Yb~(3+)/Ho~(3+)/Tm~(3+)三掺杂ZnO微晶玻璃中的上转换白光（英文）

通过熔融淬冷及热处理方法制备出Yb~(3+)/Tm~(3+)、Yb~(3+)/Ho~(3+)共掺杂和Yb~(3+)/Tm~(3+)/Ho~(3+)共掺杂ZnO微晶玻璃,利用X射线衍射和透射电子显微镜表征了ZnO微晶在玻璃基质中析出。在980 nm激发下,该玻璃体系中可以清晰观察到分别源于Tm~(3+):1G4→3H6、Ho~(3+):5S2、5F4→5I8及5F5→5I8辐射跃迁产生的高效蓝光(477 nm)、绿光(545 nm)和红光(660 nm)上转换发光。上转换发射强度与激发功率依赖关系的数据表明,蓝光发射是三光子过程,而绿光和红光发射是双光子过程。通过优化Yb~(3+)/Ho~(3+)/Tm~(3+)共掺杂微晶玻璃中离子掺杂浓度可获得白光发射。980nm激发下2Yb~(3+)/0.1Ho~(3+)/0.01Tm~(3+)共掺杂和2Yb~(3+)/0.2Ho~(3+)/0.03Tm~(3+)共掺杂微晶玻璃上转换发光的CIE坐标分别为(X=0.32, Y=0.34)和(X=0.33, Y=0.32),非常接近标准白的CIE色坐标(X=0.33, Y=0.33),表明该材料在白光发射领域具有良好的应用前景。     

Er~(3+)/Ho~(3+)掺杂碲酸盐玻璃光谱性能和能量传递研究

采用熔融淬冷法制备了新型Er~(3+)/Ho~(3+)掺杂的多组分碲酸盐玻璃。测试了样品的吸收光谱、1.53μm发光光谱和上转换发射光谱,研究了980 nm激发下Er~(3+)/Ho~(3+)掺杂的碲酸盐玻璃的光谱性能和能量传递机理。结果表明:在Er~(3+)/Ho~(3+)掺杂碲酸盐玻璃中可以观察到明显的以525 nm,546 nm和659 nm为中心的绿色和红色发射。Ho~(3+)的共掺通过Er~(3+)与Ho~(3+)间存在良好的能量传递改善了上转换荧光强度,抑制了1.53μm的发光。在Ho_2O_3掺杂量为0.3mol%时Er~(3+)/Ho~(3+)共掺样品上转换发光达到最佳,可见Er~(3+)/Ho~(3+)掺杂的70TeO_2-13BaO-7La_2O_3-10GeO_2玻璃在光纤激光器上转换发光方面有潜在的应用前景。     

溶剂热法制备NaBiF_4:Yb~(3+)/Er~(3+)及掺杂Rb~+离子增强其上转换荧光

采用溶剂热法合成了Na Bi F_4:Yb~(3+)/Er~(3+)上转换发光纳米材料,讨论了在溶剂热阶段反应温度、反应时间对Na Bi F_4:Yb~(3+)/Er~(3+)物相组成、形貌及发光性能的影响。结果表明:在反应阶段,适当增加反应温度、延长反应时间,可以增强Na Bi F_4:Yb~(3+)/Er~(3+)的结晶度,进而提高上转换发光效率,但溶剂热阶段反应温度高于220℃时,容易生成金属铋。此外,通过Rb~+离子掺杂可进一步增强Na Bi F_4:Yb~(3+)/Er~(3+)的上转换发光强度。Rb~+掺杂量为5%(摩尔分数)时,绿光和红光分别增加至原来的1.73和1.5倍。最后基于荧光强度比(I_(FIR))技术,研究了样品在300～500 K温度范围的I_(FIR)变化曲线,结果表明:Na Bi F_4:Yb~(3+)/Er~(3+)样品在温度传感领域有潜在应用价值。     

Tm~(3+)/Ho~(3+)/Yb~(3+)掺杂Ga_2O_3-GeO_2-Li_2O玻璃的上转换发光性能研究

采用熔融淬冷法制备了Tm~(3+)/Ho~(3+)/Yb~(3+)掺杂的Ga_2O_3-GeO_2-Li_2O玻璃。测试了样品的拉曼光谱、吸收光谱、980 nm和808 nm泵浦下的上转换发射光谱。详细调查了在980 nm和808 nm激发下不同的Yb2O3掺杂含量对Tm~(3+)/Ho~(3+)掺杂的镓锗锂玻璃的上转换发射光谱的影响,分析了稀土离子间的能量传递。研究发现:980 nm泵浦下样品观察到明显的545 nm和657 nm发射和微弱的476 nm发射峰。随着Yb~(3+)浓度的增大,由于Yb~(3+)对Tm~(3+)和Ho~(3+)的有效的能量传递增强了红光和绿光发射强度,红光的增长率是快于绿光的,Yb_2O_3的掺杂量为0.7 mol%时I657/I545强度比率达到最高。808 nm激发下可以观察到弱的476 nm的蓝光和545 nm的绿光及强烈693 nm发射。     

