蓄能发光新材料及其开发动向

介绍了发光材料及其分类,详述了蓄能发光颜料用荧光体的发光特性,对其发光性能进行了比较。     

发光塑料的研制

分别将ZnS类发光颜料及碱土铝酸盐类发光颜料加入到聚丙烯中,制成ZnS发光塑料和碱土铝酸盐发光塑料,测定其辉度、余辉时间及光稳定性．结果表明,在低强度光的激发下,碱土铝酸盐发光塑料较ZnS发光塑料吸光慢,初始辉度低,但余辉时间长;在高强度光的激发下,碱土铝酸盐发光塑料辉度高,余辉时间长;在日光照射下,碱土铝酸盐发光塑料的耐光性能明显优于ZnS发光塑料,碱土铝酸盐发光塑料无论是发光性能还是耐光性能均优于ZnS发光塑料。     

Printing the light

This paper explores the relationship between additive and subtractive mixing for colour printing. Using Spectraval mica pigments (Merck)—marketed as RGB pigments—colour is generated by selective reflection and prints are based on additive colour mixing principles, that when printed onto black paper, create white and a range of colours. Although currently used mostly for decorative effects, they can be the basis of additive 'process' inks, that present new opportunities for and challenges to traditional print markets. The viewing angle dependency of their selective reflection favours applications in security printing similar to the holograms on bank cards for example. Traditional measurement and modelling methods are difficult to apply due to the layering and irregular dispersion of pigments.     

染料掺杂发光聚氨酯复合材料的制备及性能

为合理探讨使发光聚氨酯智能化的方法,本研究采用涂层整理的方式制备出具有热敏变色功能的柔性发光聚氨酯复合材料（LPC）。扫描电子显微镜（SEM）观察到材料表面粗糙不平;X射线衍射仪（XRD）分析表明涂层工艺和颜料的添加未影响材料中稀土发光材料的物相结构;反射率和发射光谱测试显示材料具有优异的热敏变色发光特性,标准光源下材料自身颜色可通过人体体温来改变（由红色变为白色）,经紫外-可见光源激发后,在黑暗环境中形成低温红光-高温白光的体系,充分展示其在智能可穿戴设备领域的应用潜力。     

Synthesis of ZnS–Mn nano-luminescent pigment for ink applications

In the present study, ZnS–Mn nano-luminescent pigments were synthesized, using co-precipitation method. Polyvinylpyrrolidine (PVP) surface modifier and Mn dopant concentrations were considered as affecting parameters. The luminescent ink was loaded with two different concentrations of pigments. The obtained ink was silk-screened on different types of fabrics mainly treated cotton, cotton and nylon. Structure, microstructure, luminescent properties of nano-pigments, inks and fabrics and also rheological properties of the inks were investigated. The results showed that the ceramic ink prepared with nano-luminescent pigment had high photoluminescence (PL) intensity. Moreover, the optimum concentrations of Mn and PVP for obtaining maximum PL intensity were found as 2 and 5 wt%, respectively. SEM images of fabrics indicated that nanoparticles were loaded, nonuniformly, on the fibers. The treated linen and nylon fabrics showed maximum and minimum PL intensity, respectively, due to ink penetration depth in the fabrics. Furthermore, washing fastness estimated for all fabrics was in the proper range.     

New insight into the coloration mechanism and synthesis of ultrafine Pr-ZrSiO4 yellow pigments

It is of particular significance to unveil the authentic coloration mechanism of the multivalent praseodymium colored ZrSiO₄ yellow pigments for advanced decoration applications. We herein adopted a facile strategy to modulate the fluorine-assisted zircon crystallization and thereby obtained ultrafine Pr-ZrSiO₄ yellow pigments, which have a remarkably narrow size distribution and average diameters within 250–400 nm. By virtue of some cogent combinative spectra of reflection, absorption, excitation, and emission from three types of elaborately-designed H₂-, air-, and O₂-based pigments, the coloration mechanism for the Pr-colored zircon was systematically unveiled: both Pr⁴⁺ and Pr³⁺ coexist invariably in the pigments, while the former contributes primarily to the ligand-to-metal charge transfer from O_2p to Pr(IV)_4f for the blue–violet absorption to generate the yellow hue, and the latter is inclined to discolor the pigments. Therefore, an oxidizing atmosphere is preferable to produce brilliant Pr-ZrSiO₄ pigments with enhanced chromatic properties. The stark spectroscopic distinctions between the wide-band absorption from the nonluminescent tetravalency and the narrow-band absorption from the luminescent trivalency can expand our understanding to the rare-earth-based inorganic pigments.     

