铽芳香羧酸丙烯酰胺共聚丙烯酸乙酯发光聚合物的合成与性能研究

采用先配合后聚合的方法,制备了5种新的铽芳香羧酸丙烯酰胺共聚丙烯酸乙酯聚合物.利用红外光谱、紫外光谱分析对它们的结构进行了表征;用热分析仪研究了它们的热性能;并采用荧光光谱仪对它们的发光性能进行了研究.结果表明,所合成的铽芳香羧酸丙烯酰胺共聚丙烯酸乙酯聚合物均具有良好的热性能和发光性能,其发光强度均随配合物单体含量的增加而增大.同时,铽配合物单体与丙烯酸乙酯单体聚合后,由于分子结构的改变,使配体的能量传递效率发生了变化,从而引起铽芳香羧酸丙烯酰胺共聚丙烯酸乙酯聚合物的发光强度大小顺序与铽芳香羧酸丙烯酰胺配合物单体的发光强度大小顺序不同.     

铕-噻吩甲酰三氟丙酮-活性配体三元配合物的合成及发光性能研究

以噻吩甲酰三氟丙酮为第一配体,顺丁烯二酸酐、十一烯酸、油酸、丙烯腈为活性第二配体,合成了四种新的反应型三元铕配合物。通过元素分析,EDTA配位滴定分析,红外、紫外、荧光光谱分析,对标题配合物的组成、结构进行了表征,并研究了它们的发光性能,结果表明,四种新的反应型三元配合物具有良好的发光性能,且配合物中引入了能与其它单体共聚的活性第二配体,为合成具有优异发光性能的键合型稀土高分子功能材料提供了一条新的途径。     

氨基硅烷改性芳香二酰氯及其稀土配合物的制备与荧光性能

以3-氨基丙基三乙氧基硅烷(KH550)与芳香二酰氯制备改性配体,然后与硝酸铽的六水合物反应制备出发光稀土铽配合物。研究了不同反应条件对铽配合物生成产率和荧光强度的影响,确定了最佳反应时间、温度和铽离子与改性配体的配比。并通过红外光谱、紫外光谱、EDTA滴定以及荧光光谱的测定,推测了铽配合物的结构,探讨了其能量传递过程。结果表明,配体经硅烷偶联剂改性以后,能较好地将吸收的能量传递给Tb~(3+),敏化其发光过程,从而表现出铽较强的荧光特征吸收峰,成功的制备了具有荧光性质的稀土配合物。     

室温固相法合成苯甲酸铕与苯甲酸铽荧光粉

以稀土氯化物、苯甲酸、六次甲基四胺为原料,采用固相反应法合成苯甲酸铕与苯甲酸铽配合物。TG-DTA数据显示,六次甲基四胺盐在200℃左右发生热分解;FT-IR、PL测试结果表明,加入六次甲基四胺后,苯甲酸转化成羧酸盐,与稀土离子形成稳定的配合物,合成配合物具有理想的光致荧光性能。     

2,3,5-吡啶三酸与重稀土配合物的合成、表征及光致发光性质

采用水做溶剂,用2,3,5-吡啶三酸做配体和重稀土铽、镝、铒、镱、镥、钇六种稀土元素的氯化物在常温下反应合成了六种重稀土的配合物。通过EDTA络合滴定分析,确定了六种配合物中稀土离子含量;并对配合物进行了熔点测定、红外光谱测试,并测试了铽和镝配合物的光致发光性质,结果表明,铽和镝配合物在紫外光的激发下具有良好的发光性质。     

Tb(p-ABA)2(acac)phen-TDI-MDA共聚物合成及其性质

以对氨基苯甲酸、β-二酮和邻菲哆啉为配体合成了一种高荧光强度、高缩聚活性的铽配合物单体，并将铽配合物单体与TDI，MDA进行共缩聚，合成了含稀土配合物的聚脲共聚物。通过元素分析、摩尔电导、红外光谱、X射线光电子能谱和荧光光谱对配合物和共聚物的结构和性质进行了表征。结果表明：配合物具有高的荧光强度，在DMF中配合物为非电解质，铽配合物参与了共缩聚反应，共聚物的发射光谱与配合物相似，荧光强度随铽配合物含量增加而增强。采用高浓度的酸碱对键合型聚脲共聚物和直接掺杂型稀土配合物／聚脲进行长时间浸泡，结果表明键合型聚脲共聚物比直接掺杂型稀土配合物／聚脲具有更好的荧光稳定性。     

