聚乙烯的结晶形态及高分辨电子显微学研究

高分辨电子显微学研究能从分子水平上直接观察到其他手段所无法得到的信息。但是由于衬度低和耐辐照性能差的缘故使其在高聚物特别是柔性链高分子结晶行为的研究上受到了很大的限制。本论文的研究工作从高聚物样品的统计电子噪声分辨率的各种影响因素出发，对样品的制备，电镜观察状态，底片及成像条件等各个方面进行了系统的分析和改进，克服了柔性链高分子耐辐照性能差的限制，首次成功地得到了聚乙烯这种极不耐辐照损伤的柔性链聚合物晶体的高分辨结构像，为高分辨电子显微学在柔性链聚合物中的应用提供了新的信息和依据，拓宽了高分辨电子显微学的应用领域，也为高分子的凝聚态结构和结晶行为研究提供了新的信，急。聚合物的形态研究，尤其是单晶的形态结构研究，一直是高分子物理中的一项重要研究内容。因为高分子的形态研究是联系高分子结构与高分子材料性质的桥梁和纽带，而且高分子熔体结晶的研究比溶液结晶更接近实际的加工情况，因此研究熔体单晶的形态结构对高分子材料的物理性能具有非常重要的意义。茂金属短链支化聚乙烯具有分子量分布窄，支化分布均匀的特点，其独特的结构使其具有很好的加工性能，而且在学术研究方面可以作为结构模型研究含有支链的高分子结晶行为，有很高的学术研究价值。在本论文的研究中得到了支化聚乙烯的熔体单晶，而且获得了不同温度下熔体单晶随温度变化的形态的改变。随着结晶温度的改变，茂金属催化短链丁基支化聚乙烯的熔体单晶的形态发生了一系列的变化，在结晶温度114℃时，单晶的形态为截顶菱形，可以明显的观察到直的｛110}生长面，在118℃时的透镜形单晶中｛110｝生长面很小而不能被观察到，仅能观察到弧形化的｛200｝生长面。在所有的结晶温度下熔体单晶的形态是沿着b轴不对称生长的。单晶形态的不对称是由于折叠链的倾斜导致单晶内部结构的不对称而引起的。在相同的结晶温度下形成的同一单晶的厚度是不均一的，这主要是由于分子链的倾斜使得两个侧向的｛200｝生长面内的折叠链的表面自由能不同，从而分子链的折叠长度不同而导致单晶出现两种不同的厚度。在低结晶温度下形成的弯曲形的丁基支化聚乙烯其弯曲的径向生长上都是沿着b轴方向生长的，弯曲作用主要是由于两个｛200）区域的生长速率不同引起的。

Molecular beam epitaxy of GaSb on GaAs substrates with AlSb/GaSb compound buffer layers

GaSb films with AlSb/GaSb compound buffer layers were grown by molecular beam epitaxy on GaAs (001) substrates. The crystal quality and optical properties were studied by high resolution transition electron microscopy and low temperature photoluminescence spectra (PL), respectively. It was found that the AlSb/GaSb compound buffer layers can restrict the dislocations into GaSb epilayers. The intensity of PL spectra of GaSb layer becomes large with the increasing the periods of AlSb/GaSb superlattices, indicating that the optical quality of GaSb films is improved.

CERIUM SILICIDE FORMATION IN THIN CE SI MULTILAYER FILMS

Alternating layers of Si(200 angstrom thick) and Ce(200 angstrom thick) up to 26 layers altogether were deposited by electron evaporation under ultrahigh vacuum conditions on Si(100) substrate held at 150-degrees-C. Isothermal, rapid thermal annealing has been used to react these Ce-Si multilayer films. A variety of analytical techniques has been used to study these multilayer films after annealing, and among these are Auger electron spectroscopy, Rutherford backscattering, X-ray diffraction, and high resolution transmission electron microscopy. Intermixing of these thin Ce-Si multilayer films has occurred at temperatures as low as 150-degrees-C for 2 h, when annealed. Increasing the annealing temperature from 150 to 400-degrees-C for 1 h, CeSi2 forms gradually and the completion of reaction occurs at approximately 300-400-degrees-C. During the formation of CeSi2 from 150-400-degrees-C, there is some evidence for small grains in the selected area diffraction patterns, indicating that CeSi2 crystallites were present in some regions. However, we have no conclusive evidence for the formation of epitaxial CeSi2 layers, only polycrystals were formed when reacted in the solid phase even after rapid thermal anneal at 900-degrees-C for 10 s. The formation mechanism has also been discussed in combining the results of the La-Si system.

