燃烧法合成SrAl12O19:Eu2+

利用相应的金属硝酸盐和尿素之间发生的氧化还原反应，在600℃的炉温下，制备了发蓝光的铝酸盐发光粉SrAl12O19:Eu^2 ，产物为六方晶系。研究结果表明，在制备Eu^2 激活的铝酸盐发光粉时，适当量的尿素用量和相对密闭的反应体系有利于获得纯相和单一发光颜色的产物。     

LaPO4:Eu3+的PEG2000辅助水热法制备及发光特性

采用水热法,以聚乙二醇2000(PEG2000)为添加剂,成功制备了铕掺杂的磷酸镧纳米颗粒。通过扫描电子显微镜(SEM)观察到所制得的纳米颗粒分散性较好,呈球形放射状结构。用X射线粉末衍射仪(XRD)对其结构进行了表征,实验表明:LaPO4属单斜晶系,独居石结构,700℃煅烧2 h基本晶化完全。研究了不同合成条件、煅烧时间、煅烧温度及不同铕含量对材料发光性质的影响,荧光光谱(FS)数据表明:最佳制备条件是pH等于9的条件下180℃反应14 h;随着煅烧温度的升高,激发峰及各个发射峰的强度都增大,850℃时,煅烧1 h发光强度最大,随着时间的延长发光强度反而减小;随着铕含量的增加,发光强度先增强后减弱,Eu3 的掺加量在4%(摩尔分数)时,纳米粒子的荧光强度最强,更高的掺杂浓度将导致荧光猝灭。     

Hierarchical and Complex ZnO Nanostructures by Microwave-Assisted Synthesis: Morphologies,Growth Mechanism and Classification

Zinc Oxide is an important and multi-purpose material in various industries due to its particular chemical and physical properties. Discovering a cheap, fast, clean, safe, and easy to use method, to synthesize this oxide nanoparticle has attracted a lot of attention in recent applications. The unique properties of the microwave and its special heating capabilities have yielded desirable outcomes by combining different synthesis methods. In the recent years, the vast majority of studies focus on the microwave-assisted synthesis of zinc oxide nanoparticles. This review article attempts to go over the recent advancements on the synthesis of zinc oxide nanoparticles with the aid of microwave, different morphologies and applications obtained by this method. Various microwave-assisted synthesis methods are classified, including the solution-based methods such as hydrothermal, sol-gel, and combustion methods. Morphology of the nanoparticles can affect the properties, and subsequently, applications of these nanoparticles. On the other hand, there is great diversity of morphological and synthesis conditions of zinc oxide nanoparticles. Thus, categorizing the synthesis techniques and providing features of them, facilitates the selection of appropriate method for designing new hierarchical structures with potential properties for future applications. Also it is endeavored to focus on the formation mechanisms of these methods. Finally, the various morphologies obtained under microwave radiation and their formation mechanisms are discussed and the effective factors in the synthesis are analyzed and presented. The potential and suitable fields of development and progress in the future studies are also proposed.     

铕(Ⅲ)掺杂含氧磷酸镧纳米晶的燃烧法合成及其发光性质

采用燃烧法合成了新型红色纳米发光材料La3PO7∶Eu3 ,并用X射线粉末衍射对其结构进行了表征。XRD分析证实样品La3PO7为单斜相。测定了其激发光谱和发射光谱,光谱数据表明:对应于Eu3 的5D0→7F2跃迁的发射强度远大于5D0→7F1跃迁的发射强度,La3PO7∶Eu3 形成红色发光材料。推测是由于基质结构的不对称性,Eu3 在基质La3PO7中占据非对称中心的格位所致。在不同温度下退火后,发现退火温度越高,Eu3 的5D0→7F2跃迁辐射越强,表明样品结晶越好。     

Synthesis of Single Crystalline ZnO Nanoparticles by Salt-Assisted Spray Pyrolysis

LiNO₃ was used as a shield in the preparation of single crystalline ZnO particles by a spray pyrolysis process in order to prevent agglomeration and enhance the crystallinity of the ZnO. LiNO₃ was added to a precursor solution of zinc acetate dihydrate prior to its atomization by means of an ultrasonic transducer. Agglomerate-free particles having a mean particle size of 26 nm were successfully obtained after washing the product. X-ray diffractometry, field-emission scanning electron micrograph and transmission electron micrograph data indicate that the size and morphology of ZnO were strongly influenced by the operating temperature used and the residence time of the particle in the reactor.     