邻氨基苯甲酸稀土固体配合物的光致发光

合成了一系列组成为Tb1-xYxA3(A=邻氨基苯甲酸,x=0～1.0)的固体配合物。利用红外光谱和荧光光谱研究了配合物的结构和荧光性质。红外光谱的结果表明,掺杂配合物的结构与未掺杂的邻氨基苯甲酸铽相似。荧光光谱的结果显示,Y3+对Tb3+的发光有显著的增敏作用,对荧光增敏的机理进行了探讨。     

铽及其掺杂对苯二甲酸冠醚配合物的合成与荧光性能研究

合成了铽及掺荧光惰性镧、钆、钇的铽冠醚对苯二甲酸配合物。通过元素分析、摩尔电导及红外光谱推测出了配合物的组成;实验结果表明,半径大的稀土离子与18冠6的氧原子直接配位,而半径小的稀土离子则通过水分子配位;对苯二甲酸作为桥连配体连接两个稀土冠醚配合物。测定了配合物的荧光激发光谱和发射光谱,表明铽配合物发出较强的荧光。探讨了配合物中的传能过程,结果表明,配体能较好地将吸收的能量传递给T b3+,不发光稀土离子(L a3+、G d3+和Y3+)对发光稀土离子(T b3+)具有很强的敏化作用,比较这三个含有惰性稀土离子的配合物,发现L a3+的敏化作用最强。     

稀土铕,铽β-二酮配合物的合成与发光性能

采用Claisen缩合反应合成了一种新型的β-二酮化合物1-(4-溴苯)-3-苯基丙烷-1,3-二酮(L),并以其为第一配体,邻菲罗啉(phen)为第二配体,合成出新型稀土铕,铽二元及三元配合物。通过元素分析、红外光谱、紫外光谱、荧光光谱对合成的配体及配合物进行了表征。元素分析确定了配合物的组成。红外光谱的分析表明第一配体L中的氧原子以及第二配体phen中的氮原子与稀土离子进行了配位。紫外光谱表明第一配体L为能量的给体,第二配体phen起协同作用。通过荧光光谱研究了配合物的发光性质,结果显示三元配合物的发光强度大于二元配合物,三元配合物Eu(L)3phen表现出Eu3+的特征发射,在593,615,653,701 nm处的发射峰分别归属于Eu3+的5D0→7Fj(j=1,2,3,4)能级间的跃迁,并且以位于615 nm处的5D0→7F2电子跃迁所发出的荧光强度最大;而铽配合物中并没有出现Tb3+的特征发射。进一步的研究表明,这是由于配体L的最低三重态能级较适合Eu3+的发射能级,配体L吸收的能量可以有效的通过Antenna效应传递给稀土中心离子,使得三元配合物Eu(L)3phen的发光强度较大。     

对苯基苯甲酸铕、铽配合物的合成、表征及荧光性能研究

分别合成了以对苯基苯甲酸为配体,铕、铽及掺杂铕、铽为中心的固态配合物。经元素分析、摩尔电导及差热-热重分析,推测其组成分别为:铕配合物:EuL3.3H2O、Eu0.5La0.5L3.3H2O、Eu0.5Y0.5L3.3H2O;铽配合物:TbL3.2H2O、Tb0.5La0.5L3.2H2O、Tb0.5Y0.5L3.3H2O(L=■-■-COO-。红外光谱、紫外光谱及核磁共振氢谱分析表明,对苯基苯甲酸的羧基氧原子与稀土离子配位。配合物的荧光光谱测定表明,铕系列和铽系列配合物都可发出其特征荧光,铕异核稀土配合物的荧光强度与相同配体的铕配合物相比,均有不同程度提高。     

