含有萘酰亚胺单元的铕配合物合成及其发光性能研究

通过在邻菲哕啉中性配体上引入萘酰亚胺发色团，合成了新型含有萘酰亚胺单元的铕配合物Eu（DBM）3（PNI—phen）．通过控制激发，可以得到具有萘酰亚胺和Eu^3＋特征友射的荧光光谱．通过荧光光谱和激发光谱研究了铕配合物的能量传递及发光机制．     

柠檬酸-邻菲哕啉-稀土三元配合物的合成与表征

在无水乙醇溶液中,以邻菲哆啉（Phen）、柠檬酸（H3Cit）为配体,合成了7种稀土三元固体配合物。通过元素分析、摩尔电导率测定、红外光谱和热重差热分析等手段确定配合物的组成为RE（Cit）·Phen·2H2O（RE=La^3＋,Pr^3＋,Nd^3＋,Sm^3＋,Eu^3＋,Tb^3＋,Dy^3＋）。     

国内工业陶瓷文献题录及文摘（四十六）

2012124 Y3Al5O12：Eu^3＋荧光材料的合成及其真空紫外发光特性·硅酸盐学报，2012，04 采用凝胶-燃烧法合成了掺Eu^3＋的Y3Al5O12（YAG：Eu^3＋）荧光粉。分别采用X射线衍射（XRD）、扫描电子显微镜（SEM）、发光光谱等测试手段分析了不同温度下煅烧所得粉体的物相、形貌与发光性质。     

铕高分子配合物荧光强度与铕离子浓度的关系

稀土离子发光材料性能优良,既可电致发光又可光致发光,广泛应用于生物分析化学,激光材料,防伪商标等领域。本文以邻菲哕啉为小分子配体,聚丙烯酸-甲基丙烯酸甲酯为高分子配体,制备铕的高分子荧光配合物,研究了配合物中荧光强度与铕离子浓度的关系,发现Eu^3＋的浓度在1．25×10^-5mol／L和2．0×10^-4mol／L之间配合物的荧光强度与Eu^3＋的浓度呈线性关系,其加标回收率为98．6—101．3％,在该浓度范围内可对配合物中Eu^3＋浓度进行定量测定。     

开链冠醚Schiff碱配体与过渡金属离子相互作用研究

合成了开链冠醚Schiff碱配体H2L（H2L=N,N′-双（邻羟苯亚甲基）-3,6-二氧杂-1,8-二氨基辛烷）.详细研究了该配体在不同溶剂中和过渡金属离子存在下的荧光光谱,探讨了溶剂极性和不同金属离子对其荧光光谱的影响.结果表明：溶剂的极性和金属离子对其荧光性质有较大影响,随着溶剂极性的减小,配体的荧光增强,且谱峰发生蓝移.金属离子Zn2＋、Cd2＋对配体具有荧光增敏作用,Ni2＋、Cu2＋具有荧光猝灭作用.探讨了配体与金属离子结合的pH范围,结果显示最佳pH值为7—8.     

Y2O3：Eu^3＋薄膜的制备及发光性能的研究

以稀土氧化物为原料，用溶胶-凝胶法制备前驱液，加入适量的聚乙烯醇做成膜物质，用浸渍拉提法在石英玻璃表面上得到均匀的薄膜，然后经过适当的干燥和热处理得到Y2O3：Eu^3＋发光薄膜．讨论了Eu^3＋的掺杂浓度和热处理温度对薄膜发光性能的影响．试验表明：Eu^3＋的最佳掺杂浓度为8％（摩尔分数），薄膜的发光性能随热处理温度提高而增强，当热处理温度达到700℃后，薄膜的发光性能基本上稳定．同时用原子力显微镜和X射线衍射分析了薄膜的表面形貌和结构．     

YVO4：Eu^3＋，Bi^3＋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：Eu^3＋，Bi^3＋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Bi^3＋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：Eu^3＋，Bi^3＋荧光粉为单相结构、粒径在1um左右、无团聚现象；Bi^3＋对Eu^3＋离子有敏化作用，在一定浓度下使荧光粉的发射强度增加。     