Synthesis and Characterization of ZnO Nanoparticles and Their Natural Rubber Composites

Abstract

Nanoparticles of zinc oxide were synthesized by a solution combustion method. The average size of these particles was analyzed by using X-ray diffraction. Composites of natural rubber and the ZnO nanoparticles were prepared by a latex blending method. The matrix phase was cured by using the crosslinking agent, pentane-1,5-diylidenediamine. Effects of crosslinking and incorporation of nanoparticles on the tensile and solvent transport properties of the natural rubber were studied in detail. The nature of the dispersion of the nanoparticles was analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). It was observed from the tensile studies that the addition of the curing agent and the ZnO nanoparticles increased the stability considerably. Incorporation of the nanoparticles also considerably increased the solvent resistance of the cured natural rubber. We suggest the addition of ZnO nanoparticles at a low loading level provided better properties compared to other reinforcements, such as carbon black and nano-clay.     

NaYF_4∶Eu~(3+)纳米粒子和六棱柱的水热控制合成与发光性质

以柠檬酸三钠为螯合剂,通过控制反应条件,利用水热法分别合成出立方相NaYF4:Eu3+球形纳米粒子和六角相NaYF4:Eu3+六角微米棱柱。利用X射线粉末衍射(XRD)、场扫描电子显微镜(SEM)、红外吸收(FTIR),以及发光光谱等手段对产物的物相结构、形貌和荧光性能进行了分析。结果显示产物的晶格结构和柠檬酸分子的选择性吸附是晶体形貌可控的主要原因。在395nm光激发下,NaYF4:Eu3+样品显示出较强的橙色(588nm)和红色(614nm)发光,分别来自于Eu3+离子5D0→7F1和5D0→7F2的跃迁。从5D0→7F2与5D0→7F1跃迁的强度比可以推断在立方相纳米粒子的晶格中Eu3+离子更多地占据反演中心的格位。     

Zno纳米粒子在PS中空微反应器中的合成与光学性能

通过种子乳液聚合合成核壳结构的聚甲基丙烯酸甲酯/聚苯乙烯(PMMA/PS)复合微球,通过酸碱溶胀法进一步制备出次微米级的PS中空微球. 将此中空微球作为微反应器,使在ZnO纳米粒子前驱体溶液中溶胀, 最终ZnO纳米粒子在PS中空微球中原位生成. 实验表明, 组成ZnO纳米粒子前驱体溶液的两种组 分(CH₃COO)₂Zn和LiOH的滴加顺序不同对最终生成的ZnO纳米粒子的尺寸和负载效率有很大的影响,但并不改变ZnO纳米粒子的晶型. 复合物的光致发光和UV-Vis吸     

对流速度对燃料液滴火焰形态及燃烧的影响

考虑气相非稳态及液滴内部环流,建立运动液滴非稳态蒸发燃烧模型.模型采用动网格方法精确追踪液滴表面位置,采用守恒方程组更新液滴表面边界条件.根据单步全局化学反应机理,仿真研究正庚烷燃料液滴在不同对流速度下的火焰形态及燃烧.结果表明:运动液滴内部环流使液滴内部低温区向环流中心移动.当液滴运动速度大于某临界值后,火焰形态由包覆火焰转变为尾迹火焰.包覆火焰的富燃区范围、高温区范围及燃烧速率明显较尾迹火焰大;包覆火焰的液滴表面温度及表面蒸发流率分布也明显不同于尾迹火焰.     

ZnO粉末的直流电致发光特性研究

用溶胶凝胶法制备了几种ZnO粉末, 测量了它们的直流电致发光. 在样品中观察到了较强的绿带（556 nm）发射; 对十二胺处理的样品, 绿带发光强度最高可提高8倍, 十八胺处理的样品, 绿带发光强度最高可提高12倍. 在同电压下, 十八胺处理的ZnO的发光强度也较十二胺处理的ZnO的发光强度大1.5～2倍; 并在十二胺处理的样品中, 还观察到了强度较小的蓝光谱带（406 nm）. 在一定电压范围内, ZnO电致发光强度随直流电压增强而线性增强. 所得ZnO样品在2V/μm场强下起亮, 在测量的近1 h内, 发光强度稳定, 重复性好. 分析认为：406 nm处的蓝光谱带是由于VZn空位在禁带中（距离价带0.3 eV）形成缺陷能级, 从导带到价带跃迁的结果, 而556 nm处的绿色发射带是由ZnO中氧空位所导致.     

