X射线晶体学结合电子晶体学在复杂无机晶体结构解析中的应用

自然界中的材料,比如无机材料,有机材料,生物材料等等,均有其独特的物理和化学性质。而材料的性能又与材料的结构息息相关,只有充分了解了材料的结构,才能更加深入的研究材料性质。因此,材料结构的确定在化学、物理、生物等学科中的显得尤为重要。X射线晶体学作为传统的结构解析技术仍然是目前最重要的结构解析手段,但是对于复杂结构,X射线衍射晶体学解析结构也存在一些不足,往往需要其他技术手段相补充才能完成复杂结构的结构解析。电子晶体学虽然起步比X射线晶体学晚,但是,经过近几十年的发展,已经是结构解析领域一个非常重要的手段。本文将主要介绍X射线晶体学结合电子晶体学在复杂无机晶体结构解析中的应用。     

A new method of recording diffraction patterns in gas-phase electron diffraction

A new design of the recording unit of an electron diffractometer for gas-phase electron diffraction has been suggested, in which a fixed luminescent screen is used instead of photo plates. The diffraction pattern of a compound displayed on the screen is input to a reading device with contact photographic recording and is transmitted to a computer as digital two-dimensional intensity maps.     

Position determination of scatter signatures--a novel sensor geometry

A novel diffraction sensor geometry able to provide the diffraction pattern of a suspect material without prior knowledge of the samples location is introduced. The sensor geometry can also resolve diffraction patterns originating from multiple unknown materials overlapped along the primary X-ray beam path. This is achieved through tracking Bragg peak maxima that linearly propagate from the inspection volume at a series of X-ray detector positions. A series of simulations and experiments have been performed to verify this technique and provide an insight into its characteristics. Such a technique could have widespread appeal in the security industry. Areas of most relevance include the materials characterisation of volumes such as those prevalent in an airport screening environment or equally the rapid screening for illicit drugs trafficked through the postal system.     

Use of imaging plates (IPs) in the gas-phase electron diffraction (GED) experiments on the EG-100 M apparatus. The tetrachloromethane molecule as a test object

The gas-phase electron diffraction (GED) experiment at the Moscow State University was carried out for the first time using imaging plates (IPs). The response of the Fuji BAS-MP IPs calibrated by means of ¹⁴C standard sources was found to be linear in a broad dynamic interval (larger than 10⁴). The GED study of tetrachloromethane was carried out in order to test the applied technique (IP reader FLA7000) and the developed software. The determined structural parameters of the CCl₄ molecule are in excellent agreement with those obtained in experiments with photographic registration.     

Analytical electron microscopy of materials

Analytical electron microscopy enables combined crystallographic and chemical information with a high spatial resolution to be gained from microregions of electron-transparent specimens. This is reached by the combined application of imaging, diffraction and spectroscopic methods, using either a dedicated scanning transmission electron microscope or a conventional high-resolution electron microscope (having a strong objective lens) equipped with suitable X-ray or electron spectrometers. Of the diffraction methods especially the technique of convergent beam diffraction is used, yielding valuable information on crystal structures, lattice parameter changes, symmetry variations and crystal perfection, respectively. For chemical analysis, either energy-dispersive X-ray spectroscopy (EDX) is used or electron energy loss spectroscopy (EELS). Finally, high-resolution electron microscopy in the lateral resolution range of some 0.1 nm allows the reliable geometrical inspection of extreme microregions.     

Synthesis and gas-sensing characteristics of WO3 nanofibers via electrospinning

WO(3) nanofibers were synthesized using an electrospinning method and characterized by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The obtained WO(3) nanofibers were used as sensitive materials for the detection of NH(3). Indirect-heating sensors based on WO(3) nanofibers were prepared. When the WO(3) nanofiber-based sensors were exposed to 100 ppm NH(3) at 500°C, the response is 5.5, and the response and recovery times are 1 and 5s, respectively. These results indicate that the gas sensors based on WO(3) nanofibers express high and fast response and recovery characteristics to NH(3), and the WO(3) nanofibers are promising sensitive materials for NH(3) detecting.     

X‐Ray Diffraction as a Local Probe Tool

For the structural characterization of nanoscale objects, X‐ray diffraction is widely used as a technique complementing local probe analysis methods such as scanning electron microscopy and transmission electron microscopy. Details on strain distributions, chemical composition, or size and shape of nanostructures are addressed. X‐ray diffraction traditionally obtains very good statistically averaged properties over large ensembles—provided this averaging is meaningful for ensembles with sufficiently small dispersion of properties. In many cases, however, it is desirable to combine different analysis techniques on exactly the same nano‐object, for example, to gain a more detailed insight into the interdependence of properties. X‐ray beams focused to diameters in the sub‐micron range, which are available at third‐generation synchrotron sources, allow for such X‐ray diffraction studies of individual nano‐objects.     

