Au@PS纳米颗粒掺杂PDMS/(PVDF-TrFE)复合薄膜的制备及介电-疏水性能

结合乳液聚合和还原法在250 nm的聚苯乙烯(PS)微球表面均匀负载了Au纳米颗粒. 通过溶液共混法, 使Au@PS纳米颗粒与聚二甲基硅氧烷(PDMS)/聚偏氟乙烯-三氟乙烯[P(VDF-TrFE)](质量比为2∶3)均匀混合, 制备出结构致密、 Au@PS均匀分布的微突起的复合薄膜. 研究了不同Au@PS纳米颗粒掺杂量对复合薄膜的结构、 熔融结晶行为和介电疏水特性的影响. 研究发现, Au@PS纳米颗粒的引入阻碍了P(VDF-TrFE)的β相的产生, 但对PDMS/P(VDF-TrFE)复合薄膜的化学健结构没有显著影响; 随着Au@PS纳米颗粒含量的增多, 复合薄膜结晶温度和玻璃化转化温度升高, 熔点略有降低. 由于界面极化和微电容效应协同作用, 掺杂Au@PS复合薄膜的介电常数有显著提升. PS球表面均匀负载的Au纳米颗粒减少了导电网络的构成, 使介电损耗维持在较低值. 掺杂5%(质量分数)Au@PS的复合薄膜介电常数达到22(100 Hz), 分别为纯PDMS和PDMS/P(VDF-TrFE)的8.8倍和3.14倍, 同时具有优异的疏水特性, 接触角达到112.31°.     

Ba0.6Sr0.4TiO3/聚偏氟乙烯-聚甲基丙烯酸甲酯复合材料的制备及其介电性能

采用流延热压工艺制备Ba_0.6Sr_0.4TiO₃(BST)/聚偏氟乙烯(PVDF)?聚甲基丙烯酸甲酯(PMMA)复合薄膜,研究了PMMA含量对复合材料微观组织结构和介电性能的影响规律。结果表明,BST相能够均匀分散在聚合物基体中,归因于PMMA与PVDF良好的相容性,2种聚合物之间的界面不分明;随着PMMA含量的增加,复合材料的介电常数先降低后升高,耐击穿强度和介电可调性先增加后减少。PMMA含量(体积分数)为15%的BST/PVDF?PMMA₁₅复合材料的综合性能最佳:介电常数为23.2,介电损耗为0.07,耐击穿强度为1412 kV·cm^-1,在550 kV·cm^-1偏压场下,介电可调性为26.2%。     

一步法制备PNIPAAm-g-PAN/PSt载银复合微球及其抗菌性能研究

以AgNO3为金属源,通过乙醇将与聚N-异丙基丙烯酰胺接枝聚丙烯腈/聚苯乙烯（PNIPAAm-g-PAN/PSt）聚合物微球表面酰胺基团配位的银离子（Ag+）还原,一步法制备了PNIPAAm-g-PAN/PSt载银复合微球。通过傅立叶变换红外（FTIR）和紫外-可见光光谱表征发现,由Ag+还原所得的Ag纳米颗粒被成功地固载在PNIPAAm-g-PAN/PSt 微球上;用透射电子显微镜（TEM）对载银微球的大小和形态进行了表征;热重分析（TGA）结果表明,固载在微球表面的银纳米颗粒的含量（质量分数）为12%;抗菌实验结果表明,所制备的载银微球具有抗革兰氏阴性菌的活性。     

银/碳纳米管纳米复合物制备及性质研究

基于苯环与碳纳米管之间较强的π-π共轭效应和醛基对银氨溶液的还原作用,利用吸附在碳纳米管上的香草醛分子原位还原[Ag(NH3)2]+,成功获得了纳米银/碳纳米管(Ag-NPs/CNTs)复合纳米材料。紫外-可见吸收光谱和荧光光谱结果表明,碳纳米管对香草醛分子有较强的吸附作用及银纳米粒子的形成。透射电镜结果表明,碳纳米管表面形成了大小约5.0 nm银纳米颗粒。所制备的纳米复合材料表现出较明显的荧光特性,且对浓度为1.0×10-7～6.0×10-7 mol/L的H2O2表现出较好的电催化还原能力。     

