蓝光激发的Na_2ZnSiO_4:Eu~(3+)红色荧光粉的合成及发光特性

以H3BO3作助熔剂,采用溶胶–凝胶法合成了Na2Zn Si O4:Eu3+红色荧光粉。用X射线衍射、荧光光谱分析对样品的结构及发光特性进行了表征,探讨了H3BO3助熔剂添加量和掺Eu3+量对Na2Zn Si O4:Eu3+发光性能的影响。结果表明:所得样品属于单斜晶系,样品的激发光谱主要由一系列线状谱峰组成,激发主峰为465 nm,归属于Eu3+的7F0→5D2特征跃迁。在波长为465 nm蓝光激发下发射红光,发射峰分别为578、591、613、653和701 nm,对应于Eu3+的5D0→7FJ(J=0,1,2,3,4)跃迁,发射主峰位于613 nm(5D0→7F2)处。当Eu3+和H3BO3的摩尔掺杂量分别为5%和0.8%时,样品的荧光发光强度最大。Na2Zn Si O4:Eu3+有望成为蓝光激发的白光发光二极管(w-LED)用红色荧光粉。     

Li2SrSiO4:Eu2+,Tb3+中Eu2+和Tb3+的发光特性和能量传递

用高温固相法在N2/H2=95/5(v/v)还原气氛下合成了Li2SrSiO4:Eu2+,Tb3+荧光粉发光材料,通过荧光光谱研究其发光特性,并从理论上探讨了Eu2+与Tb3+之间的能量转移类型。结果表明:该发光材料主发射峰值550nm,与Eu2+在4f7-4f65d1产生跃迁有关;通过掺杂,共存于Li2SrSiO4基质中的Tb3+通过电多级相互作用将能量传递给Eu2+;在500~650nm范围内对Eu2+具有很强的敏化作用,使其在主发射峰550nm的发射强度显著增强;当名义化学组成为Li2Sr0.995SiO4:0.005Eu2+,0.010Tb3+时,发光强度为最佳。     

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).     

M1.95P2O7:0.05Eu3+（M=Ba,Sr,Ca）红色荧光粉的制备及其发光性能

以尿素为燃料,采用溶液燃烧法合成出M2P2O7:Eu3+(M=Ba,Sr,Ca)红色荧光粉。利用X射线衍射和荧光光谱研究了激活剂Eu3+对3种荧光粉晶体结构和发光性能的影响。结果表明,制得样品分别为纯相的六方晶系Ba2P2O7、正交晶系Sr2P2O7和四方晶系Ca2P2O7。光谱分析表明,M2P2O7:Eu3+(M=Ba,Sr,Ca)的激发峰位置和发射峰位置均基本相同。M1.95P2O7:0.05Eu3+(M=Ba,Ca)发射红光,其对应于5D0→7F2电偶极跃迁的612nm发射峰强度高于对应于5D0→7F1磁偶极跃迁的588nm和593nm发射峰,说明Eu3+在M2P2O7(M=Ba,Ca)基质中处于非对称格位;而Sr1.95P2O7:0.05Eu3+发射橙红光,Eu3+在Sr2P2O7基质中处于对称格位。在394nm激发下,M1.95P2O7:0.05Eu3+(M=Ba,Sr,Ca)的色度坐标分别为(0.35,0.21)、(0.24,0.15)、(0.35,0.21)。这3种荧光粉均能被394 nm紫外光和464 nm蓝光有效激发,发射红光或橙红光。     

Y3Al5O12:Tb3+粉体的制备及其发光特性

以AlF3和H3BO3作助熔剂,经过固相反应,在1 350℃保温4 h成功制备出结晶较好、粒度分布均匀且粒径为0.5～2.0μm的Y3Al5O12:Tb3 (YAG:Tb)单相粉末样品.通过对样品的紫外光和真空紫外光激发下的发光特性研究,发现在147 nm真空紫外光的激发下,YAG:Tb样品的真空紫外激发光谱(λem=543nm)由位于140～190nm之间的铝酸根基团吸收、O2-→Y3 电荷迁移带吸收以及Tb3 的特征吸收组成,其发射光谱由激活离子的特征发射峰构成,发光强度有明显提高.     