Modeling of scattering on the residual gas in an electron diffraction experiment

The scattering on the residual gas in an electron diffraction chamber is modeled. A comparison with experimental data reveals that is this scattering that may make a major contribution to the extraneous signal inevitably present in the recorded diffraction pattern. Practical recommendations on the development of the electron diffraction apparatus design are given.     

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.     

Neutron diffraction using an electron linear accelerator

The Harwell electron linear acceleratorhelios has been used for studying the crystal structures of polycrystalline materials by neutron diffraction. Atomic positions and atomic vibrational amplitudes can be determined equally well with the pulsed method as with the more conventional method employing a high-flux nuclear reactor as source. The powder pattern can be indexed more easily with pulsed neutrons.     

Study of interaction between microclusters of silver and arsenious trisulphide

Interaction between clusters of silver and arsenious trisulphide have been investigated using electron diffraction and EDAX. The results of the study show the possibility of bulk reactions when clusters of two different materials are brought in contact. The chances of formation of complexes between the clusters are also considerable.     

Low voltage tunable liquid crystal Fibonacci grating

ABSTRACT

In this article, we disclose low voltage tunable liquid crystal Fibonacci gratings (FbG). Photoalignment technique has been used to create two domains of Fibonacci structure using a photomask. Switchable properties of LC are used to tune the diffraction efficiency of different orders by modulating the phase using the electric field. Position of split first orders shows good agreement with the golden ratio characteristic of the FbG. An increase in first-order diffraction efficiency from 3.7% to 6.7% has been achieved with a response time of 5.1 ms. The diffraction almost diminishes at 15 V with a very fast response time of 100 µs, the relaxation time is relatively slower ~26 ms, which is primarily due to higher viscosity. Variation and switching of the intensity of different orders in FbG, by the application of the electric field, can be utilised for selective far-field super-resolution imaging and different photonic applications.     

金属离子对溴碘化银乳剂微晶体的掺杂效应——Ⅰ.Fe3+的掺杂

应用常规感光测定法、电镜法、介电损耗仪和微波光导仪研究了Fe³⁺对卤化根乳剂微晶的掺杂效应,结果表明:Fe³⁺使卤化银乳剂的感光度降低,灰雾降低,而反差变化不大。电镜观察和介电损耗测量表明:Fe³⁺在物理成熟过程中对乳剂颗粒大小和离子电导率的影响不大,而微波光导数据表明,掺杂对电子电导的影响是明显的。上述结果表明:在AgBr中,Fe³⁺起了深的电子陷阱作用,使光电子徙动路程缩短,影响潜影的形成效率。     

The influence of size on phase morphology and Li-ion mobility in nanosized lithiated anatase TiO2

Sustainable energy storage in the form of Li-ion batteries requires new and advanced materials in particular with a higher power density. Nanostructuring appears to be a promising strategy, in which the higher power density in nanosized materials is related to the dramatically shortened Li-ion diffusion paths. However, nanosizing materials also changes intrinsic material properties, which influence both ionic and electronic conductivity. In this work neutron diffraction is used to show that in addition to these two aspects, nanostructuring changes the phase behavior and morphology. Lithiated 40-nm TiO(2) anatase crystallites become single phase, either having the Li-poor original anatase phase, or the Li-rich Li-titanate phase, in contrast to microsized crystallites where these two phases coexist in equilibrium within one crystal particle. In addition, Li(x)TiO(2) compositions occur with stoichiometries that are not stable in micron-sized crystallites, indicating enhanced solid solution behavior. Reduced conduction electron densities at the sites of the Li ions are observed by NMR spectroscopy. This is accompanied by reduced spontaneous Li-ion mobility, suggesting a correlation between the electron density at the Li-ion site and the Li-ion mobility. The present results show that in the case of lithiated anatase TiO(2), significant effects on phase composition, morphology, and electronic configurations are induced, as well as slower intracrystallite Li diffusion.     

Long-range molecular organization of an organic monolayer grafted on a mineral substrate.

Structured and functional materials are of the utmost importance for the development of microelectronic technology. We report on a method to obtain a highly ordered organic molecular layer on a mineral substrate. We took advantage of the regular array of reactive sites present at the single-crystal surface of topaz to perform a liquid-phase silanization reaction. The grazing-incidence diffraction technique was used to characterize the bare and covalently coated surfaces. The ordering of the monomolecular organic layer reproduces the perfect single-crystal structure of the cleaved surface over millimeter distances.     