纳米复合材料Ag/MxOy-TiO2(MxOy=ZnO、Al2O3和Fe2O3)的制备及其微波辅助光催化降解甲基橙

采用溶胶-凝胶-程序升温溶剂热一步法,利用表面活性剂EO₂₀PO₇₀EO₂₀(P123)作为模板剂,分别制备了三元纳米复合材料Ag/ZnO-TiO₂、Ag/Al₂O₃-TiO₂和Ag/Fe₂O₃-TiO₂。通过XRD、氮气吸附-脱附测定、TEM以及扫描电子显微镜配合X-射线能量色散谱仪(SEM-EDS)等对合成的3种催化剂进行了对比表征分析。结果表明,复合材料Ag/M_xO_y-TiO₂中Ag以单质形式存在并较好地分布在M_xO_y-TiO₂表面上。所合成产物颗粒尺寸较小(约10 nm左右),形貌较好。其中,Ag/ZnO-TiO₂的比表面积与Ag/Al₂O₃-TiO₂十分相近,略大于Ag/Fe₂O₃-TiO₂。光催化活性研究中,以甲基橙为模型分子且辅以微波场作用。结果显示,上述三元复合材料的活性均明显高于未掺杂银的二元复合材料,其中Ag/ZnO-TiO₂的光催化活性最好,在90 min内对甲基橙的降解率高达86%。     

高介电常数、低介电损耗的聚合物基复合材料*

考虑到高介电常数、低介电损耗聚合物基复合材料在电气、电子行业的广泛重要应用,本文对其研究进展进行了回顾。重点讨论了功能填料、聚合物基体及它们两者的相互作用等因素对聚合物基复合材料介电性能的影响规律,试图为建立高介电常数、低介电损耗的聚合物基复合材料的设计和制备原理理清思路。指出该领域在未来的主要发展方向是涉及制备结构、形貌、尺寸可控的新的功能填料,探索新型简单的复合工艺和界面控制技术,从理论上分析建立功能填料的结构和介电性能的关系模型等。     

玻璃微珠/Ag/TiO2可见光催化剂的制备与表征

通过离子交换法将Ag纳米颗粒负载于玻璃微珠的表面及浅表层,并以钛酸四丁酯的乙醇溶液为前驱体,将TiO₂负载于包含银的玻璃微珠表面,制得一种玻璃微珠/Ag/TiO₂复合光催化剂。由于纳米银的表面等离子体吸收效应,该复合光催化剂具有一定的可见光响应特性。利用XRD、SEM对样品进行表征,可发现玻璃微珠表面形成一层均匀多孔的锐钛矿TiO₂,其粒径均在50 nm左右。由漫反射光谱可得出该催化剂具有较强的可见光吸收,并在降解甲基橙溶液的试验中表现出较好的可见光催化活性。     

TiO_2分级结构/Ag_3PO_4复合材料的可见光催化性能

制备了具有分级结构的海胆状TiO2纳米材料,并通过原位沉积法将可见光响应的Ag3PO4纳米颗粒沉积到TiO2的纳米分级结构上,合成了具有高效稳定可见光催化性能的系列TiO2分级结构/Ag3PO4复合材料,对比测试了系列材料对罗丹明B(RhB)的光催化降解性能.结果表明,TiO2分级结构/Ag3PO4复合材料光催化性能明显高于纯相的Ag3PO4光催化剂,同时也明显优于TiO2(P25)/Ag3PO4复合光催化剂,其中分级结构TiO2与Ag3PO4摩尔比为1∶1的复合材料具有最强的光催化性能,在可见光照射6min内可实现RhB的完全脱色.分析结果表明,与纳米颗粒TiO2相比,具有海胆状纳米结构的TiO2可为Ag3PO4的负载提供更多的担载位点,增加TiO2和Ag3PO4的接触面积,进而提升Ag3PO4光激发产生的光生电子-空穴的分离效率.同时在光降解过程中,Ag3PO4表面存在的少量Ag+会逐渐还原成单质Ag0,通过Ag0的等离子体共振效应,可增加对光子的吸收转换能力,从而进一步提高该复合材料光催化降解染料的性能.     