Growth of GaAs on Si by using a thin Si film as buffer layer

We report a novel technique for growing high-quality GaAs on Si substrate. The process involves deposition of a thin amorphous Si film prior to the conventional two-step growth. The GaAs layers grown on Si by this technique using metalorganic chemical vapor deposition exhibit a better surface morphology and higher crystallinity as compared to the samples gown by conventional two-step method. The full width at half maximum (FWHM) of the x-ray (004) rocking curve for 2.2 mu m thick GaAs/Si epilayer grown by using this new method is 160arcsec. The FWHM of the photoluminescence spectrum main peak for this sample is 2.1 meV. These are among the best results reported so far. In addition, the mechanism of this new growth method was studied using high-resolution transmission electron microscopy.

Fabrication of Silicon Crystal-Facet-Dependent Nanostructures by Electron-Beam Lithography

Silicon crystal-facet-dependent nanostructures have been successfully fabricated on a (100)-oriented silicon-on-insulator wafer using electron-beam lithography and the silicon anisotropic wet etching technique. This technique takes ad-vantage of the large difference in etching properties for different crystallographic planes in alkaline solution. The mini-mum size of the trapezoidal top for those Si nanostructures can be reduced to less than 10nm. Scanning electron microscopy(SEM) and atomic force microscopy (AFM) observations indicate that the etched nanostructures have controllable shapes and smooth surfaces.

Polymorphous silicon nanowires synthesized by plasma-enhanced chemical vapor deposition

Polymorphous Si nanowires (SiNWS) have been successfully synthesized on Si wafer by plasma enhanced chemical vapor deposition (PECVD) at 440degreesC,using silane as the Si source and Au as the catalyst. To grow the polymorphous SiNWS preannealing the Si substrate with Au film at 1100 degreesC is needed. The diameters of Si nanowires range from 15 to 100 urn. The structure morphology and chemical composition of the SiNWS have been characterized by high resolution x-ray diffraction, scanning electron microscopy, transmission electron microscopy, as well as energy dispersive x-ray spectroscopy. A few interesting nanowires with Au nanoclusters uniformly distributed in the body of the wire were also produced by this technique.

Strong red light emission from silicon nanocrystals embedded in SIO2 matrix

In this study, silicon nanocrystals embedded in SiO2 matrix were formed by conventional plasma enhanced chemical vapor deposition (PECVD) followed by high temperature annealing. The formation of silicon nanocrystals (nc-Si), their optical and micro-structural properties were studied using various experimental techniques, including Fourier transform infrared spectroscopy, micro-Raman spectra, high resolution transmission electron microscopy and x-ray photoelectron spectroscopy. Very strong red light emission from silicon nanocrystals at room temperature (RT) was observed. It was found that there is a strong correlation between the PL intensity and the substrate temperature, the oxygen content and the annealing temperature. When the substrate temperature decreases from 250degreesC to RT, the PL intensity increases by two orders of magnitude.

The photon scanning tunneling microscope and its applications

A simple photon scanning tunneling microscope (PSTM) is described. Its lateral resolution (similar to 10nm with a maximal scanning range of 10 mu m x 10 mu m ) is much better than that of a conventional optical microscope. Its principle, the fiber optic tip fabrication and PSTM images of different samples such as mica, HDPE and LiNbO3 are presented.

Fabrication of nano-sized grains by pulsed laser surface melting

In this work, the formation and characterization of nano-sized grains on the modified surfaces of GCr15 and H13 steels have been investigated. The material was processed by pulsed laser surface melting (LSM) under different depths of de-ionized water. The microstructures and phases of the melted zones were examined by x-ray diffraction, environmental field emission scanning electron microscopy and high resolution transmission electron microscopy. The results indicate that LSM under water can successfully fabricate nano-scaled grains on the surfaces of steel, due to the rapid solidification and crystallization by heterogeneous nucleation. The elemental segregation of chromium and activated heterogeneous nucleation mechanism of austenite in liquid metal play a key role in the formation of nano-sized grains at high cooling rates. This one-step technique provides us a new way to prepare uniform nano-scaled grains, and is of great importance for further understanding the growth of nano-materials under extreme conditions.

