高分子复合材料界面结构研究

高分子材料表、界面的结构变化或化学反应常影响该材料的性能。聚合物的表面结构及复合物的界面结构研究,对于工程材料、粘合及涂料工业都有重要的意义。近十几年来迅速发展起来的光谱技术,使这项研究工作可以普及到许多实验室去进行。其中X射线光电子能谱(XPS或称为ESCA)、俄歇电子能谱(AES)、离子散射光谱(ISS)、穆斯     

Janus复合材料调控界面

Janus材料集成不同组成/功能于一体,具有明确的空间分区特征,是一类特殊的高分子复合功能材料.有机高分子链提供亲水/亲油及响应特性,无机组成提供丰富的光、电、磁、热等功能性.两亲性的Janus材料在高效稳定界面同时,还能赋予界面功能性并可在外场作用下实现操控.本文重点总结了不同结构和功能的Janus材料在稳定界面和调控界面的近期主要进展,包括聚集行为、固体乳化剂、界面增容、界面催化、功能涂层、细胞诊断与治疗等方面.     

热塑性碳纤维复合材料界面研究

综述了热塑性碳纤维复合材料界面研究的新进展。指出由于热塑性复合材料基体树脂是高聚物,熔体牯度很大,很难均匀地分布在增强纤维之中并与纤维形成良好浸溃,存在界面结合不良的问题,因此对其界面优化设计要有一个新的认识。界面上没有化学键结合,界面结合不良,但只靠短化学键的连接,界面结合也不良,必须有一个强韧结合的界面,既有强结合又具有界面松弛能力,同时又能与高聚物基体融合的界面缓冲层的优化设计。对于Plueddemann偶联剂的概念中偶联剂“必须成为树脂的一部分”,作者认为最好的方法是就是树脂本身,即它既与纤维化学键键合,又与树脂良好相容,界面匹配。这将是热塑性复合材料界面层设计的一种新方法。     

纤维增强复合材料界面剪切强度及界面微观结构的表征

界面在纤维增强复合材料中具有特别重要的作用,它不但是纤维增强复合材料中增强相和基体相连接的纽带,也是应力及其他信息传递的桥梁。良好的界面粘结才能使纤维的性能得到充分发挥,进而纤维增强复合材料的力学性能得到提高,因此对纤维增强复合材料的界面粘结性能、界面微观结构的研究非常重要。本文总结了纤维增强复合材料界面剪切强度、界面微观结构的表征方法,包括单纤维拔出试验、纤维断裂试验、纤维压出试验等,并侧重介绍了拉曼光谱对纤维增强复合材料界面粘结性能、界面微观结构的研究。     

纳米无机粒子/聚合物复合材料界面结构的研究

纳米粒子具有许多特性,聚合物中加入纳米粒子可以制备得到性能更加优异的复合材料,其中纳米粒子和聚合物基体间的界面对决定纳米复合材料的性能起着重要作用.本文综述了近些年来表征纳米无机颗粒/聚合物复合材料中界面结构的研究手段,如红外光谱(FTIR)、热重(TGA)、电子显微镜、小角中子散射(SANS)及小角X射线散射(SAXS)等,及界面结构与复合材料力学性能和热稳定性关系的研究进展.同时也介绍了纳米粒子对复合材料的渗透、光催化、阻燃、介电及导电性能的影响.最后对这一领域的研究进行了展望.     

玄武岩纤维增强树脂基复合材料界面改性策略

近年来,工业界和学术界都将注意力聚焦在可持续天然纤维复合材料的开发上。玄武岩纤维具有高强度、高模量、耐高温、耐酸碱、隔热隔音、热振稳定性好、介电性能优异、绿色无污染及成本低等优点,玄武岩纤维增强树脂基复合材料凭借其优异的机械性能和可设计性被广泛地应用于飞行器、汽车、船舶、建筑、石油化工管道及风力发电机叶片等领域。然而,玄武岩纤维与聚合物基底间差的相容性导致玄武岩纤维增强树脂基复合材料存在诸多缺陷和不足。其中,界面强度不够高、界面相易被破坏的问题成为制约玄武岩纤维增强树脂基复合材料发展的瓶颈之一,因此许多玄武岩纤维增强树脂基复合材料研究工作集中在提高其界面结合能力上。本文介绍了玄武岩纤维增强树脂基复合材料的主要研究方向,以及几种常见的复合材料界面作用机理,并综述了近年来国内外关于玄武岩纤维增强树脂基复合材料界面增强改性方面的研究工作。     