Gd3Al5O12：Eu^3＋柠檬酸盐硝酸盐燃烧法合成及其发光性能研究

采用柠檬酸盐硝酸盐燃烧法，在较低的温度（900℃）下成功地合成单一晶相Gd3Al5O12：Eu^3＋发光粉体，紫外激发荧光光谱分析表明，粉体615m和593m荧光发射源于Eu^3＋的^5D0-^7F2和^5D0-^7F1跃迁．该方法中各工艺条件（如pH值、柠檬酸／金属离子比、煅烧温度）对Gd3Al5O12：Eu^3＋发光性能均有影响，通过试验得出了获得最佳发光性能荧光粉体的工艺参数．     

PDMS改性蓖麻油基水性聚氨酯的制备及防污性能

本研究以低成本的二甲基二甲氧基硅烷为主要原料，通过水解缩合反应制备合成了聚二甲基硅氧烷（PDMS），进而将其引入蓖麻油基水性聚氨酯（CWPU-SOP）中制备了具有防污性能的蓖麻油基水性聚氨酯(PDMS/CWPU-SOP)。结果表明，当PDMS引入量为8%时，与CWPU-SOP薄膜相比，PDMS/CWPU-SOP薄膜接触角提高了25?，达110?，PDMS/CWPU-SOP薄膜的吸水率下降了7%，为15%；PDMS提高了薄膜疏水性和耐水性。PDMS/CWPU-SOP薄膜在不同酸碱性的液滴在其表面可自由滚落且不留痕迹，具有一定的防污性能。     

BaMoO4：Eu^3＋红色荧光粉的制备及发光性质

采用柠檬酸溶胶-凝胶法制备了BaMoO4：Eu^3＋红色荧光粉,差热（DSC）和X射线衍射（XRD）研究结果表明,经过700℃高温烧结后可得到BaMoO4纯物相。粒度分析结果表明,经700℃烧结后样品的粒径约为200nm,随着烧结温度的升高,产物的粒径明显增大,当烧结温度为800℃时,样品的粒径约为500 nm。分别以392 nm的近紫外光和462 nm的可见光激发样品,BaMoO4：Eu^3＋荧光粉发红光,对应于Eu3＋的4f-4f跃迁,其中以615nm附近的5D0→7F2电偶极跃迁发光最强,当Eu3＋的掺杂浓度约为25 mol%时,在616 nm处的发光强度最大。荧光粉在392 nm和462 nm的吸收分别与紫外光和蓝光LED芯片相匹配。因此,BaMoO4：Eu^3＋荧光粉是一种可能应用在白光LED上的红色荧光材料。     

温度控制的Eu3+和Dy3+掺杂α-NaYF4微晶玻璃的荧光光谱研究

采用熔融冷却退火法制备了Eu3+单掺杂和Eu3+-Dy3+共掺杂的四方相α-NaYF4微晶玻璃,通过x射线衍射研究了Eu3+掺杂的α-NaYF4微晶玻璃的结构。在25~300℃温度范围内,测试了Eu3+单掺杂和Eu3+-Dy3+共掺杂α-NaYF4微晶玻璃的变温光谱,研究了温度对Eu3+和Dy3+发射光谱的调制作用。结果发现温度的增加导致了Eu3+和Dy3+离子发射峰的荧光强度逐渐减弱。     

Silica encapsulating lanthanum complexes using the sol–gel technique

BACKGROUND: Because of its properties, silica gel is an excellent host for different compounds. Many types of chemical species (organics, organometallics, proteins, enzymes, etc.) can be encapsulated in xerogels, and the sol–gel technique has been shown to be very useful for this aim. RESULTS: Some host–guest systems based on silica and complexed lanthanum were prepared in order to develop fluorescence properties. Three pathways were used to prepare such systems: (1) obtaining the lanthanum complex with a dimethylsiloxane‐based ligand and its incorporation into a silica network; (2) preparation of a silica network having hydroxyazomethine groups and in situ lanthanum complexation; and (3) preparation of polydimethylsiloxane (PDMS)/silica composites that possess hydroxyazomethine groups on the silica and in situ lanthanum complexation. The sol–gel technique was used in all cases. CONCLUSION: The photophysical properties of the prepared compounds were evaluated using fluorescence spectroscopy. The investigations revealed that the systems belonging to the second series are the most fluorescent. In the third series, the presence of PDMS provokes a decrease of the fluorescence intensity, until its complete quenching when the PDMS content exceeds a certain threshold value. However, there is a range of silica/PDMS ratio for which fluorescent free‐standing films can be obtained. The presence of complexed lanthanum induces changes in the morphology of the silica/PDMS matrix, as evidenced by scanning electron microscopy studies. Copyright © 2008 Society of Chemical Industry     