有机掺杂长余辉发光材料的研究进展

纯有机长余辉发光材料具有制备方法简单、成本低廉、可柔性化、环境友好等优点,被广泛应用于防伪、信息保密、生物成像等领域。其中,基于掺杂体系的纯有机长余辉发光材料,可通过调控主客体之间的配位关系,实现长余辉时间和颜色的可调性,并可在室温下制备出性能优异的长余辉发光材料,是目前有机长余辉发光材料研究的热点。本文分别从小分子基质体系、大分子基质体系、聚合物体系等方面综述了该领域的研究进展,介绍了相关材料在信息加密与防伪、生物成像、柔性纤维薄膜等领域的应用。最后,指出了目前有机掺杂长余辉发光材料研究中还存在的一些问题,并展望了其发展前景。     

Color reproduction of authenticable luminescent backlit transmissive color images

We propose a method for creating authenticable color images under UV excitation backlight by printing an invisible luminescent white emissive ink layer on the verso side of a transmissive substrate and a classical cmy image on the recto side of the substrate. In order to obtain a backlit image whose colors are as close as possible to the original image colors, we map the input image sRGB color gamut into the gamut formed by the emissive white source attenuated by the classical ink halftones. The relationship between surface coverages of the classical cmy ink halftones and the resulting backlit colors is obtained by accounting for the transmission of the emissive white through the paper substrate and through the classical cmy ink halftones. The transmittance of the classical ink halftones is modeled by a new halftone absorbance prediction model. The lightness range of the luminescent backlit color gamut is expanded by printing a black and white UV‐absorbing instance of the original color image in superposition with the luminescent white emissive layer and in registration with the cmy image printed on the recto side. Luminescent backlit color images provide a high anticounterfeiting security, as they combine a verso printed invisible luminescent ink layer, a verso printed black and white instance of the original image and a matching recto printed cmy instance of the original image. The resulting luminescent backlit image colors are close to the original image colors only when observed in transmission mode under UV light. © 2013 Wiley Periodicals, Inc. Col Res Appl, 39, 331–340, 2014     

荧光黄颜料的合成

本文以苊为原料经硝化、氧化、缩合、还原等工序合成了４－氨基－Ｎ－间甲苯基－１,８－萘二甲酰亚胺和４－氨基－Ｎ－邻甲苯基－１,８－萘二甲酰亚胺两种荧光黄颜色的荧光体,并对影响合成反应的诸因素进行了讨论。制得的两种化合物经光谱测定,证明有很好的荧光性能。     

Chromophoric potential of the 4(3H)-quinazolinones: a review

The last few decades have seen significant developments in the use of heterocyclic compounds in dyestuff and pigment chemistry. The design of newer heterocyclic systems has been a major target area and has focused on economically viable synthesis, absence of effluent problems and freedom from carcinogenic and mutagenic effects. The present article reviews the chemical and patent literature on the chromophoric potential of the 4(3 H )-quinazolinone ring system, including dyes, pigments, fluorescent brightening agents, luminescent inks, electroluminescent devices, photographic couplers, colour formers and photographic fog inhibitors.     

Using extraction and sorption processes to obtain nanosized powders of calcium silicates and functional materials on their basis

The review presents summary data on extracting agents and the application of sorption processes during the cycle of studies on the joint processing of calcium and silicon-containing raw materials on the production of calcium silicates and composite materials on their basis. It is found that, in processes of the production of synthetic calcium silicates from various types of calcium and silicon-containing raw materials, ionic and nonionic surfactants, including extractants, serve as structuring additives that hinder crystal growth and impede their agglomeration. The sorption properties of amorphous and crystalline nanopowders of calcium silicates and hydrosilicates synthesized from water-soluble materials are studied with respect to cations of base and rare metals. It has been found that the studied samples have high sorption capacity for cations of Eu3+, Pr³⁺, Tb³⁺, Er³⁺ and may be used as the basis for producing functional composite materials. The efficiency of applying the extraction-pyrolytic method has been shown to provide homogeneity and predetermined composition of the desired products, for the production of ceramic pigments and luminescent materials based on calcium silicates.     