含液晶聚合物的原位复合材料中界面相容性的改善策略

综述了近年来含液晶聚合物的原位复合材料中增容技术的一些进展,主要了四种增容技术,即加入具有增容作用的第三组分;在分散相液晶聚合物的主链上引入与基体树脂主链中相同或相似的单元,酯交换反应和多元共混技术,简要描术字原位复合材料的发展趋势。     

PS/MWNT复合材料界面上的化学反应性

利用悬浮聚合法制备了可溶于甲苯的聚苯乙烯／多壁碳纳米管（PS／MWNT）复合材料,通过透射电镜观察到MWNT完全或部分被PS包裹。拉曼光谱分析表明,复合材料中MWNT的两个特征峰D峰和G峰的位置均发生了红移,且D峰的强度及ID／IG值也较MWNT明显增大。凝胶渗透色谱测得复合材料的分子量相对于纯PS的分子量有较大幅度提高。同时比较共混法与悬浮聚合法制得的复合材料在甲苯中的溶解性。可以认为悬浮聚合法制备复合材料的过程中,MWNT参与了PS的聚合反应,与PS形成了化学键从而完全或部分地被PS包裹。     

热塑性聚氨酯及其复合材料的界面形态与流变特性

以聚酯型热塑性聚氨酯(thermoplastic polyurethane,TPU)、玻璃纤维(glass fiber,GF)和玻璃微珠(glass bead,GB)为主要原料制备了TPU/GF、TPU/GB共混物,考察了复合体系的热性能、微观结构、动态流变特性.研究发现,TPU是温敏型聚合物,其温敏性与材料的硬段含量有关,在加工过程中,除考虑剪切速率的影响外,需重点考虑温度对其加工性能的影响;GF,GB填充TPU体系具有良好的分散形态和界面结合牢度,GF和GB的加入能够增加体系的黏度,降低TPU的温敏性,加宽TPU的加工温度窗口,从而改善其成型加工性,并能一定程度地提高其耐热性.研究还发现,复合体系黏度的增加程度不仅和填料的含量有关,而且与填料的形状有关,可用等效直径表征.另外,从比表面积的角度比较了玻璃纤维和玻璃微珠对体系热稳定性的影响.     

尼龙6/碳纤维微复合材料的界面微观力学

选用微球脱黏实验,在其基础上改进了制样方法,并分析了界面参数对界面微观力学性能的影响.结果显示,树脂微球脱黏时的力值Fmax随着纤维在树脂基体中的包埋长度le增大而以斜率k的趋势线性增大,截距为b;界面剪切强度τIF与le呈双曲线函数关系,随着le增大而增大,并最终趋向于一个极限值k′.此外,还讨论了不同的界面参数,如函数Fmax(le)的斜率k,截距b值,对函数Fmax(le)和τIF(le)的曲线分布的影响,以及试样形貌对实验数据分散性的影响。     

基于透射电子显微镜的沸石分子筛结构研究进展

透射电子显微镜是解析沸石分子筛新结构、 分析结构缺陷和研究活性位点等的有力工具. 应用于分子筛研究的透射电子显微术总体上可以分为图像法和衍射法, 包括透射电子显微镜和扫描透射电子显微图像、 选区电子衍射和三维电子衍射, 通常结合其中的几种方法进行分析. 近年来, 随着电子显微镜硬件性能的不断提升, 特别是球差矫正器的广泛应用及各种适用于分子筛等电子束敏感材料的探测器和图像处理技术的不断革新, 在原子尺度观察分子筛的结构已成为可能. 此外, 利用原位电子显微镜技术研究分子筛的生长和催化反应机理也在逐步展开. 本文按电子显微镜方法分类, 综述了近些年基于电子显微镜的分子筛研究, 包括新结构解析、 手性确认和金属负载等的最新进展.     