纳米复合材料中界面动态特性的扫描静电显微技术研究

纳米复合材料中的微观界面结构和界面作用对材料的宏观介电性能, 如介电常数、介电损耗、击穿强度等有十分重要的影响. 本文发展了一种基于扫描静电显微探针技术的测量方法, 可以直接表征二氧化钛/环氧树脂纳米复合材料的微观界面结构及相应的动态介电响应行为. 实验中利用扫描探针的纳米尺度分辨能力, 探测到不同温度下环氧树脂纳米复合材料的局域动态介电响应变化过程, 从而获得纳米颗粒与高分子界面相互作用及极化相关的温度特性. 进一步通过对二氧化钛纳米颗粒进行表面修饰, 得到了两种不同特性的二氧化钛/环氧树脂界面, 验证了不同界面作用引起的复合材料界面区域与非界面区域高分子链介电损耗图像的反差.     

LFP/C掺杂型PVDF-HFP隔膜及其电化学性能研究

本论文向聚偏氟乙烯-六氟丙烯中添加磷酸铁锂纳米颗粒制备得到PVDF-HFP/LFP复合隔膜材料。通过这种掺杂改性,提升了隔膜的吸液率,湿润性,热稳定性,以此提升电池的放电比容量和循环性能。电池正极使用经过碳包覆的磷酸铁锂材料,负极使用金属锂片,通过制备的不同隔膜组装电池探究磷酸铁锂纳米颗粒的添加对PVDF-HFP隔膜性能的影响,并研究了不同比例的磷酸铁锂纳米颗粒对聚合物隔膜的影响。     

Achieving high electric energy storage in a polymer nanocomposite at low filling ratios using a highly polarizable phthalocyanine interphase

Polymer nanodielectrics have become attractive for practical applications such as electric energy storage and electromechanical actuation. However, to enhance the apparent dielectric constant of polymer nanodielectrics, a significant amount (>30 vol %) of spherical particles needs to be incorporated into the polymer matrix. As a consequence, melt-processing of polymer nanodielectrics into uniform thin films becomes difficult at such a high filler content, and electric breakdown strength will greatly decrease. In this work, we describe a three-phase composite approach towards high energy density nanodielectrics at low filling ratios. In this approach, a highly polarizable tetrameric metallophthalocyanine (TMPc) initiator is coated onto 68 nm BaTiO₃ nanoparticles, from which poly(methyl methacrylate) (PMMA) brushes are grafted using atom transfer radical polymerization for the nanoparticles to be uniformly dispersed in a poly(vinylidene fluoride-co-hexafluoropropylene) [P(VDF-HFP)] matrix. For comparison, two-phase P(VDF-HFP)/BaTiO₃ composites without the TMPc interfacial layer are also prepared. Owing to the high polarizability of the TMPc interface layer, the three-phase composite films exhibit higher dielectric constant and thus higher energy density than the two-phase composite films at volume-filling ratios below 5 vol %. Therefore, these high energy density three-phase nanodielectrics with a low filling ratio are promising for melt-processing into thin dielectric films. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1669–1680     

Investigations on the structural,mechanical, thermal,and electrical properties of Ce-doped TiO2/poly(n-butyl methacrylate) nanocomposites

This study focused on the fabrication of poly(n-butyl methacrylate) (PBMA) nanocomposites with various concentrations of cerium-doped titanium dioxide (Ce–TiO₂) nanoparticles via in situ polymerization technique. The structural characterization and the material properties of all the composites were analyzed by UV–visible, FTIR, XRD, SEM, DSC, TG, and tensile strength measurements. The UV–visible and FTIR studies confirmed the effective inclusion of Ce–TiO₂ nanoparticles into the PBMA matrix. The change in amorphous morphology of PBMA to a crystalline structure was observed from the XRD pattern. The SEM morphology revealed the attachment of nanoparticles in the polymer matrix. The inclusion of Ce–TiO₂ nanoparticles enhanced the glass transition temperature, and thermal stability of the PBMA matrix was revealed from DSC and TG, respectively. The tensile strength of PBMA was greatly enhanced by the addition of Ce–TiO₂ nanoparticles. The AC conductivity, dielectric constant, and dielectric loss studies were also performed in the frequency range 10²–10⁶ Hz, and it was observed that addition of Ce–TiO₂ nanoparticles greatly enhanced the electrical properties of PBMA. The change in dielectric constant with the addition of nanoparticles was correlated with a theoretical modeling study. This work also extended to study the role of Ce–TiO₂ nanoparticles in the reinforcing mechanism of the nanocomposite by comparing the actual tensile strength of the composite with different theoretical modeling. The high dielectric constant and tensile strength of composite are beneficial in designing lightweight and highly efficient nanoelectronic materials based on the family of polybutyl acrylates.