Ethylene glycol-assisted ultrafast synthesis and luminescent properties of novel multifunctional EuSr2F7 and TbSr2F7 nanostructures for WLEDs,displays and anti-counterfeiting

In this paper, novel EuSr₂F₇ and TbSr₂F₇ nanostructures were successfully synthesized via an ultrafast wet-chemical route at room temperature. The elemental compositions, morphology, luminescent behaviors, thermal stability, decay curves and quantum yields of the as-prepared samples were investigated. The fabricated white light-emitting diodes (WLEDs) exhibited excellent color rendering index and correlated color temperature values. The security inks and soft polydimethylsiloxane films were prepared for potential anti-counterfeiting and flexible display applications. Eventually, under low accelerating voltage and filament current, the as-prepared samples showed strong cathodoluminescence emission intensity. The above results suggest that the novel EuSr₂F₇ and TbSr₂F₇ nanostructures with outstanding luminescent performances could be promising for field-emission displays, WLEDs, flexible display films, and anti-counterfeiting applications.     

A Review of Pigments Derived from Marine Natural Products

Since the early 20th century, a number of active natural pigments have been identified from marine sources, especially algae and marine microorganisms. This review presents 81 marine pigments, covering over 90 % known natural marine pigments. The objective of this article is to provide an overview on the types of pigments, their structural characterization, origins and biological functions that make them unique. We divide the major categories of pigments by chemical structure, either as carotenoids, indole derivatives (quinones and violacein), alkaloids (prodiginines and tambjamines), polyenes, macrolides, peptides, or terpenoids. Many of these pigments have a variety of biological activities, including antitumor, antibacterial, antioxidant and anti‐inflammatory. In addition, we discuss the development of biotechnology, and the contribution and utilization of marine natural pigments and the potential applications in the field of pharmaceutical research.     

微生物催化在靛蓝及靛蓝类色素生产中的应用

靛蓝及靛蓝类色素的微生物催化合成因其环境友好、安全稳定等优点成为当前的研究热点。本论文从基因工程、诱变育种、发酵工艺、辅酶再生及双液相催化的应用方面,对微生物法合成靛蓝及靛蓝类色素的技术应用进行阐述,并结合微生物合成靛蓝方面的实际应用,为靛蓝及靛蓝类色素的微生物合成的产业化应用提供指引。     

Synthesis of ultrastable eu‐complex/polystyrene composite luminescent nanoparticles using a solvent swelling method

Nanoparticles composed of Eu‐complex, Eu(TTA)₃Phen, and polystyrene (PS) were successfully synthesized through an improved solvent swelling method. The unstable Eu(TTA)₃Phen could be protected by the hydrophobic shell of PS nanoparticles. This method is very appropriate to embed unstable luminescent molecules into polymer nanoparticles. The as‐synthesized luminescent PS nanoparticles have been turned out to be water‐dispersible, strong red luminescent, ultrastable in strong acid and alkali, and luminescence lifetime enhanced. A cell imaging assay was further carried out and strong luminescent signal could be obtained, which showed that the as‐synthesized luminescent Eu‐complex/PS nanoparticles are a good candidate to be used as luminescent nanoparticles in tumor cell detection. This solvent swelling method is simple, easy to scale‐up, and has great potential in the preparation of other luminescent nanoparticles. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Properties and Photoactivity of Rhodopsin Mutants

A variety of spectroscopic and biochemical studies of recombinant site-directed mutants of rhodopsin and related visual pigments have been carried out. These studies have elucidated key structural elements common to visual pigments, such as a conserved disulfide bond. In addition, systematic analysis of the chromophore-binding pocket in rhodopsin and cone pigments has led to an improved understanding of the mechanism of the opsin-shift, and of particular molecular determinants underlying color vision in humans. Identification of conformational changes which occur upon rhodopsin photoactivation has been of particular recent concern. Assignment of these molecular alterations to specific regions in the receptor has been attempted by studying native opsin regenerated with synthetic retinal analogues or recombinant opsins regenerated with 11-cis-retinal. Individual molecular groups that undergo structural alterations during photoactivation have been identified. Analysis of particular mutant pigments in which specific groups are locked into their respective “on” or “off” states has provided a framework to identify determinants of the active conformation as well as the minimal number of intramolecular transitions required to switch between inactive and active conformations. A simple model for the active state of rhodopsin can be compared to structural models of its ground state to localize chromophore-protein interactions that may be important in the photoactivation mechanism.     