Y_2O_3:Yb~(3+)/Er~(3+)纳米片的制备及其上转发光性能研究

采用共沉淀法制备了Yb~(3+)/Er~(3+)共掺的Y_2O_3上转换荧光材料,利用X-射线衍射仪(XRD)、扫描电镜(SEM)、荧光光谱仪(以980 nm激光器作为光源)对合成样品的结构、形貌、发光性能进行了表征。分析结果表明:所制备的样品物相与Y_2O_3基质的物相基本一致;在扫描电子显微镜观察下,Y_2O_3:Yb~(3+)/Er~(3+)呈片状;当用980 nm激光激发样品时,可以观测到波长位于525 nm、550 nm处的绿色发射和波长位于660 nm处的红色发射光谱,分别对应于Er~(3+)的2H11/2,4S3/2→4I15/2和4F9/2→4I15/2特征跃迁。     

Tm~(3+)掺杂65GeS_2-25Ga_2S_3-10CsI微晶玻璃光谱特性

采用适当的热处理工艺制备了系列掺Tm~(3+)的透明GeS_2-Ga_2S_3-Csl硫卤微晶玻璃。测试了基质玻璃和微晶玻璃样品的密度、显微硬度、红外光谱以及在800nm激光泵浦下的近红外及中红外荧光光谱。结果表明:热处理后样品析出的晶相颗粒为Ga_2S_3和GeS_2的混合体,晶粒尺寸限制在100nm以内;而原本掺杂在玻璃基质中的Tm~(3+)富集在析出的Ga_2S_3和GeS_2晶体的周围,引起了Tm~(3+)周围环境的改变。因此,热处理后的微晶玻璃样品的近红外和中红外荧光强度增强。     

Nd~(3+)/Yb_(3+)/Tm~(3+)共掺杂NaY(WO_4)_2纳米晶的制备及其上转换发光性能

采用水热法合成出Nd~(3+)/Yb~(3+)/Tm~(3+)共掺杂NaY(WO_4)_2纳米晶。通过X射线衍射、扫描电子显微镜、红外光谱、荧光光谱等,对合成样品的晶体结构、形貌和上转换发光性能进行表征。结果表明:合成的样品均为纯四方相的NaY(WO_4)_2,粒径在50~55 nm之间。利用聚乙二醇(PEG-2000)作为表面活性剂制得的上转换纳米粒子,尺寸小、分散性好并且具有一定的水溶性。在808 nm近红外光激发下,观察到469 nm处的蓝光发射峰以及539 nm处的绿光发射峰,其中蓝光来自Tm~(3+)的~1G_4→~3H_6能级跃迁,绿光由Tm~(3+)的~1D_2→~3H_5跃迁产生。并研究了共掺杂体系中Nd~(3+)→Yb~(3+)→Tm~(3+)的能量传递过程及其上转换发光机理。     

Tb3+/Gd3+/Ce3+/Sb3+和Eu3+/Bi3+/Sb3+共掺玻璃的发光性能研究

为了得到显色改善的绿色和红色发光玻璃,本文采用高温熔融技术制备了Tb~(3+)/Gd~(3+)/Ce~(3+)/Sb~(3+)和Eu~(3+)/Bi~(3+)/Sb~(3+)共掺杂的硼硅酸盐透明玻璃。通过对共掺样品紫外可见吸收光谱的分析和长波紫外激发下的激发光谱及荧光光谱的分析,研究了Tb~(3+)/Gd~(3+)/Ce~(3+)/Sb~(3+)和Eu~(3+)/Bi~(3+)/Sb~(3+)共掺杂离子在玻璃基质中的发光性能,结果表明,在高能紫外光激发下,Tb~(3+)/Gd~(3+)/Ce~(3+)/Sb~(3+)共掺杂样品发射典型纯正绿光荧光的能力较强,Eu~(3+)/Bi~(3+)/Sb~(3+)共掺杂样品发射红光荧光的能力较强。     

掺杂Er~(3+)、Yb~(3+)对玻璃陶瓷发光性能的影响

稀土离子Er~(3+)、Yb~(3+)掺杂的透明玻璃陶瓷,通过调整组分及热处理条件,可以实现对玻璃网络结构和玻璃化能力的调节,达到析晶可控与稀土在纳米晶相中重掺的目的。它兼具晶体和玻璃的一些优点,具有高发光效率、高透过率、高稳定性和发光波段可调等性能。而且其热导性和耐热冲击性比较好,使之更适合用作大功率激光工作物质。本文介绍了掺杂Er~(3+)、Yb~(3+)稀土离子的玻璃陶瓷发光机理,并探讨了其影响因素。     

烧结温度对Er~(3+)/Yb~(3+)共掺氟氧化物粉末上转换发光的影响

采用高温固相法在600～1100 ℃范围内选择6个不同烧结温度制备了系列相同配方的Er~(3+)/Yb~(3+)共掺氟氧化物上转换发光粉末.在室温下对各样品采用波长为980 nm泵浦光激发,肉眼均可观察到峰值位于658 nm、539 nm和523 nm处的上转换红光和绿光,分别对应于Er~(3+)的~4F_(9/2)→~4I_(15/2)和~4S_(3/2)/~2H_(11/2)→~4I_(15/2)能级跃迁,且红光强度大于绿光强度.通过比较,各样品的上转换图谱形状完全相同,而红绿上转换发光强度明显不同,800 ℃烧结制得样品的红绿荧光强度最强.样品的绿色荧光强度与红色荧光强度的比值随烧结温度升高而增加.通过各样品的X射线粉末衍射图谱(XRD)分析其成分结构,发现烧结温度对样品的成分含量有较大影响.通过测量不同烧结温度下制得样品的上转换发光强度与激发功率的变化关系,发现不同烧结温度可改变样品的上转换发光机理.     

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