     

多级Ag/Bi/氮空位g-C3N4/Ti3C2Tx肖特基结的构筑及其全光谱催化性能

采用原位溶剂热反应制备多级 Ag/Bi/Nv-g-C₃N₄(氮空位-g-C₃N₄)/Ti₃C₂T_x肖特基结, 并对其物相组成和晶体结构、微观形貌和孔结构、表面元素组成和化学态、光学和光电化学性质进行了表征。由于 Ag、Bi和 Ti₃C₂T_x协同的表面等离激元共振效应,Ag/Bi/Nv-g-C₃N₄/Ti₃C₂T_x表现出全光谱吸收特性。由载流子浓度差驱动的界面极化电荷转移诱导形成的肖特基结, 显著提高了光生载流子(包括热电子和热空穴)的分离效率和利用率。因此, 与 Nv-g-C₃N₄、Ti₃C₂T_x、Ag/Nv-g-C₃N₄、Bi/Nv-g-C₃N₄和 Ag/Bi/Nv-g-C₃N₄相比, Ag/Bi/Nv-g-C₃N₄/Ti₃C₂T_x表现出显著增强的全光谱催化活性, 其在可见光和近红外光照射下光催化降解四环素的反应速率常数分别为 0.033和 0.008 6 min^-1, 为对比样品的 10~2.1倍和 8.6~1.8倍。     

Enhanced dielectric performance of TPU composites filled with Graphene@poly(dopamine)-Ag core-shell nanoplatelets as fillers

A new type of graphene@poly(dopamine)-Ag (Gns@PDA-Ag) core-shell nanoplatelets was designed to improve the dielectric properties of thermoplastic polyurethane (TPU) composites. The microstructure, dielectric performances and the effects of Ag nanoparticles’ content on the dielectric properties of composites were investigated. Results showed that the addition of Gns@PDA-Ag nanoplatelets could effectively improve the dielectric constant of the composite. When tested at low frequency (below 100 Hz), the highest dielectric constant of the TPU/Gns@PDA-0.78Ag (3 wt%) composite was 118.82, which was 14 times higher than that of pure TPU (8.39). This increase in dielectric constant should be attributed to the strong polarization effect of conductive graphene nanoflakes (Gns) and Ag nanoparticles to TPU molecules. The PDA shell could prevent direct contact between Gns and Ag nanoparticles, limit the formation of conductive pathways, which kept the dielectric loss of the composites at a low level and maintained the breakdown strength in a stable state. Compared with pure TPU (0.29), the minimum dielectric loss of composites was only 0.36. Moreover, after Gns@PDA-Ag nanoplatelets with higher Ag content were doped into TPU, the composite showed a higher dielectric constant, and due to the existence of the Coulomb blocking effect, the dielectric loss did not increase significantly. The scalability and simplicity of the described method will provide a promising route to polymer composites for highspeed integrated circuits and energy storage applications.     

PMMA: A key macromolecular component for dielectric low-κ hybrid inorganic-organic polymer films