高档有机颜料的简介（二）

高档有机颜料必须通过三个考验：在技术应用上必须是胜任的，在客户的经济价值中必须是合适的，在环境安全的审核下，必须合乎潮流的。因此所谓的高档颜料不仅其应用性能良好，也能提供品质均一的生产制品，更重要的是市场也能接受其高超的性价比。该文就喹吖啶酮，苝红，二苯基吡咯并吡咯酮的合成，应用作简单的介绍。     

高档有机颜料的简介（一）

高档有机颜料必须通过三个考验：在技术应用上必须是胜任的，在客户的经济价值中必须是合适的，在环境安全的审核下，必须合乎潮流的。因此所谓的高档颜料不仅其应用性能良好，也能提供品质均一的生产制品，更重要的是市场也能接受其高超的性价比。该文就喹吖啶酮，苝红，二苯基吡咯并吡咯酮的合成，应用作简单的介绍。     

Preparation and luminescent modulation of KGaSiO4:Eu3+ phosphors using for multiple anti-counterfeiting

Anti-counterfeiting technology is of great significance to information security. To obtain high-quality anti-counterfeiting materials, the developments of inorganic materials are crucial. In this paper, a series KGaSiO₄:xEu³⁺ phosphors with persistent luminescence, photoluminescence, and thermochromic have been successfully prepared and the application of quadruple anti-counterfeiting is realized. The X-ray diffraction and Rietveld refinement indicate that the phosphors are pure phase. With Eu³⁺ ions doping, the structure change, site occupancies, and color-tunable phenomenon are carefully investigated. Different from another Eu³⁺ doping phosphor, the emission of KGaSiO₄:0.2% Eu³⁺ phosphor changes with the excitation light in the region of 240 nm–306 nm. The emission color can be modulated with the surrounding temperature. Surprisingly, this phosphor can emit green afterglow light, which is attributed to the different luminescent properties of the matrix and doping of Eu³⁺ ions. The series of phosphors exhibit abundant luminescent properties. Based on their wavelength dependence, concentration quenching, long afterglow, and thermochromic properties, the KGaSiO₄:xEu³⁺ phosphors can be effective materials for quadruple-modal anti-counterfeiting devices.     

Application of nanostructured titanium dioxide pigments in paper coating: a comparison between prepared and commercially available ones

Nano-TiO₂ pigments in pure crystallographic anatase and rutile phases have been successfully prepared by hydrothermal at 120°C and hydrolysis methods, respectively. The laboratory-prepared pigments were characterized parallel to two commercial pigments of the same crystal structure. All pigments were applied in paper coating mixtures, and their influence on coated paper properties was systematically investigated. X-ray diffraction investigation showed that the laboratory-prepared pigments using the hydrothermal method at 120°C were pure anatase, whereas hydrolysis method produced pure rutile phase pigment. The application of the prepared nanopigments and the corresponding commercial TiO₂ phases in paper coating revealed that clay/rutile nano-TiO₂ pigments in paper coating mixture decreased coated paper roughness more than blending clay with anatase nano-TiO₂ pigments. Commercial nano-TiO₂ pigments increased porosity of coated paper at both the 30% and 50% addition of nano-TiO₂ pigments to clay, while laboratory-prepared nano-TiO₂ pigments highly decreased it at 30% addition of nano-TiO₂ to clay, compared to clay only. Blending of clay/nano-TiO₂ pigments improved both brightness and opacity of the coated paper where commercial pigments are more effective. Burst, tensile strength, stretching, and TEA were improved in the case of all pigments. The 50% addition of the prepared and commercial nanopigments in conjunction with clay improved the mechanical coated paper properties more than 30% addition (except the cases of stretching and TEA of the commercial pigments). The coated paper samples were offset printed. It was found that blending of clay/nano-TiO₂ pigments improved print density. Commercial nano-TiO₂ pigments improved print gloss more than the laboratory-prepared ones. This result was found consistent with the results of coated paper roughness.