Probing of surface Eu ions present in ZnO:Eu nanoparticles by covering ZnO:Eu core with Y2O3 shell: Luminescence study

Eu³⁺ doped ZnO nanoparticles are known to have significance extent of surface Eu³⁺ ions due to a large difference in ionic radii. Effect of such Eu³⁺ ions on the luminescence properties of ZnO:Eu nanoparticles has been understood from the luminescence studies of ZnO:Eu nanoparticles covered with Y₂O₃ shell. Based on the asymmetric ratio of luminescence and extent of energy transfer, it is established that when ZnO:Eu nanoparticles are covered with Y₂O₃ shell, a part of Eu³⁺ ions present with ZnO:Eu core migrate to Y₂O₃ shell and occupy Y³⁺ lattice positions.     

ZnO纳米颗粒中的表面态发射特性研究

研究了不同粒径ZnO纳米颗粒样品(17～300nm)的时间光谱,通过对各粒径样品时间积分光谱的谱带结构进行高斯拟合解迭,发现光子能量位于ZnO谱带低能侧的高斯拟合成份Xc3的荧光中心波长随粒径的减小而红移,同时发光带的寿命也随之缩短.基于ZnO谱带低能侧的高斯拟合峰发光带强烈依赖于ZnO样品粒径的谱带特性,提出了与ZnO禁带内的表面态能级有关,同时研究表明,表面态在尺寸降到一定程度的纳米体系中起着重要的作用.     

尿素用量对燃烧法合成CaAl2O4：Eu2+,Nd3+长余辉材料发光性能的影响

利用金属硝酸盐和尿素的氧化还原反应,通过燃烧法在600℃的炉温下合成了蓝紫色长余辉发光材料CaAl₂O₄:Eu²⁺,Nd³⁺。在金属硝酸盐溶液浓度不变的条件下,通过改变尿素与硝酸根的量的比,合成了多组长余辉材料样品。当尿素用量较少时,Eu³⁺不能完全被还原为Eu²⁺;随尿素用量增加,样品的Eu³⁺特征发射减弱,余辉初始亮度和持续时间均得到改善;当尿素的用量达到理论用量的5倍时,样品余辉特性最好,继续增加尿素用量,余辉亮度和持续时间反而下降。将燃烧法制备的各组样品用活性炭密封,在1000℃条件下反应2h,使Eu³⁺完全被还原为Eu²⁺,同时除去燃烧法反应不完全的杂质,可以一定程度提高材料的余辉发光性能。     

ZnO及其掺杂Mn纳米粒子的微乳液法合成

纳米材料的制备是纳米科学发展的基础,微乳液法与传统的制备方法相比具有明显的优势。本文用双微乳液混合法制备纳米ZnO粉末,通过实验从ZnSO4和NaCO3制备纳米粒子,同时采用在制备过程中掺杂Mn2+,讨论对其性质的改变的影响,并采用荧光发射分析和XRD表征。     

Photoluminescence characteristics of ZnO doped with Eu powders

In this work, we have investigated the photoluminescence spectra of europium-doped zinc oxide crystallites prepared by a vibrating milled solid-state reaction method. X-ray diffraction, scanning electron microscopy, luminescence spectra and time-resolved spectra analysis were used to characterize the synthetic ZnO:Eu³⁺ powders. XRD results of the powders showed a typical wurtzite hexagonal crystal structure. A second phase occurred at 5 mol% Eu₂O₃-doped ZnO. The ⁵D₀-⁷F₁ (590 nm) and ⁵D₀-⁷F₂ (609 nm) emission characteristics of Eu³⁺ appeared after quenching with more than 1.5 mol% Eu₂O₃ doping. The Commission Internationale d’Eclairage (CIE) chromaticity coordinates of a ZnO:Eu³⁺ host excited at λ_ex=467 nm revealed a red-shift phenomenon with increase in Eu³⁺ ion doping. The lifetime of the Eu³⁺ ion decreased as the doping concentration was increased from 1.5 to 10 mol%, and the time-resolved ⁵D₀→⁷F₂ transition presents a single-exponential decay behavior.     

