉在395 nm左右有高的激发效率,发射主峰位置位于615 nm是近紫外LED中一种比较有应用价值的红色荧光粉。     

白光LED用红色发光粉La_(9.33)(SiO_4)_6O_2:Eu~(3+)的制备和发光特性

采用高温固相法合成具有磷灰石结构的La9.33(Si O4)6O2:Eu3+红色荧光粉。该荧光粉的性质通过X射线粉末衍射、荧光光谱来表征。La9.33(Si O4)6O2:Eu3+的激发光谱主要由以285 nm为中心的宽谱峰以及一系列由Eu3+离子f-f跃迁的锐线峰组成,在近紫外区有一个最强的激发峰在393 nm。在393 nm激发下,可以观察到La9.33(Si O4)6O2:Eu3+在612 nm处产生强烈的红光。发光特性表明,La9.33(Si O4)6O2:Eu3+荧光粉可能成为潜在近紫外芯片用红色荧光粉。     

Eu~(3+)/Tb~(3+)/MoO_4~(2–)掺杂钨酸钙体系荧光粉的结构及其发光性能

采用化学共沉淀法合成了Ca0.75Mg0.2Tb0.02Eu0.03(WO4)1-x(Mo O4)x(x=0~1.0)系列荧光粉,并对荧光粉的晶体结构和发光性能进行了表征。结果表明:不同Mo O42–掺杂量的样品均为四方相Ca0.75Mg0.2Tb0.02Eu0.03(WO4)1-x(Mo O4)x固溶体。在273 nm波长紫外光激发下,随着x的增大,Eu3+离子的发光强度先增强后减弱,当x=0.6时发光强度最强,为未掺杂Mo O42–样品的6倍。Mo O42–共掺杂改变了稀土离子周围的配位环境和局部晶体场的对称性,促进Eu3+离子4f电子的超敏跃迁,提高Eu3+的O2–→Eu3+电荷迁移跃迁,增加基体、Tb3+离子与Eu3+离子之间的能量传递。     

Eu3+在LiSrPO4中的发光及浓度猝灭机理

采用高温固相法合成了白光发光二极管用LiSrPO4:Eu3+红色荧光粉.测量了LiSrPO4:Eu3+的激发和发射光谱,结果显示材料的发射光谱为一系列尖峰,主峰位于616 nm,具有很强的红光发射;激发光谱中O2-→Eu3+的电荷迁移态CTS (220～310 nm)非常低,Eu3+的f→f (310～500 nm)跃迁吸收很强,主峰位于393 nm,与InGaN(350～410 nm)管芯匹配.比较了LiSrPO4:Eu3+与LiCaPO4:Eu3+、LiBaPO4:Eu3+发射光谱的差异,这三种晶体中Eu3+占据的格位对称性按Ca、Sr、Ba顺序逐渐增加.根据Dexter理论判定Eu3+在LiSrPO4中的浓度猝灭机理为电四极-电四极(q-q)相互作用.加入电荷补偿剂Li+、Na+和Cl 均提高了LiSrPO4:Eu3+材料的发射强度.LiSrPO4: Eu3+是一种适合白光发光二极管激发的红色荧光粉.     

Ferroelectric Ceramics in the PbMg1/3Nb2/3O3-PbCd1/3Nb2/3O3 System

Solid solutions (1-x)PbMg_1/3Nb_2/3O₃ + xPbCd_1/3Nb_2/3O₃ with x = 0-0.30 are investigated with purpose to work out a capacitor ceramics with good dielectric properties and low sintering temperature. It is found that the perovskite phase forms at sintering near to 980°C and begins to decompose at higher temperatures. When x grows from 0 to 0.30, the Curie temperature linearly grows from -10°C to +25°C, the dielectric permittivity ε_m in the Curie point T_C decreases from 18000 to 6800 and the phase transition becomes more diffused. The dielectric permittivity at room temperature is rather high and the temperature stability is improved. The system is of interest, because it can serve as a base for working out some ceramic materials for capacitors with low sintering temperature, which needs of no special atmosphere at burning.     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇（BBMP）为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷（BrMMO）。讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响。通过实验确定的最佳工艺条件为：BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4h时,BrMMO产率为65%。最终产品经元素分析、IR和1HNMR检测确定为BrMMO。该试验工艺简单,原料易得,且溶剂便于回收、污染小。     

3-叠氮甲基-3-甲基氧丁环的合成

以三羟甲基乙烷与碳酸二乙酯为原料,经环化反应合成了3-羟甲基-3-甲基氧丁环(HMM O)。在低温下,HMM O与对甲苯磺酰氯反应生成3-磺酸酯甲基-3-甲基氧丁环(M TM O)。M TM O和叠氮化钠发生叠氮化反应形成叠氮单体3-叠氮甲基-3-甲基氧丁环(AMM O)。三步反应收率分别为76%,96%,85%。用核磁、红外、元素分析和DSC表征了化合物的结构与性能。结构鉴定表明为目标化合物AMM O。     

3-溴甲基-3-甲基氧杂环丁烷的合成

以2,2-二溴甲基丙醇(BBMP)为初始原料,通过与碱发生关环反应生成3-溴甲基-3-甲基氧杂环丁烷(BrMMO).讨论了碱的种类和用量对BBMP关环产率的影响以及反应体系中碱的浓度、反应温度和反应时间对合成BrMMO产率的影响.通过实验确定的最佳工艺条件为:BBMP与NaOH摩尔比为1.0∶1.1,NaOH醇溶液的质量分数为12%,反应温度为78℃,反应时间为4 h时,BrMMO产率为65%.最终产品经元素分析、IR和1HNMR检测确定为BrMMO.该试验工艺简单,原料易得,且溶剂便于回收、污染小.     

