基于氧化铁颗粒与聚合物的纳米复合材料磁电容特性研究

对由Fe3O4纳米颗粒-聚二甲基硅烷(PDMS)聚合物材料所组成纳米复合材料磁电容特性进行了研究,提出了该复合材料的制备方法,并对其进行了表征、磁化特性测试以及零磁场环境下介电特性测试;分析了该复合材料的相对介电常数随环境磁场的变化关系以及具有不同含量、粒径纳米颗粒的复合材料磁电容特性差异.实验结果显示,该复合材料的相对介电常数随环境磁场的增大而增大,其变化曲线有一定的滞后特性;复合材料的相对介电常数变化量随材料中纳米颗粒粒径以及含量的增大而增大,但含有较大颗粒复合材料的相对介电常数变化曲线具有较大的滞后性.研究表明,该复合材料在环境磁场中能够产生磁电容效应,其相对介电常数随环境磁场的变化率、饱和值以及滞后性都会受到材料中包含的纳米颗粒的含量以及磁化特性(磁导率、饱和磁化强度、矫顽力)所影响.     

高介电常数TiO2纳米晶的表面态研究

将钛酸四丁酯和硬脂酸在熔融状态下混合均匀后置于冷水浴中,使其凝固成凝胶,通过控制烧结过程中氧气的含量,成功地制备出粒度均匀、介电性能好的纳米晶TiO2.通过采用X射线光电子能谱和表面光电压谱对纳米晶TiO2表面状态的分析发现,材料表面存在大量的氧空位缺陷,暴露在粒子表面上的主要是一些金属Ti4+.纳米材料的这种表面状态对其极化性质具有重要的影响,使其在接近静态条件下的低频介电常数远大于常规材料的介电常数.     

纳米晶钛酸铅表面态对介电性能的影响

将醋酸铅、钛酸四丁酯和硬脂酸在熔融状态下混合均匀后置于冷水浴中，使其凝固成凝胶，经不同温度焙烧，制成纳米晶PbTiO3.用X射线衍射光谱、红外光谱对产物进行表征.采用X射线光电子能谱和表面光电压谱对纳米晶PbTiO3表面状态分析,发现材料表面的不完整性主要是由氧空位造成.暴露在粒子表面的主要是金属离子.随着晶粒尺寸的减小，材料表面氧空位缺陷浓度增加，表面光伏效应增强，谱带变宽.纳米晶PbTiO3材料的表面状态对其极化性质有着重要的影响，使其静态介电常数远大于常规材料的静态介电常数.     

十六烷基胺稳定的CdSe纳米晶体的合成与表征

用CdO通过高温化学方法制备了具有高发光特性的CdSe胶体纳米晶.通过改变配体十六烷基胺在反应体系中的含量,合成了3种不同粒径的CdSe纳米晶.利用TEM、XRD和光谱等手段对合成出来的CdSe纳米晶的形貌结构和发光特性进行了表征.结果表明,随着十六烷基胺在反应体系中量的增多,CdSe纳米晶的粒径增大.通过调整十六烷基胺在反应体系中的量可以方便地控制纳米晶的尺寸.     

立方体纳米Cu2O吸附热力学及动力学的粒度效应研究

采用不同粒径的单一(100)晶面的立方体纳米Cu₂O作为模型材料, 研究了粒径和温度对其吸附动力学和吸附热力学性质的影响规律. 基于已建立的纳米材料吸附热力学和动力学理论, 推导出了单一(100)晶面立方体纳米Cu₂O材料的吸附热力学和吸附动力学性质与粒径之间的关系式. 实验结果与理论预测结果一致: 随着纳米Cu₂O粒径的减小, 吸附速率常数增大而吸附活化能和吸附指前因子减小; 标准摩尔吸附Gibbs自由能 Δ_a $G^{\rlap{-}0}_{m}$减小而标准吸附平衡常数ln $K^{\rlap{-}0}$、 标准摩尔吸附焓 Δ_a $H^{\rlap{-}0}_{m}$和标准摩尔吸附熵 Δ_a$S^{\rlap{-}0}_{m}$均增大, 且以上参数均与粒度的倒数具有较好的线性关系.     