爆轰和燃烧法合成SrAl2O4：Eu2+，Dy3+纳米发光粉

 在低温条件下分别用爆轰法和燃烧法制备出了SrAl₂O₄：Eu²⁺,Dy³⁺ 纳米发光粉。从合成条件、热处理温度等方面详细对比了爆轰法和燃烧法对所制备的SrAl₂O₄：Eu²⁺,Dy³⁺纳米发光粉的晶体生长行为、粒子形貌和光学性质等的影响。研究表明,随着热处理温度的升高,爆轰法制备的纳米发光粉的平均粒径逐渐增大,而燃烧法制备的纳米发光粉的平均粒径先减小后增大,在600 ℃时平均粒径存在一个极小值。在同样热处理温度下,爆轰法制备的纳米发光粉的平均粒径增长明显高于燃烧法合成的纳米发光粉的平均粒径。最后讨论了长余辉的发光机理,并给出了如何改进合成方法的建议。     

Nanoparticles of BaSO4:Eu for heavy-dose measurements

Nanoparticles of BaSO₄:Eu with grain size in the range 30-50 nm have been prepared by the chemical co-precipitation method and characterized by UV-visible spectrometry and X-ray diffraction (XRD). Shape and size of the prepared nanomaterials were observed by a scanning electron microscope (SEM). The optical energy band gaps of the micro- and nanocrystalline BaSO₄:Eu were determined and are found to be 3.39±0.0136 and 3.48±0.0139 eV, respectively. The thermoluminescence (TL) glow curve of BaSO₄:Eu nanoparticles has been studied and compared with that of the corresponding microcrystalline powder. It has been observed that the TL glow peak at 497 K, seen prominently in the microcrystalline sample, appeared as a small peak in nanocrystalline powder, while that observed as a shoulder in the former at 462 K dominates in the latter. The observed TL sensitivity of the prepared nanocrystalline powder is less than that of the microcrystalline sample at low doses, while it is more at higher doses. This nanophosphor exhibits a linear/sublinear TL response to γ-radiation over a very wide range of exposures (0.1 Gy to 7 KGy), which is much wider compared to that of the microcrystalline counterpart (0.1-10 Gy). This response over a large span of exposures makes the nanostructure form of BaSO₄:Eu useful for its application to estimate low as well as high exposures of γ-rays.     

小尺寸铕(Ⅲ)配合物荧光纳米颗粒的制备

利用再沉淀法分别制备出了小尺寸(~10nm)纯相和杂相的Eu³⁺配合物荧光纳米颗粒。所制备的纯相的荧光纳米颗粒在水溶液中容易聚集,并且荧光猝灭严重。相比较而言,掺有适量疏水性硅烷的杂相纳米颗粒则具有较强的荧光、均匀的尺寸和良好的分散性。硅烷在碱性环境下(pH=9)迅速地水解,而后在纳米微粒的表面形成二氧化硅薄层。亲水的二氧化硅薄层消除了Eu³⁺配合物纳米颗粒间的疏水相互作用,进而防止了纳米颗粒的聚集,从而导致了杂相荧光纳米颗粒发光性能的提高。     

稀磁ZnO纳米颗粒的生长和性能

利用Zn、Fe、Mn、Co的铜铁试剂盐为前驱体,胺为表面包裹剂,在200℃N2保护下生长了2%的过渡金属离子掺杂的ZnO稀磁纳米晶体,研究了纳米晶体的结构、形态、光学和磁学性能。所有ZnO纳米晶体均为近圆形的颗粒,晶体结构为六角纤锌矿结构,无其他氧化物相的析出,但过渡金属离子的掺入使纳米颗粒的尺寸增大。在掺杂纳米颗粒的吸收谱和发射谱中均可以观察到明显的激子吸收和发射峰,所有纳米颗粒在温度高于43K时只有顺磁性。     

Nanoparticles of: Synthesis and superparamagnetic properties

By using oil in water micelles, cobalt ferrite particles having an average diameter around 3 nm were synthetised. These nanoparticles are characterized by the presence of cation vacancies and no Fe(II) is observed, as it has been described in literature previously. Chemical interfacial treatment allows to coat the particles with citrate derivatives. The magnetic properties of uncoated and coated particles strongly diluted in a polymer substrate are compared by magnetization measurements and ⁵⁷Fe M?ssbauer spectroscopy. The anisotropy constant is shown to be independent of coating, whereas the magnetization is found to be larger in the uncoated particles. Received 3 February 1998