SrMoO_4∶Tb~(3+)绿色发光材料的微波辐射法合成及发光性能

以活性炭粒为吸收剂采用微波辐射法合成了SrMoO4∶Tb3+绿色发光材料。用X射线粉末衍射仪、荧光分光光度计对样品进行了分析和表征,探讨了微波反应时间、Tb3+的摩尔掺杂量、助熔剂等对样品结构和发光性质的影响。结果表明:所合成的SrMoO4∶Tb3+晶体结构与SrMoO4相似,属四方晶系结构,I41/a空间群。样品的激发光谱是由位于200~350nm的1个宽带和350~500nm的一系列尖峰构成。宽带吸收与Mo--O的电荷转移和Tb3+的4f8--4f7 5d1跃迁过程有关,最强峰位于287nm左右。350nm以后的吸收峰是由于Tb3+的4f--4f跃迁引起的。发射光谱主要由4个发射峰组成:主峰位于544nm处,属于Tb3+的5 D4→7 F5跃迁发射;另外3个弱发射峰位于490、587、622nm处,分别属于Tb3+的5 D4→7 F6、5 D4→7 F4、5 D4→7 F3跃迁。当反应时间为30min,微波功率为中高火(560W),Tb3+摩尔量为0.06,助熔剂H3BO3的用量为4%(质量分数)时,样品的发光强度最大。     

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.     

Ca2B5O9Cl:Eu2+蓝色荧光粉的发光特性

采用高温固相法合成了Ca2B5O9Cl:Eu2 蓝色荧光粉,并对其发光性质进行了研究.该荧光粉在近紫外370 nm激发下的发射光谱为峰值位于453 nm的宽带发射,对应了Eu2 的4f65d→4f78S7/2特征跃迁发射.监测453nm的发射峰,得到其激发光谱为250～450nm的宽带,与产生350～410nm辐射的紫外发光二极管(ultraviolet light-emitting diode,UV-LED)管芯匹配很好.当CaCl2用量为理论用量的1.1倍,H3BO3用量为理论用量的1.3倍,Eu2 掺杂浓度为6%时,蓝光发射最强.Ca2B5O9Cl:Eu2 是适合UV-LED管芯激发的白光发光二极管用高亮度蓝色荧光粉.     

白光二极管用荧光粉LiBaPO_4:Tb~(3+)的制备及发光性质

采用高温固相法合成白光发光二极管用绿色荧光粉LiBaPO4:Tb3+,并研究荧光粉的发光性质。测定荧光粉的激发光谱和发射光谱,发射峰由位于436nm(5D3→7F4)、490nm(5D4→7F6)、544nm(5D4→7F5)、587nm(5D4→7F4)及621nm(5D4→7F3)的五组线状峰构成,对应Tb3+的特征跃迁,其中544nm处的最强,样品呈现绿色发光。激发光谱由4f75d1宽带吸收(200～280nm)和4f–4f电子跃迁吸收(330～390nm)组成,其中以380nm处的激发峰最强,可被紫外发光二极管(ultraviolet-light-emittingdiode,UV-LED)有效激发。研究Tb3+掺量(摩尔分数,下同)对发光亮度的影响,结果显示:当Tb3+掺量为9%时,荧光粉的亮度最高,之后出现浓度淬灭现象。Na+、K+和Cl–作为电荷补偿剂均能提高发光亮度,以Cl–作为电荷补偿剂的效果最好。Ce3+对Tb3+具有明显的敏化作用。结果表明:LiBaPO4:Tb3+是一种适用于白光发光二极管用的绿色荧光材料。     

绿色荧光粉Ca_9Al(PO_4)_7:Tb~(3+),Ce~(3+)的发光特性

采用固相法合成Ca9Al(PO4)7:Tb3+,Ce3+绿色荧光粉,研究了材料的发光性质。结果表明,以377 nm近紫外光作为激发源时,Ca9Al(PO4)7:Tb3+呈现出多峰特征,主峰位于491、545、589和623 nm,分别对应Tb3+的5D4→7F6,5D4→7F5,5D4→7F4和5D4→7F3跃迁发射,其中545 nm发射峰最强,从而材料整体发射绿光;监测545 nm发射峰,对应的激发光谱为多峰特征,覆盖300~390 nm;增大Tb3+的掺杂量,发现Ca9Al(PO4)7:Tb3+的发射强度逐渐增大,在实验范围内,并未出现浓度猝灭现象;通过添加A+(A=Li、Na和K)以及敏化剂Ce3+,有效增强了Tb3+在Ca9Al(PO4)7中的发射强度。测量了不同Tb3+掺杂量下材料的色坐标,发现Ca9Al(PO4)7:Tb3+的色坐标基本不变,位于绿色区域。     

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-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。     

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%。     

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.     

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