Pb_(1-x)La_xTi_(1-x/4)O_3纳米晶的结构

纳米材料的表面效应和尺寸效应能够使材料性质发生显著变化 .铁电纳米晶体是制备铁电纳米陶瓷和铁电复合材料的基础 ,薄膜材料亦可看作零维纳米材料在二维平面上扩展生长形成的 ,因此铁电纳米晶体结构研究具有重要意义 .对于纯ＰｂＴｉＯ3纳米晶 ,铁电 顺电相变温度随粒径减小而降低 ,并求得了室温下铁电 顺电相变消失、粒子成为顺电体的临界晶粒尺寸[1,2 ].近年来 ,有关Ｌａ改性钛酸铅 (ＰＬＴ)薄膜和纳米粉制备、结构和性质的研究引起了各国学者的重视[3～ 6 ],但对于其微观结构 ,缺乏系统的研究 .我们研究了ＰＬＴ纳米晶的结构和临界晶粒…     

纳米CeO2∶Er荧光粉的光声光谱和荧光光谱研究

采用燃烧法合成了CeO2∶Er纳米荧光粉, 研究了不同粒径大小的CeO2∶Er的晶型和晶貌.TEM结果表明无定形CeO2∶Er包围着纳米晶CeO2∶Er, 可起到表面修饰的作用.光声光谱在保持纳米材料表面状态不改变的前提下, 分析了不同粒径的CeO2∶Er的光谱性质, 解释了随纳米粒径减小CeO2光谱峰吸收峰有蓝移而Er3+没有明显谱峰位移的原因.在荧光光谱中, 发现小粒径的CeO2∶Er有较大的红绿发射比, 并对该现象进行了解释.     

掺杂ZnS纳米粒子的制备及应用

近年来,掺杂ZnS半导体纳米材料作为一类新型发光材料,因其独特的光学特性和在众多领域中的广阔应用前景而成为研究的热点。由于量子尺寸效应,随着纳米粒子粒径减小,掺杂ZnS纳米粒子量子产率增加、带隙能增大,导致吸收光谱和荧光激发光谱发生蓝移,而荧光发射光谱红移。本文详细讨论了影响掺杂ZnS纳米粒子发光性能和量子产率的因素,并综述了掺杂ZnS纳米材料制备及其应用的研究进展。     

基于纳米材料的固相萃取在痕量元素及其形态分析中的应用

作为新型材料的典型代表,纳米材料具有粒径小、比表面积大、表面原子活性高等优点,已成为一类极具潜力的固相萃取材料,在痕量元素及其形态分析领域得到了广泛的应用.本文对不同类型纳米材料与原子光/质谱相结合在痕量元素及其形态分析中的应用现状进行了评述,包括零维纳米材料(如纳米球、富勒烯、量子点等)、一维纳米材料(如碳纳米管、纳米棒、纳米线等)、二维纳米材料(如纳米纤维、石墨烯/氧化石墨烯、层状双氢氧化物等)及三维纳米材料(如三维碳材料、纳米海绵、树枝状大分子等).为了改善其选择性、拓宽其在不同实际样品中的应用潜力、或进一步提高其吸附容量,一些新型的纳米材料包括离子印迹材料、限制性进入材料、金属有机框架材料等也被用于环境及生物样品中痕量元素及其形态的分析,推动了其在该研究领域的进一步发展.     

微波辅助法制备形貌可控CeO_2纳米材料

通过微波辅助法合成粒径均一的CeO2纳米颗粒、纳米立方体和纳米棒。结果表明,通过简单改变微波反应时间可以控制氧化铈形貌的变化。紫外可见光分光光谱测试表明不同形貌的纳米CeO2的紫外吸收能力是不同的,同时CeO2纳米材料的禁带宽度随着形貌由纳米粒子转变到纳米棒而减小。根据对不同微波反应时间的CeO2纳米晶的尺寸、形貌的观察,以及XRD图谱的计算,提出了一种符合实验结果的CeO2纳米材料的生长机制。     

Melting temperature: from nanocrystalline to amorphous phase

By extrapolating the mean grain size of nanocrystal to an infinitesimal value, an amorphous phase has been obtained from the Voronoi construction. The molecular dynamics simulations indicated that for nanocrystal, the grain size variation of melting temperature exhibits two characteristic regions. As mean grain size above about 4 nm for Ag, the melting temperatures decrease with decreasing grain size. However, with grain size further shrinking, the melting temperatures almost keep a constant. This is because the dominant factor on the melting temperature of nanocrystal shifts from grain phase to grain boundary. As a result of fundamental difference in structure, the amorphous phase has a much lower solid-to-liquid transformation temperature than that of nanocrystal.     