X-ray Diffraction Mapping for Cultural Heritage Science: a Review of Experimental Configurations and Applications

X-ray diffraction (XRD) mapping consists in the acquisition of XRD patterns at each pixel (or voxel) of an area (or volume). The spatial resolution ranges from the micrometer (μXRD) to the millimeter (MA-XRD) scale, making the technique relevant for tiny samples up to large objects. Although XRD is primarily used for the identification of different materials in (complex) mixtures, additional information regarding the crystallite size, their orientation, and their in-depth distribution can also be obtained. Through mapping, these different types of information can be located on the studied sample/object. Cultural heritage objects are usually highly heterogeneous, and contain both original and later (degradation, conservation) materials. Their structural characterization is required both to determine ancient manufacturing processes and to evaluate their conservation state. Together with other mapping techniques, XRD mapping is increasingly used for these purposes. Here, the authors review applications as well as the various configurations for XRD mapping (synchrotron/laboratory X-ray source, poly-/monochromatic beam, micro/macro beam, 2D/3D, transmission/reflection mode). On-going hardware and software developments will further establish the technique as a key tool in heritage science.     

Improved efficiency of the sputtering technique for pyrite surface and its effect on reduction of electron beam damage

A quick and highly efficient method is described for the preparation of clean and well‐characterised (100) pyrite surfaces on natural crystals based on a sputter/annealing procedure in an ultra‐high vacuum (UHV) chamber. The improvement has been achieved by controlling the ingress of the key contaminants water and oxygen and restricting the annealing temperature to 560 K, which is below the SO₂ dissociation temperature. Low‐energy electron diffraction (LEED) and X‐ray photoelectron spectroscopy (XPS) data were used to study the surface. As well as improving the efficiency of the sputtering technique for this surface, a further major benefit is its high stability against electron beam damage as investigated by a quantitative LEED study. Copyright © 2008 John Wiley & Sons, Ltd.     

1-Furoylthiourea-Sonogel-Carbon electrodes: Structural and electrochemical characterization

A new type of sensor based on Sonogel-Carbon materials modified with 1-(2-furoyl)-3-(1-naphthyl)thiourea is presented to be used as an amperometric sensor for metals. Different percentages of modifier were tested in order to optimise the structural and mechanical properties, as well as the electrochemical behaviour.Scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS), Fourier transform-infrared spectroscopy (FTIR), single crystal X-ray diffraction (XRD) and powder XRD were used for the structural characterization of these electrodes. The 1-(2-furoyl)-3-(1-naphthyl)thiourea did not modify significantly the structural and mechanical properties of the Sonogel-Carbon electrodes, being similar to other modifications carried out previously in these materials. For the study of the electrochemical response, anodic stripping differential pulse voltammetry (ASDPV) was employed, optimising other parameters of measurement such as pH of the buffer, potential and accumulation time and pulse amplitude. The electrochemical response of the modified electrodes improved significantly with respect to the non-modified electrode, giving good signals and acceptable detection limit.     

Ultrafast electron diffraction: oriented molecular structures in space and time.

The technique of ultrafast electron diffraction allows direct measurement of changes which occur in the molecular structures of isolated molecules upon excitation by femtosecond laser pulses. The vectorial nature of the molecule-radiation interaction also ensures that the orientation of the transient populations created by the laser excitation is not isotropic. Here, we examine the influence on electron diffraction measurements--on the femtosecond and picosecond timescales--of this induced initial anisotropy and subsequent inertial (collision-free) molecular reorientation, accounting for the geometry and dynamics of a laser-induced reaction (dissociation). The orientations of both the residual ground-state population and the excited- or product-state populations evolve in time, with different characteristic rotational dephasing and recurrence times due to differing moments of inertia. This purely orientational evolution imposes a corresponding evolution on the electron scattering pattern, which we show may be similar to evolution due to intrinsic structural changes in the molecule, and thus potentially subject to misinterpretation. The contribution of each internuclear separation is shown to depend on its orientation in the molecular frame relative to the transition dipole for the photoexcitation; thus not only bond lengths, but also bond angles leave a characteristic imprint on the diffraction. Of particular note is the fact that the influence of anisotropy persists at all times, producing distinct differences between the asymptotic "static" diffraction image and the predictions of isotropic diffraction theory.     

卤化银感光材料的现状和未来以及学会的作用

接着以前的几篇文章,作者从光吸收、潜影形成效率、最小潜影中心的尺寸以及材料储存期的稳定性角度,分析了卤化银感光材料已达到的性能现状.潜影形成的效率取决于由吸收的光子产生的量子产率、敏化中心对电子的俘获和光电子与正空穴间的复合.可以肯定,感光材料的性能提高尚有很大的余地.依据上述的考察及其与静态数字照相的比较,可预测未来世界的卤化银感光材料生产的发展会趋缓.有一点应清楚,感光科学与技术彼此间已互动促进了许多年,生产出了高精细、高复杂的感光材料,此类科学与技术不是一些后来者能轻而易举超越的,而且它们所取得的各项进展无不依赖于感光科学和技术学会的种种活动.