Mn2+对掺Ce3+BiB3O6纳米材料发光强度的影响

采用溶胶-凝胶的方法合成了一系列掺杂Mn2+,Ce3+的BiB3O6纳米发光材料.通过激发光谱和发射光谱研究了其发光性质,并探讨了Mn2+对Ce3+发光性能的影响.BiB3O6:Ce3+的发射光谱有位于370nm和405nm处的2个发射峰,由于Mn2+对Ce3+的敏化作用,Ce3+在BiB3O6:Ce3+,Mn2+中的发光强度有了显著的增强.     

BaSO4∶Ce3+/Tb3+发光材料的制备与表征研究

采用溶胶凝胶-沉淀法在800℃退火处理后合成了 BaSO4-SiO2∶Ce3+/Tb3+及BaSO4∶Ce3+/Tb3+发光材料.通过X射线衍射(XRD)、傅里叶红外光谱(FTIR)以及激发光谱、发射光谱对材料的物相及发光性能进行了表征和分析.实验考查了 Ce3+离子浓度和正硅酸乙酯(TEOS)掺入对材料荧光性能的影响...     

稀土离子(Gd~(3+),Ce~(3+)/Ce~(4+),Eu~(3+))对Tb~(3+)掺杂硅酸盐玻璃发光性能的影响

研究了(Gd3+,Ce3+/Ce4+,Eu3+)对Tb3+掺杂硅酸盐玻璃发光性能的影响.结果表明:Tb3+掺杂硅酸盐玻璃可以发出弱蓝光(400～460 mm)和较强的绿光(480～600mm).Gd3+对Tb3+的发光起敏化作用,可提高TB3+掺杂硅酸盐玻璃的发光强度.在空气中熔制的玻璃中Ce3+和Ce4+同时存在,Ce3+对Tb3+发光起敏化作用;而Ce4+对Tb3+发光起淬灭作用.由于Ce4+比例比较高,CeO2加入导致TB3+发光强度降低,同时也缩短了Tb3+发光余辉.加入Eu2O3时,Eu3+自身发光分散了激发Tb3+发光的能量,使Tb3+的特征发射强度降低.     

Cr2O72-/Cr3+和Ce4+/Ce3+电解液作媒质间接合成对甲氧基苯甲醛

在高剪切混合乳化机搅拌下,通过对Cr2O72-/Cr3+和Ce4+/Ce3+两种媒质间接合成对甲氧基苯甲醛槽外反应的研究,得到合成对甲氧基苯甲醛的优选条件分别为:原料配比n(Cr2O72-):n(p-CH3O-C6H4-CH3)=1:6,反应温度80℃,反应时间10min,对甲氧基苯甲醛反应收率90.5%;原料配比n(Ce4+):n(p-CH3O-C6H4-CH3)=1:1,反应温度30℃,反应时间6min,对甲氧基苯甲醛反应收率97.1%.结果表明,Ce4+/Ce3+做媒质产品时-空效率较低,这是Ce4+/Ce3+媒质存在的本质缺陷;而Cr2O72-/Cr3+做媒质产品时-空效率提高近2倍,显著地增加产品的产量,提高了经济效益.     

Ce~(3+):LiYF_4和Ce~(3+):LiLuF_4晶体生长与其紫外光谱特征

采用提拉法在CF4气氛中生长高质量掺Ce3+的LiYF4和LiLuF4晶体.测试了晶体的紫外光谱,并从配位场理论角度解释了Ce3+在2种氟化物晶体中紫外光谱特性的差异.结果表明:Ce3+在LiYF4晶体的吸收谱宽度比在LiLuF4晶体中更宽.Ce3+:LiYF4晶体的吸收峰和荧光峰的位置相对Ce3+:LiLuF4晶体的出现紫移.认为其主要原因是由于在LiYF4晶体中,Ce3+和相邻的F的距离更近,Ce3+的d电子与F之间的相互排斥作用更大.     