Preparation of polyimide/BaTiO3‐nanocrystal hybrid thin films and their dielectric property

High dielectric constant is highly desirable in capacitors and memory devices. In this work, oleic acid (OA)‐capped BaTiO₃ nanocrystals were synthesized by a two‐phase approach. Polyimide (PI)/BaTiO₃‐nanocrystal composite thin films with high dielectric constant have been successfully fabricated. The morphologies and dielectric properties of the hybrid films were exploited. The results showed that BaTiO₃ nanocrystals can be uniformly dispersed in the PI thin films owing to the surface modification of OA‐capped BaTiO₃ nanocrystals. It was found that the dielectric constant of composite film varies with the volume fraction of BaTiO₃ nanocrystals and sintering temperatures and reaches a maximum value of 44.1, which is around 13 times higher than that of pristine PI thin film (3.2). These results demonstrated that PI/BaTiO₃‐nanocrystal composite films have considerable application potential in microelectronic fields.     

Counterion and solvent effects on the dilute solution viscosity of polystyrene ionomers

We present an analysis of data on the intrinsic viscosity [η] of sulfo-polystyrene ionomers in several solvents for a variety of sulfonation levels and counterions. For solvents of low dielectric constant, 2 < ε < 18, [η] decreases from the base polymer value [η]₀ with increasing substitution level. This behavior was attributed to intramolecular association of ionic dipoles. The ratio [η]/[η]₀ was found to depend on a single reduced variable α_Aα_Sx, where x is the fractional substitution, α_A depends only on the counterion, and α_S ∝ ε^?1 depends only on the solvent. For solvents of high dielectric constant, 36 < ε < 47, [η] increases approximately as x³, and counterion effects are small. This behavior was attributed to ionic dissociation, giving rise to a polyelectrolyte effect. Implications of the low ε results are discussed in relation to association-induced gelation behavior and possible generalizations of the reduced variables approach.     

烟酸二聚体的结构与性质

用密度泛函理论B3LYP方法选取6-311+G(d,p)基组对烟酸-烟酸复合物进行了量子化学计算研究, 通过在相同水平下的频率振动分析发现了势能面上存在7个极小值点, 其最稳定构型1对应一N…H—O型强氢键, 其结合能在消除基组重叠误差后为-48.3 kJ·mol-1. 通过自然键轨道(NBO)分析, 研究了电荷转移及轨道相互作用. 通过自洽反应场(SCRF)理论中的极化连续模型(PCM)在介电常数分别为1.0(真空)、2.247(苯)、10.36(二氯乙烷)、20.7(丙酮)、32.63(甲醇)、78.39(水)的不同溶剂环境下重新优化烟酸复合物势能面上最稳定构型1, 研究了溶剂对烟酸复合物几何构型及结合能的影响. 发现溶剂化作用增大了烟酸复合物分子间的结合能, 导致N…H距离减小. 当溶液介电常数在1.0-32.63范围时, 溶剂效应十分显著, 当介电常数大于32.63后, 溶剂化作用趋于稳定.     

Minimization and molecular dynamics studies of guanosine and Z-DNA modified by N-2-acetylaminofluorene

The modeling program AMBER 3.0 was used to study the conformations adopted by the C8-substituted guanosine adduct of the carcinogen N-2-acetylaminofluorene (AAF), called dGuo-AAF. This conformational study was extended to the hexamer d(CGCGCG)₂ in the Z form, modified by AAF at guanine G4 with the carcinogen situated at the helix exterior in two different orientations (named ZAAF-5′ and ZAAF-3′). Considering the importance of electrostatic interactions in case of charged molecules like nucleic acids, minimization and molecular dynamics (MD) were performed using different electrostatic parameters (dielectric functions and scale factors). For that purpose, a subroutine allowing the use of a sigmoidal distance-dependent dielectric function ε_cal has been added to the program. For dGuo-AAF, the results show a great importance of the starting conformation and of the force field parameters on the minimization and MD behaviors. For the AAF-modified Z-DNA, the results display a pronouned dependence on the choice of the set of electrostatic parameters as well. With the distance-dependent dielectric function ε = r, the force field parameters favor the formation of intramolecular H bonds, which can lead to important distortions of Z-DNA. The use of ε = 4r or ε = ε_cal attenuates effectively such a tendency, except in full MD simulations. The dielectric function ε_cal is computing intense, but often similar results are obtained with ε = 4r, especially with the use of the BELLY option. AAF appears to prefer the ZAAF-5′ conformation, i.e., with the fluorene ring stacking on the sugar phosphate backbone of the following 5′ C-G bases. Such a conformation is further stabilized by an intramolecular hydrogen bond between the amino group of the 3′ cytosine and the carbonyl group of AAF. The fluorene ring, although mobile around its long axis, does not flip-flop between its two main orientations, ZAAF-5′ and ZAAF-3′. The presence of the AAF does not prevent the Z_I to Z_II transitions. Whatever the electrostatic parameters, the presence or absence of AAF, the cytosine sugars stay in the C₂′-endo pucker domain. In unmodified Z-DNA, the guanine sugars stay in the C₃′-endo region, except for the terminal guanines which transit to the C₂′endo region. In modified Z-DNA, the sugar of the modified guanine behaves as a terminal guanine sugar.     