Luminescence of Terbium Complexes Incorporated into Silica Matrix

Ｔｈｅｓｏｌ ｇｅｌｍｅｔｈｏｄｈａｓｓｈｏｗｎａｓｕｉｔａｂｌｅａｐｐｒｏａｃｈｆｏｒｔｈｅｐｒｅｐａｒａｔｉｏｎｏｆｎｏｖｅｌｌｕｍｉｎｅｓ ｃｅｎｔｍａｔｅｒｉａｌｓ .Ｍａｎｙｒｅｃｅｎｔｗｏｒｋｓｈａｖｅｆｏ ｃｕｓｅｄｏｎｔｈｅｄｅｖｅｌｏｐｍｅｎｔｏｆｓｏｌｉｄ ｓｔａｔｅｔｕｎａｂｌｅｄｙｅｌａｓｅｒｍｅｄｉａｕｓｉｎｇｏｒｇａｎｉｃｄｙｅｄｏｐａｎｔｓ[1 ,2 ]ａｎｄｔｒｉｓ( 2 ,2′ ｂｉｐｙｒｉｄｉｎｅ)ｒｕｔｈｅｎｉｕｍ (Ⅱ )ｃｏｍ ｐｌｅｘ[3 ,4 ] ｗｈｉｃｈｃａｎｈａｖｅｓｏｍｅｐｏ…     

Highly luminescent europium and terbium complexes based on succinimide and N-hydroxysuccinimide

The preparation of two highly luminescent europium(III) and terbium(III) complexes with succinimide(SI) and N-hydroxysuccinimide(NHSI) were reported,which were further investigated through elemental chemical analysis,thermal analysis,FT-IR,powder X-ray diffraction,SEM and fluorescence spectroscopy.Data collected through these analysis revealed the formation of the Eu(III) and Tb(III) complexes with the above mentioned ligands at a metal to ligand(M:L) molar ratio of 1:3.Interesting conclusions regarding the efficient sensitization through the coordination site of the lanthanide luminescent centers were retained from the photoluminescent spectra investigation.Strong luminescence emission was observed in case of Eu(III)-SI and Tb(III)-NHSI complexes while the corresponding Eu(III)-NHSI and Tb(III)-SI complexes exhibited no photo luminescent properties.Newly obtained luminescent lanthanide complexes may be of particular interest for various applications in optoelectronics.     

Ti—6242S合金在β区的锻造工艺研究

采用光学显微镜、扫描电和力学性能测试等设备了Ｔｉ－６２４２Ｓ合金相变点以上４５℃加热,变形量为７０％空冷的锻造工艺,经双重退火处理,获得细小网篮状组织。这种组织为α＋β两相区锻造下的等轴组织相比,不但具有良好的室温和高温力学性能,而且还提高了材料的高温持久、蠕变强度、冲击和断裂韧性,该合金的β区锻造工艺,放于加工航空发动机压气机盘模锻件。     

Synthesis, characterization and enhanced luminescence of terbium complexes with 2-pyrazinecarboxylic acid and butanedioic acid by inert-fluorescent lanthanide ions

Ten solid terbium complexes with 2-pyrazinecarboxylic acid (Hpyca) and butanedioic acid (BDAH) were synthesized via coprecipitation method and characterized by elemental, EDTA titration, inductively coupled plasma (ICP), thermogravimetry-differential scanning calorimetry (TG-DSC) and infrared (IR) analyses. The results showed that the complexes had the compositions of Tb(pyca)(BDA)·2H2O, Tb0.5Y0.5(pyca)(BDA)·2H2O, Tb0.5La0.5(pyca)(BDA)·3H2O, Tb0.5Gd0.5(pyca)(BDA)·2H2O, Tb0.7Y0.3(pyca)(BDA)·3H2O, Tb0.7La0.3(pyca)(BDA)·0.5H2O, Tb0.7Gd0.3(pyca)(BDA)·H2O, Tb0.6Y0.4(pyca)(BDA)·2.5H2O, Tb0.6La0.4 (pyca)(BDA)·2.5H2O and Tb0.6Gd0.4(pyca)(BDA)·3H2O. IR spectra indicated that the rare earth ions coordinated with the carboxylic oxygen atoms of Hpyca and BDAH. Luminescence spectra showed that the doped La3+, Y3+ or Gd3+ ions did not affect the luminescence emission peak positions, but remarkably increased the luminescent intensities of terbium complexes. Furthermore, the doped lanthanide complexes showed longer luminescence lifetimes and higher quantum yields than pure terbium complex. The enhanced luminescence efficiencies of Tb3+ ions in the doped complexes might result from the antenna effect of the two carboxylate ligands as well as the decrease of the self-quench of the Tb3+ ions induced by the doped lanthanide ions.     