Cracked titanium film on an elastomeric substrate for highly flexible,transparent, and low-power strain sensors

Strain-dependent cracking behaviors in thin titanium (Ti) films on polydimethylsiloxane (PDMS) substrates were systematically investigated for their application to sensitive, flexible, transparent, and portable strain sensors. When uniaxially elongated, vertical cracks were developed in the low-strain range, and beyond a critical strain, tilted cracks appeared to intersect the vertical cracks. The cracking behaviors were also dependent on Ti film thickness. The varying strain-dependent crack patterns produced a significant resistance change in response to the applied strain, particularly, in the high- and broad-strain range. For a 180-nm-thick Ti film on PDMS substrate, a gauge factor of 2 was achieved in the range of 30% to 50% strain. The operation power was extremely low. All the Ti films on PDMS substrates were transparent, highly flexible, and very easy to fabricate. These results suggest that cracked Ti films on PDMS substrates could be a viable candidate for realizing a low-cost, flexible, transparent, and portable strain sensor.     

Novel functional polymers: Poly(dimethylsiloxane)–polyamide multiblock copolymer. IV. Gas permeability and thermomechanical properties of aramid–silicone resins

Poly(dimethylsiloxane) (PDMS) and aromatic polyamide (aramid) multiblock copolymers (PASs) ranging from 26 wt % to 75 wt% in PDMS content were prepared and cast into transparent, ductile, and elastomeric films from N,N′-dimethylacetamide solutions. The gas permeation properties and dynamic thermomechanical properties of the PAS films were investigated. It was found that the PASs containing < 75 wt % of PDMS had two-phase morphologies due to the great difference between the solubility parameters of the two components, in spite of the relatively low molecular weight of each segment. PASs containing ≥ 35 wt % of PDMS showed the PDMS continuous phase and interfacial mixing occurred clearly between the two phases at the higher PDMS contents. PAS containing ≥ 53 wt % of PDMS showed high enough gas permeability compared with conventional silicone rubbers. The gas permeation properties can be well predicted by the PDMS contribution to the continuous phase rather than by the modulus behaviors alone. © 1996 John Wiley & Sons, Inc.     

配合物Eu(Sal)_2(phen)_2(NO_3)的合成及荧光性能的研究

用硝酸铕、水杨酸与邻菲罗啉为原料合成了配合物Eu(Sal)2(phen)2(NO3),考察了配体用量和溶剂用量等因素对反应的影响。通过元素分析、红外光谱和紫外光谱确定了配合物的组成及结构,并通过荧光光谱对其荧光性质进行了研究。     

Photoluminescent Polymer Composites Based on New Tb(III) and Eu(III): Maleimide Complexes

The paper reports the preparation of two photoluminescent polymer composites by embedding two newly prepared Tb(III) and Eu(III) complexes into poly(4-styrenesulfonic acid) matrices using maleimide as ligand. In the first step, the photoluminescent complexes were prepared at 1:3 metal-to-ligand ratio. Prior to the embedment into the polymer matrix the complexes were investigated by chemical and thermal analysis, FT-IR, powder X-ray diffraction and fluorescence spectroscopy. The prepared composites preserve the photoluminescent properties of the complexes and provide them with long-term stability. Thin films of the composites were spin–coated on glass slides and investigated by SEM and AFM techniques. The remarkable photoluminescent properties of the composites prepared in bulk or deposited in thin films on various substrates recommend them for applications in optical devices as photonic conversion mediums.     

Modifying polysulfone into a bidentate Schiff base type macromolecular ligand and study on photoluminescence property of polymer–rare earth complexes of Eu(III) and Tb(III)