Offcenter Molecular Charge Distribution Corrections to Born Equation Electrostatic Solvation Energies

Use of simple model charge distributions and classical multipolar dielectric theory has allowed investigation of the corrections appropriate to the Born equation for structured ion solutes. Among the results obtained for centrosymmetric charge distributions, but presumably of general consequence, are the demonstration of nonlinear dependence and great sensitivity of polarization to charge-cavity boundary proximity, rapid falloff of effects upon continued subdivision of charge, and the significance of solvation energy differences for 2- and 3-dimensional charge distributions. That 50% or greater corrections to the Born energy may readily be obtained in real ion systems, and the lack of sensitivity of such corrections to the dielectric of the medium for ε > 10 are also results of general interest. Analytical approximations for the electrostatic work equations appropriate to high dielectric solvation are included, and how uncertainties in charge magnitude and position for real ions might affect the analysis are also briefly considered.     

Ice nanocrystals in glycerol-water mixtures

We discuss the minimum size of ice nanoparticles in water-rich glycerol-water mixtures, as studied by broadband dielectric spectroscopy (BDS) in the frequency range from 1 Hz to 250 MHz and differential scanning calorimetry (DSC) at the temperature interval from 138 to 313 K. It is known that the extra water which is free from the glycerol hydrogen bond network forms the water cooperative domain. This cooperative domain leads to a freezing of water. With the formation of the frozen water state, another distinct water structure forms on the interface between the ice nanocrystal and mesoscopic glycerol-water domain. The mole fractions of different stages of water (i.e., water molecules in the mesoscopic domain, ice nanocrystals, and the interface between the two) were determined, and the minimum number of water molecules that can gain the bulk ice properties was estimated as approximately 300 water molecules.     

EuF3 纳米晶/PNIPAm复合水凝胶的制备及荧光温敏性能

以十一烯酸为表面活性剂, 采用液体-固体-溶液法(LSS)制备了EuF3纳米晶; 将其用CCl4处理, 得到表面修饰有C-Cl基团的功能化EuF3纳米晶; 通过原子转移自由基聚合(ATRP)制备EuF3 /聚N-异丙基丙烯酰胺(EuF3/PNIPAm)复合温敏水凝胶. 采用HRTEM, XRD, FTIR, DSC及PL等对EuF3 纳米晶及EuF3/ PNIPAm 复合凝胶的微观结构与性能进行了表征, 用变温荧光光谱研究了环境温度对复合凝胶荧光性能的影响. 结果表明, EuF3纳米晶呈六方相晶型; 粒径呈多分散分布, 且相对集中于10, 20和50 nm. 该复合凝胶的较低临界溶解温度(LCST)随纳米晶含量的增加而下降, 环境温度与纳米晶含量对复合凝胶的荧光特性产生明显影响.     

衬底温度对Fe3N薄膜生长和磁性的影响

采用直流磁控溅射方法, 以Si(100) 单晶片为衬底, 在衬底温度为150～450 ℃的范围内得到了ε-Fe3N薄膜样品. 利用 XRD, SEM和VSM等表征手段, 研究了衬底温度对ε-Fe3N薄膜的生长和磁性的影响. 实验结果表明, 随着衬底温度的升高, 薄膜的生长速率、晶粒尺寸和单位质量磁化强度均增大, 而矫顽力呈现先增加后减小的变化趋势, 当衬底温度为350 ℃时, 矫顽力达到最大值18.72 kA/m, 可以认为此时薄膜样品的晶粒尺寸接近于交换作用长度.