竹纤维/聚丙烯复合材料界面相容性研究进展

竹纤维具有密度低、强度高、价格低和可再生等优点,是工程结构材料中的理想增强材料。以竹纤维增强聚丙烯是目前制备高性能聚丙烯复合材料的研究热点,也是可持续发展的重要方向之一。为得到高性能的复合材料,需要对竹纤维和聚丙烯基体界面进行处理。本文综述了改善竹纤维与聚丙烯基体界面相容性的三种方法,包括竹纤维的表面改性、聚丙烯基体的改性和添加第三组分,指出了三种方法的优缺点,并展望了提高竹纤维/聚丙烯复合材料界面相容性的研究方向。     

Preparation of Polymer‐Metal Composites via In Situ Decomposition of Metal Salts by Frontal Polymerization

Composites containing powdered zinc, and zinc/lead acetate were prepared via frontal polymerization. In the case of the acetates, elemental metal was formed in an in situ decomposition process. The local area function was used to demonstrate the distribution of fillers, and the uniformity of the area fraction for the quantitative characterization of the distribution. With the use of metal acetates, composites of uniform metal distribution can be produced, unlike in systems with metal powder, where the metal particles are enriched at the margin of the sample. It can be established that the specific direct‐current resistance significantly decreases in AA‐TGDMA composites by the addition of zinc acetate, compared to that of the initial monomer mixture. On heating, the unreacted zinc acetate decomposes further, which results in the further decrease in electrical resistance.

     

MB25镁合金中的准晶体与晶体相的研究

利用透射电子显微术（ＴＥＭ）及能谱仪微区成分分析（ＥＤＳ）技术，对含有稀土元素的铸态Ｍｇ－Ｚｎ－Ｚｒ－Ｙ系高强镁合金ＭＢ２５中的稀土相鉴定发现，在铸态合金的晶界上存在准晶相，其电子衍射谱显示出５－３－２次对称的特点，为二十面体准晶相。在与准晶相连区域发现一种ＭｇＺｎ＿２型的Ｌａｖｅｓ相，其点阵常数为ａ＝０．５４２ｎｍ，Ｃ＝０．８７３ｎｍ。     

Full Metal Species Quantification of Metal Supported Catalysts Through Massive TEM Images Recognition

For a practical high-loading single-atom catalyst, it is prone to forming diverse metal species owing to either the synthesis inhomogeneity or the reaction induced aggregation. The diversity of this metal species challenges the discerning about the contributions of specific metal species to the catalytic performance, and thus hampers the rational catalyst design. In this paper, a distinct solution of dispersion analysis based on transmission electron microscopy imaging specialized for metal-supported catalysts has been proposed in the capability of full-metal-species quantification(FMSQ) from single atoms to nanoparticles, including dispersion densities, shape geometry, and crystallographic surface exposure. This solution integrates two image-recognition algorithms including the electron microscopy-based atom recognition statistics (EMARS) for single atoms and U-Net type deep learning network for nanoparticles in different shapes. When applied to the C₃N₄- and nitrogen-doped carbon-supported catalysts, the FMSQ method successfully identifies the specific activity contributions of Au single atoms and particles in butadiene hydrogenation, which presents remarkable variation with the metal species constitution. This work demonstrates a promising value of our FMSQ strategy for identifying the activity origin of heterogeneous catalysis.     