Electrochemical fabrication of single-crystalline and polycrystalline Au nanowires: the influence of deposition parameters

We report the electrochemical growth of gold nanowires with controlled dimensions and crystallinity. By systematically varying the deposition conditions, both polycrystalline and single-crystalline wires with diameters between 20 and 100 nm are successfully synthesized in etched ion-track membranes. The nanowires are characterized using scanning electron microscopy, high resolution transmission electron microscopy, scanning tunnelling microscopy and x-ray diffraction. The influence of the deposition parameters, especially those of the electrolyte, on the nanowire structure is investigated. Gold sulfite electrolytes lead to polycrystalline structure at the temperatures and voltages employed. In contrast, gold cyanide solution favours the growth of single crystals at temperatures between 50 and 65 degrees C under both direct current and reverse pulse current deposition conditions. The single-crystalline wires possess a [110] preferred orientation.

Electrochemical polymerization and characterization of polypyrrole nanowires and nanotubules

Polypyrrole nanostructure arrays, including simultaneously large quantities of nanowires and small quantities of partially filled nanotubules have been electrochemically synthesized in home-made etched ion-track polycarbonate (PC) templates. Diameter of the prepared nanostructures varies from 45 to 320 nm with their lengths up to 30 microns. Morphological studies of these nanostructures were performed by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. While optical absorption properties were studied by ultraviolet-visible-near infrared spectrophotometry (UV-vis-NIR). It has been observed that the absorption maximum of polypyrrole shifts to the longer wavelength side as the diameter of these nanostructures (nanowires and nanotubules) increases. (C) 2010 Elsevier B.V. All rights reserved.

Effect of Crystallographic Texture on Magnetic Characteristics of Cobalt Nanowires

Cobalt nanowires with controlled diameters have been synthesized using electrochemical deposition in etched ion-track polycarbonate membranes. Structural characterization of these nanowires with diameter 70, 90, 120 nm and length 30 mu m was performed by scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray diffraction techniques. The as-prepared wires show uniform diameter along the whole length and X-ray diffraction analysis reveals that [002] texture of these wires become more pronounced as diameter is reduced. Magnetic characterization of the nanowires shows a clear difference of squareness and coercivity between parallel and perpendicular orientations of the wires with respect to the applied field direction. In case of parallel applied field, the coercivity has been found to be decreasing with increasing diameter of the wires while in perpendicular case; the coercivity observes lower values for larger diameter. The results are explained by taking into account the magnetocrystalline and shape anisotropies with respect to the applied field and domain transformation mechanism when single domain limit is surpassed.

Molecularly imprinted monolithic stationary phases for liquid chromatographic separation of enantiomers and diastereomers

The method for preparation of molecularly imprinted monolithic stationary phase has been improved to achieve liquid chromatographic separation of enantiomers and diastereomers. By adopting low polar porogenic solvents of toluene and dodecanol and optimal polymerization conditions, the molecularly imprinted monolithic stationary phases with good flow-through properties and high resolution were prepared. Enantiomers of amino acid derivatives and diastereomers of cinchona alkaloids were completely resolved using the monolithic stationary phases. The influence of porogenic composition, monomer-template ratio and polymerization conditions on the chromatographic performance was investigated. Some chromatographic conditions such as the composition of the mobile phase and the temperature were characterized. Scanning electron microscopy showed that the molecularly imprinted monolithic stationary phase has a large through-pore structure to allow the mobile phase to flow through the column at very low backpressure. Accelerated separations of enantiomers and diastereomers were therefore achieved at elevated flow rates. Finally, the chiral recognition performance of the prepared stationary phase in aqueous media was investigated. Hydrophobic interaction, and ionic and/or hydrogen bonding interactions were proposed to be responsible for the recognition mechanism. (C) 2002 Elsevier Science B.V. All rights reserved.

Self-assembled 3D Architectures of LuBO3 : Eu3+: Phase-selective synthesis, growth mechanism, and tunable luminescent properties

Rhombohedral-calcite and hexagonal-vaterite types of LuBO:Eu3+ microparticles with various complex self-assembled 3D architectures have been prepared selectively by an efficient surfactant- and template-free hydrothermal process for the first time. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometry, transmission electron microscopy, high-resolution transmission electron microscopy, selected area electron diffraction, photoluminescence, and cathodoluminescence spectra as well as kinetic decays were used to characterize the samples.

Preparation and Luminescence Properties of YVO4:Ln and Y(V, P)O-4:Ln (Ln = Eu3+, Sm3+, Dy3+) Nanofibers and Microbelts by Sol-Gel/Electrospinning Process

One-dimensional YVO4:Ln and Y(V, P)O-4:Ln nanofibers and quasi-one-dimensional YVO4:Ln microbelts (Ln = Eu3+, Sm3+, Dy3+) have been prepared by a combination method of sol-gel process and electrospinning. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric and differential thermal analysis (TG-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), and time-resolved emission spectra as well as kinetic decays were used to characterize the resulting samples.