Preparation and Luminescence Properties of LB Films Based on 4-Hexadecyloxybenzoic Terbium

LB films of 4-hexadecyloxybenzoic-terbium by using the subphase containing Tb^3 were prepared. The mono-layer behavior of 4-bexadecyloxybenzoic acid (HOBA) on the subphase containing rare earth ions was studied. IR and UV spectra show that the rare earth ions were bound to carboxylic acid head groups and the coordination took place between the polar head group and the rare earth ions. The luminescence spectra show that the LB films have the fine luminescence properties, and the LB films emit strong luminescence under UV light irradiation.     

Influence of La, Y, Gd, Cu, NH4^＋ Ions and DMSO on Luminescent Property of Terbium Complexes with Sulfosalicylate

Ｔｈｅｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｏｆｏｒｇａｎｉｃｌｉｇ ａｎｄｓａｓｆｌｕｏｒｅｓｃｅｎｔｍａｔｅｒｉａｌｓｈａｖｅｒｅｃｅｉｖｅｄｅｘ ｔｅｎｓｉｖｅａｔｔｅｎｔｉｏｎ .Ｔｈｅｕｓｅｏｆｆｌｕｏｒｅｓｃｅｎｔｏｒｇａｎｏ ｌａｎｔｈａｎｉｄｅｃｏｍｐｌｅｘｅｓｒｅｑｕｉｒｅｈｉｇｈｆｌｕｏ ｒｅｓｃｅｎｃｅｉｎｔｅｎｓｉｔｙａｎｄｌｏｗｃｏｓｔｃｏｍｐｌｅｘｅｓ .Ｉｎｒｅｃｅｎｔｙｅａｒｓ ,ｔｈｅｆｌｕｏｒｅｓｃｅｎｃｅｅｎｈａｎｃｅｍｅｎｔｏｆＴｂ(Ⅲ )ｏｒＥｕ(Ⅲ )ｃｏｍｐｌｅｘｅ…     

Synthesis, Characterization and Fluorescence Properties of Europium, Terbium Complexes with Biphenyl-4-Carboxylic Acid and o-Phenanthroline

Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3 , La3 and Gd3 ; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3 is raised by inert fluorescent rare earth ions (Y3 , Gd3 and La3 ), but in Tb3 hetero-nuclear rare earth complexes the intensity of Tb3 ions are quenched by the inert fluorescent rare earth ions.     

苯甲酸-铕-铽配合物的荧光光谱研究

合成了苯甲酸－ 铕－ 铽和苯甲酸－ 铕－ 铽－ 镧系列固体配合物,研究了它们的荧光发射光谱。结果表明,Ｔｂ３＋ 对Ｅｕ３＋ 的荧光发射有很强的敏化作用,而Ｅｕ３＋ 对Ｔｂ３＋ 的荧光发射有很强的猝灭作用;但Ｅｕ３＋ 和Ｔｂ３＋ 的荧光发射峰的位置基本上保持不变。     

Characterization of luminescent hydroxyapatite@terbium complex core-shell composites using chlorobenzoic acid as ligands

Three kinds of novel hydroxyapatite@terbium complex core-shell composites were synthesized with 2-chlorobenzoic acid, 4-chlorobenzoic acid, and 2,4-dichlorobenzoic acid as the ligand, respectively. The XRD, UV/vis absorption and FT-IR results show that terbium ions are coordinated with ligands and the corresponding complexes are successfully included into composites. SEM and EDS results reveal that Tb complexes are fully and homogenously coated on the surface of hydroxyapatite (HAP) microspheres consisting of a large number of nanosized crystals. The strongest luminescence properties are obtained when 2,4-dichlorobenzoic acid is used as ligand. The study on fluorescence lifetime of composites shows that the lifetime is inversely related to emission intensity. TGA-DSC results indicate that the core-shell composites have an excellent thermal stability. Therefore, the current core-shell structure provides a cost-effective route to manufacture of biocompatible and heat-resistant highly luminescent materials.