High-Resolution Transmission Electron Microscopy Re-examined as a Tool in Solid State Chemistry

Transmission electron microscopy (TEM) can be used with crystalline solids to obtain direct images of small structural groups comprising a few coordination polyhedra with resolution nearly down to atomic scale (“lattice imaging”). More exact knowledge of the conditions required for direct imaging, as well as improvements in the instruments themselves, have now made it possible to examine very small defect regions (microdomains), faults in the stacking sequence of structural groups or atom layers (planar or Wadsley defects), and isolated defects in narrowly delimited areas that may actually be below the dimensions of the unit cell. The structural principle of the very smallest ordered regions can even be determined when X-ray structure analysis proves unable to do this. “Block structures” are particularly suitable as models for the testing and further development of the high-resolution method; the detection of three-dimensional, two-dimensional, and one-dimensional defects has been studied on such structures.     

电极界面浓差极化对锂金属沉积的影响

锂金属作为下一代高能量密度电池的理想负极材料受到研究人员广泛关注。然而,锂枝晶生长引起的安全隐患和循环寿命短等问题严重影响了锂金属电池的实用化进程。本文以电化学现象和理论为依据,从浓差极化角度详细分析锂金属电沉积过程中枝晶生长、死锂形成和全电池失效机制,并对目前研究较多的多孔宿主电极中的浓差极化及枝晶抑制进行分析,提出锂金属界面浓差电池现象。本文得到的结论为研究人员更深入地探究锂金属保护策略提供了理论依据。     

Structural and Chemical Analysis of Materials with High Spatial Resolution

 An understanding of the correlation between microstructures and properties of materials require the characterization of the material on many different length scales. Often the properties depend primarily on the atomistics of defects, such as dislocations and interfaces. The different techniques of transmission electron microscopy allow the characterization of the structure and of the chemical composition of materials with high spatial resolution to the atomic level: high resolution transmission electron microscopy allows the determination of the position of the columns of atoms (ions) with high accuracy. The accuracy which can be achieved in these measurements depends not only on the instrumentation but also on the quality of the transmitted specimen and on the scattering power of the atoms (ions) present in the analyzed column. The chemical composition can be revealed from investigations by analytical microscopy which includes energy dispersive X-ray spectroscopy, mainly quantitatively applied for heavy elements, and electron energy-loss spectroscopy. Furthermore, the energy-loss near-edge structure of EELS data results in information on the local band structure of unoccupied states of the excited atoms and, therefore, on bonding. A quantitative evaluation of convergent beam electron diffraction results in information on the electron charge density distribution of the bulk (defect-free) material. The different techniques are described and applied to different problems in materials science. It will be shown that nearly atomic resolution can be achieved in high resolution electron microscopy and in analytical electron microscopy. Recent developments in electron microscopy instrumentation will result in atomic resolution in the foreseeable future.     

Electron Diffraction with the Transmission Electron Microscope as a Phase-Determining Diffractometer—From Spatial Frequency Filtering to the Three-Dimensional Structure Analysis of Ribosomes

Chemists recognize X-ray crystal structure analysis and electron microscopy as powerful methods of analysis. In the last 20 years the basic ideas of X-ray diffraction analysis have been extended to the field of electron microscopy, whereby an image-forming apparatus is converted into an electron diffractometer, and through which an old dream of crystallographers can be realized—the measurement of the phase shift of scattered waves, a prerequisite for the direct calculation of structures. Its most important area of application, like that of the X-ray diffractometer, is in three-dimensional structure analysis—in all fields of science. However, beyond crystallography, aperiodic structures (comparable to crystals with a single unit cell) can also be analyzed three-dimensionally. In this progress report, the development of the first idea (spatial frequency filtering) to the analysis of ribosomal particles is outlined. Attention will be focused primarily on quantitative methods for the measurement of scattered rays, which are also usable beyond the conventional limit of resolution, down to atomic resolution. In the course of this work in 1968, the principle of the three-dimensional analysis of native biological crystal structures using the electron microscope, as worked with today in many laboratories, was developed. In Munich, however, further research focused on the three-dimensional analysis of aperiodic and individual (especially biological) objects. The analysis of 50S-subunits of the procaryotic ribosome of E. coli showed surprisingly good reproducibility of the results (although only within the same orientation), allowing the deduction of almost ideal average model structures from a limited number of particles.