Ca_3Sc_2Si_3O_12:Ce~(3+),Nd~(3+)近红外荧光粉的制备和发光性质

利用高温固相法在弱还原气氛中制备了Ca3-x-ySc2Si3O12:xCe3+,yNd3+近红外发光荧光粉。用X射线衍射确定了样品的相结构,并研究了样品的可见及近红外激发和发射光谱,发光强度,荧光寿命等随Ce3+,Nd3+掺杂量的变化。结果表明:Ca3-x-ySc2Si3O12:xCe3+,yNd3+体系中Ce3+的发射光谱和Nd3+的激发光谱的有效重叠,说明存在Ce3+到Nd3+的高效能量传递,Ce3+,Nd3+的掺杂量分别为x=0.1和y=0.07时,Ca3-x-ySc2Si3O12:xCe3+,yNd3+粉体具有最强的近红外发射。与单掺Na3+的样品相比,Ca3Sc2Si3O12中掺杂Ce3+和Nd3+后,样品的近红外发光增强近400倍。此外,初步分析了Ca3-x-ySc2Si3O12:xCe3+,yNd3+中Ce3+到Nd3+的能量传递机理。     

Ce3+与牛血清白蛋白的相互作用的研究

在模拟动物体生理pH值条件下,用荧光光谱法和紫外吸收光谱法研究了稀土离子铈[Ce3+和Ce2(CO3)3]与牛血清白蛋白(BSA)的结合反应. 探讨了Ce3+和Ce2(CO3)3对BSA的荧光猝灭过程机理,并分别计算了不同温度下Ce3+和Ce2(CO3)3与BSA的结合常数(KA)和实际热力学参数(DH,DG和DS),并判断了Ce3+和Ce2(CO3)3与BSA结合的作用力类型. 由于所求热力学常数都是DH<0,DS>0,由此可判断Ce3+和Ce2(CO3)3与BSA之间的作用力主要为静电引力. 实验结果表明,Ce3+和Ce2(CO3)3与BSA结合形成复合物,分别为：n(Ce3+):n(BSA)=1.8:1, n[Ce2(CO3)3]:n(BSA)=2.6:1. 导致BSA内源性荧光猝灭是由于分子内的非辐射能量转移而引起的静态猝灭.     

水热法制备SrF2:Ce3+,Tb3+荧光粉及其发光性质研究

采用水热法合成了具有立方相结构的Ce3+、Tb3+共掺杂的SrF2发光材料SrF2:Ce3+,Tb3+,利用粉末X-射线衍射( XRD)对其结构进行了表征,并研究了掺杂量、水热反应时间、激发波长对SrF2:Ce3+,Tb3+发光性质的影响.荧光光谱研究结果表明,SrF2:Ce3+,Tb3+在254 nm波长紫外光激发下...     

CeO2添加对(PbCa)(FeNb)O3介质陶瓷微观结构及微波性能的影响

研究了CeO2添加量对(Pb0.48Ca0.52)(Fe0.5Nb0.5)O3微观结构及介电性能的影响.研究表明当Ce4+含量≤2.2%(摩尔分数,下同)时,样品为单一钙钛矿相,并且Ce4+进入A位造成样品晶胞的收缩,而Ce4+进入B位造成样品晶胞的膨胀.当Ce4+含量＞2.2%时,样品中会出现未知相.样品介电常数随Ce4+含量的增加先增大,后减小,介电常数的增大是由于晶胞体积的收缩以及相对密度的增大;减小则是由于Ce4+的半径(0.087 nm)大于(Fe3++Nb5+)的平均半径(0.064 nm)以及体系中未知相的出现.此外,由于Ce4+的取代造成氧空位消除、相对密度增大以及晶粒尺寸增大,从而当Ce4+的含量超过一定值时,样品的品质因数得到提高.样品谐振频率温度系数随Ce4+取代量的增加先迅速下降,然后又逐步增加.这是由于Ce4+的取代使得B位键价增加,谐振频率温度系数τf下降;但当样品中出现未知相时,τf又增加.当Ce4+的含量为2.2%时,τf达到最小值3.5×10-6/℃,且此时样品介电常数εr及品质因数谐振频率的积Qf值分别为93.7,6 770 GHz.研究了CeO2添加(Pb0.48Ca0.52)(Fe0.5Nb0.5)O3样品中晶体结构与介电性能之间的关系.     

熔制气氛对Ce3+激活的Li2O-Al2O3-SiO2闪烁玻璃发光性能的影响

本文研究了熔制气氛对Ce3激活Li2O-Al2O3-SiO2闪烁玻璃发光性能的影响,同时采用XPS能谱研究了不同熔制气氛下制备的闪烁玻璃Ce3+/Ce4+价态变化情况,结果表明:Ce3+激活的Li2O-Al2O3-SiO2闪烁玻璃中,Ce离子以Ce3+与Ce4+两种价态存在,随着熔制气氛还原性的增强,Ce3+相对含量增加,闪烁玻璃发光强度随之增强;玻璃配合料中适量还原剂c粉的引入对闪烁玻璃的熔制具有积极作用,Si粉与铝粉由于还原性太强,引入会造成色心的产生.     

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.     

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.     

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.     

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