Chloromethylated polysulfone (CMPSF) was directly transformed into aldehyde (AL) group-functionalized polymer via Kornblum reaction, and then polysulfone was modified to a bidentate Schiff base (BS) type macromolecular ligand, PSF-ASB, via Schiff base reaction with 3-aminopyridine as reagent. Afterward, luminescent binary and ternary polymer-rare earth complexes, PSF-(ASB)₃-Eu (III) and PSF-(ASB)₃-Eu(III)-(Phen)₁ (o-phenanthroline, Phen), were prepared. The macromolecular ligand PSF-ASB and the complexes were fully characterized by FTIR, ¹H-NMR, UV spectroscopy and TGA. The photoluminescence properties and mechanisms of the complexes were investigated in depth. The experimental results show that the macromolecular ligand PSF-ASB itself emits strong fluorescence. However, after coordinating to Eu(III) ion, its fluorescence intensity weakens remarkably, implying that there occurs an intramolecular energy transfer. The complexes of Eu(III) ion exhibit stronger characteristic fluorescence emission of Eu(III) ion, whereas the complex of Tb(III) ion has no photoluminescence property, indicating that the bonded ligand ASB can effectively sensitize the fluorescence emission of Eu(III) ion and suggesting that the triplet state energy of the bonded ligand ASB is well matched with the resonant state level of Eu(III) ion. More importantly, relative to general polymer-rare earth complexes, for these luminescent polymer-rare earth complexes prepared in this study, the backbone of the macromolecular ligand PSF-ASB also takes part in the sensitization towards Eu(III) ion because of that half of aryl rings of a greater π bond conjugate system of ASB comes from PSF skeleton, displaying a great difference with other luminescent polymer-rare earth complexes.     

聚苯乙烯-聚4-乙烯基吡啶-稀土铕(Ⅲ)发光配合物的微观结构及荧光性能表征

含共轭结构氮杂环的非离子嵌段共聚物能与铕(Ⅲ)络合反应形成发光配合物,研究了该发光配合物的配位结构及其荧光性能。以聚苯乙烯-聚4-乙烯基吡啶(PS-b-P4VP)作为高分子配体,以邻菲罗啉(Phen)作为小分子配体,通过吡啶环的氮原子与Eu(Ⅲ)离子配位发生络合反应形成了以网状的Eu(Ⅲ)-P4VP核层以及PS链段为壳层的共聚物-稀土配合物,通过电子透射电镜(TEM)分析了其微观形态结构。用荧光分光光度计分别表征了嵌段聚合物-稀土铕(III)配合物不同链段的荧光发光强度并且进行了荧光强度的对比。此外,还研究了不同的Eu(Ⅲ)离子浓度对荧光强度的影响,得到了制备共聚物-稀土配合物荧光的最佳Eu(Ⅲ)离子浓度。     

Synthesis,Characterization and Fluorescence Properties of Poly(styrene-co-n-caprylamide maleic acid) and Its Europium(III) and Terbium(III) Complexes

Copolymer of poly(styrene-co-n-caprylamide maleic acid) (PSCMA, defined as HL) and its lanthanide complexes Ln(L)₃·6H₂O (Ln = Eu and Tb) had been synthesized and characterized by elemental analysis, X-ray diffraction, Fourier transform infrared spectra, UV-spectrophotometer and thermal analysis (TG–DTA). The fluorescence properties of the HL ligand and the Ln(L)₃·6H₂O complexes in the solid state were investigated. At room temperature, the HL ligand had a strong broad emission band at 410–575 nm (λmax = 458 nm) under excitation at 380 nm, while the respective characteristic emission of Eu(III) and Tb(III) ions was observed in Ln(L)₃·6H₂O complexes. This demonstrated that the HL ligand in the extra-framework channels succeeded in sensitizing Eu(III) and Tb(III) ions emission. Compared with the Eu(L)₃·6H₂O complex, the fluorescence intensity of the Tb(L)₃·6H₂O complex was much stronger. This indicated that the lowest excited triplet state energy level of HL matched well with the excited state energy level of Tb(III). With the increase of the Ln(III) ions content below 15 wt%, the fluorescence intensity increased monotonically. All the Ln(L)₃·6H₂O complexes exhibited high quantum yield, long fluorescence lifetime and good thermal stability.     

新型稀土荧光材料的合成及性能研究

以巯基乙酸、间苯二甲酸为配体,分别与Eu(Ⅲ)、Pr(Ⅲ)、Dy(Ⅲ)在乙醇溶液中反应,生成稀土-巯基乙酸-间苯二甲酸三元配合物.用元素分析、红外光谱分析确定了配合物的化学组成.用热重、荧光光谱对3种配合物的性能进行了分析.结果表明:3种配合物热稳定性较高,Eu(Ⅲ)、Dy(Ⅲ)的配合物具有相对较强的荧光性能.