Inorganic-organic composite and hybrid films find widespread applications for the development of functional materials. Polymer matrices with embedded inorganic fillers, nanoparticles or clusters are particularly appealing for optical, electronic, dielectric and magnetic applications. In particular, the development of hybrid layers with tailored dielectric properties represents a key issue in many technological fields.In this framework, poly(methyl methacrylate) (PMMA), due to its outstanding chemico-physical properties, represents a particularly suitable polymer component for the embedding of both microscopic and nanoscopic functional inorganic fillers. The wide use of such a matrix has to be traced back to the favourable combination of chemical and physical properties and easy processing. In this review, the main features and properties of PMMA, with a particular focus on dielectric ones, are firstly briefly described. Selected examples to illustrate the state-of-the art of its corresponding use as dielectric matrix are given and several examples are provided and surveyed.Finally, three case studies concerning PMMA-based hybrid films, produced for very different application fields, are described and discussed. The first example deals with the entrapment of micrometric zinc sulphide powders in PMMA, which acts as a host matrix for the electroluminescent particles in thick film-based Alternate Current Powder Electroluminescent Lamps (ACPELs). The second example describes the preparation of low-κ inorganic-organic hybrid dielectric films based on a PMMA-polyvinylchloride(PVC) blend and a hydrophobic silica powder functionalised on the surface with trimethylsiloxane groups (m-SiO₂). The composition of the investigated materials is [(PMMA)_x(PVC)_y]/(m-SiO₂)_z with z ranging from 0 to 38.3 wt% and x = y = (100 − z)/2. The third case concerns the use of PMMA as a matrix to embed zirconium oxoclusters through the formation of covalent bonds. The obtained material, characterised by a dielectric constant value remarkably lower (1.93 at 1 kHz and 25 °C) than in pristine PMMA (3.0 at 1 kHz and 25 °C), appears as very appealing for the development of microelectronic devices based on low dielectric constant polymer films such as, for instance, field-effect transistor (FET).These three cases are paradigms of three different approaches to composite and hybrid materials based on the embedding of particles in PMMA polymer matrix.     

Gd2O3:Yb3+,Nd3+,Tm3+/SiO2/Ag纳米复合材料的合成及上转换发光性质

通过多步骤的化学法合成了Gd₂O₃：Yb³⁺,Nd³⁺,Tm³⁺/SiO₂/Ag纳米复合材料。利用XRD,TEM,EDS,XPS,CLSM等方法对样品进行表征。实验结果表明,具有低声子能、稳定的化学性质的Gd₂O₃作为上转换发光的基质,当掺杂的敏化剂Nd³⁺离子浓度为1.0%（n/n）,激活剂离子Tm³⁺浓度为0.5%（n/n）时,上转换发光强度达到最大值。此外,表面吸附的Ag纳米颗粒,由于表面等离激元共振耦合作用,使得上转换发光蓝光波段的强度增强1.70倍。     

Structural, magnetic and dielectric properties of Sc modified (1 − y)BiFeO3–yBaTiO3 ceramics

In this study, the bulk ceramics with general formula (1 − y)BiFe_1−xSc_xO₃–yBaTiO₃ (x = 0.1–0.3, y = 0.1–0.3 mol%) were prepared by the traditional solid-state method. Their structural, magnetic, dielectric properties were investigated. X-ray diffraction analysis indicated that all samples crystallized in pure perovskite structure. The structural phase transition from R3c to Pm-3m occurred when the amount of BaTiO₃ exceeded 20 mol%. The room temperature M–H curves were obtained and scandium doping could decrease the magnetic coercive field. Thus the soft magnetic property of prepared solid solutions could be improved. Frequency dependence of dielectric constant and loss were studied. The results indicated that addition of an appropriate amount of scandium could reduce the dielectric loss. The dielectric losses of 0.7BiFe_1−xSc_xO₃–0.3BaTiO₃ (x = 0, 0.1, 0.2, 0.3) at 1 kHz were 0.104, 0.094, 0.043 and 0.057 respectively.     

Influence of ceramic process and Eu content on the composite multiferroic properties of the Ba6−2xLn2xFe1+xNb9−xO30 TTB system

The present work reports the optimisation of the composition and elaboration process of Ba_6−2xLn_2xFe_1+xNb_9−xO₃₀ (0.6 < x < 1.0), a composite multiferroic below 440 K. Both firing and sintering conditions have been investigated in order to lower the two spurious phases content and to improve the ceramic quality. The Eu content has also been varied, with subsequent adjustment of cationic content to maintain charge compensation and site occupancies. The evolution of phase content, dielectric and magnetic properties has been evaluated with respect to these parameters. It was found that optimal processing parameters allow a significant improvement of dielectric properties but leave magnetic properties unaffected. Eu content modification impacts both the dielectric and magnetic properties of the TTB samples and changes their dielectric behaviour from ferroelectric to relaxor.