The Preparation and Crystal Structure of TlMnCl3, TlFeCl3, TlCoCl3 and TlNiCl3

The compounds TlMnCl₃, TlFeCl₃, TlCoCl₃ and TlNiCl₃ were prepared by heating T1C1 with the corresponding transition metal dichloride in an evacuated ampoule. Atomic positions were determined from powder photographs. All four compounds were found to be related to the perovskite type structure. TlMnCl₃ has a cubic structure, space group Pm3m, with a_o = 5.025 Å. The other three compounds are hexagonal, probable space group P6₃mc, with cell dimensions (in Å) a₀ = 6.976 and c₀ = 6.008 for the Fe compound, a₀ = 6.907 and c₀ = 5.981 for the Co compound and a₀ = 6.863 and c₀ = 5.881 for the Ni compound. The three hexagonal compounds are isomorphous. A measureable concentration of basal plane stacking faults was found to occur in TlFeCl₃ and also, to a lesser degree, in TlCoCl_3.     

Tunable color emission in LaScO3:Bi3+,Tb3+,Eu3+ phosphor

LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ (x = 0 − 0.04, y = 0 − 0.05, z = 0 − 0.05) phosphors were prepared via high-temperature solid-state reaction. Phase identification and crystal structures of the LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors were investigated by X-ray diffraction (XRD). Crystal structure of phosphors was analyzed by Rietveld refinement and transmission electron microscopy (TEM). The luminescent performance of these trichromatic phosphors is investigated by diffuse reflection spectra and photoluminescence. The phenomenon of energy transfer from Bi³⁺ and Tb³⁺ to Eu³⁺ in LaScO₃:xBi³⁺,yTb³⁺,zEu³⁺ phosphors was investigated. By changing the ratio of x, y, and z, trichromatic can be obtained in the LaScO₃ host, including red, green, and blue emission with peak centered at 613, 544, and 428 nm, respectively. Therefore, two kinds of white light-emitting phosphors were obtained, LaScO₃:0.02Bi³⁺,0.05Tb³⁺,zEu³⁺ and LaScO₃:0.02Bi³⁺,0.03Eu³⁺,yTb³⁺. The energy transfer was characterized by decay times of the LaScO₃:xBi³⁺, yTb³⁺, zEu³⁺ phosphors. Moreover absolute internal QY and CIE chromatic coordinates are shown. The potential optical thermometry application of LaScO₃:Bi³⁺,Eu³⁺ was based on the temperature sensitivity of the fluorescence intensity ratio (FIR). The maximum S_a and S_r are 0.118 K⁻¹ (at 473.15 K) and 0.795% K⁻¹ (at 448.15 K), respectively. Hence, the LaScO₃:Bi³⁺,Eu³⁺ phosphor is a good material for optical temperature sensing.     

2,2,3-三氯-3-苯基-3-(3-甲基苯甲酰基)丙腈的合成研究

以苯甲酰氯、四氯化碳、间甲基苯甲酰氰为原料,合成了标题化合物。重点考察了氰化过程中不同原料配比、反应温度、时间、溶剂和催化剂用量对收率的影响。实验结果表明,其最佳反应条件为:n(1,1,2-三氯-2-苯基乙烯)∶n(3-甲基苯甲酰氰)=1∶1.2,二氯甲烷为反应溶剂,3 mmol催化剂三乙胺,室温反应5 h,总收率达80.6%。     

Thermal analyses of poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

Thermal analyses of poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB–HV)], and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB–HHx)] were made with thermogravimetry and differential scanning calorimetry (DSC). In the thermal degradation of PHB, the onset of weight loss occurred at the temperature (°C) given by T_o = 0.75B + 311, where B represents the heating rate (°C/min). The temperature at which the weight-loss rate was at a maximum was T_p = 0.91B + 320, and the temperature at which degradation was completed was T_f = 1.00B + 325. In the thermal degradation of P(HB–HV) (70:30), T_o = 0.96B + 308, T_p = 0.99B + 320, and T_f = 1.09B + 325. In the thermal degradation of P(HB–HHx) (85:15), T_o = 1.11B + 305, T_p = 1.10B + 319, and T_f = 1.16B + 325. The derivative thermogravimetry curves of PHB, P(HB–HV), and P(HB–HHx) confirmed only one weight-loss step change. The incorporation of 30 mol % 3-hydroxyvalerate (HV) and 15 mol % 3-hydroxyhexanoate (HHx) components into the polyester increased the various thermal temperatures T_o, T_p, and T_f relative to those of PHB by 3–12°C (measured at B = 40°C/min). DSC measurements showed that the incorporation of HV and HHx decreased the melting temperature relative to that of PHB by 70°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 90–98, 2001