Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide

The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13-labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.     

Melting of diamond

Radiation from a Q-switched YAG laser, focused on the (100) face of a single crystal diamond anvil in a high-pressure diamond cell, caused a portion of the diamond anvil face to melt. Potassium bromide mixed with graphite was under pressure between the anvils when melting occurred. The diamond surface melted at pressures greater than approximately 120 kilobars and graphitized at lower pressures. Evidence for the melting and graphitization of the diamond was obtained by optical and scanning electron microscopy.     

以二甲基-正丁基-磺化木质素基氯化铵为模板剂制备多孔钛材料

以碱木质素为原料合成二甲基-正丁基-磺化木质素基氯化铵两性表面活性剂,并以其为模板剂采用溶胶-凝胶法制备多孔钛材料。结果表明:二甲基-正丁基-磺化木质素基氯化铵含氮量为1.360%,含硫量1.860%;红外光谱和1H NMR证实产物中存在磺化和季胺的化学结构。溴酚蓝和亚甲基蓝实验表明二甲基-正丁基-磺化木质素基氯化铵具有两性化合物结构,溶于碱性、中性和稀酸溶液。随着模板剂与钛酸正丁酯的质量比增加,多孔钛材料的比表面积加大;继续增加模板剂的量,多孔钛材料的比表面积下降。多孔钛材料孔径分布范围较宽,为晶态,主要以锐钛矿形式存在。煅烧后的多孔材钛料中有TiO2特征吸收峰,也有少量残留的木质素。当二甲基-正丁基-磺化木质素基氯化铵与钛酸正丁酯的质量比为0.65∶1、煅烧温度为450 ℃时,可得到最大比表面积、锐钛矿晶态的多孔钛材料。      

Direct imaging of reconstructed atoms on TiO2 (110) surfaces

Determining the atomic structures of oxide surfaces is critical for understanding their physical and chemical properties but also challenging because the breaking of atomic bonds in the formation of the surface termination can involve complex reconstructions. We used advanced transmission electron microscopy to directly observe the atomic structure of reduced titania (TiO2) (110) surfaces from directions parallel to the surface. In our direct atomic-resolution images, reconstructed titanium atoms at the top surface layer are clearly imaged and are found to occupy the interstitial sites of the TiO2 structure. Combining observations from two orthogonal directions, the three-dimensional positioning of the Ti interstitials is identified at atomic dimensions and allows a resolution of two previous models that differ in their oxygen stoichiometries.     

Materials: unidirectional solidification of cast iron

The segregation of sulfur in liquid cast iron was studied under conditions of microgravity on Spacelab 1. A rod of cast iron containing carbon, silicon, sulfur, and phosphorus was unidirectionally solidified at four different rates. The influence of sulfur on the graphite structure and the stability of an aluminum oxide skin deposited on the surface of the specimen were investigated.     

Near--Atomic Resolution Imaging of Ferroelectric Liquid Crystal Molecules on Graphite by STM

Near-atomic resolution images of a two-dimensional heteroepitaxial crystal composed of the relatively "functionally rich" chiral liquid crystal mesogen MDW 74 on graphite have been obtained by scanning tunneling microscopy (STM). This work is aimed at developing an improved understanding of the commercially crucial phenomenon of liquid crystal alignment by studying well-characterized surfaces. Herein is reported molecular-level characterization of the surface underlying a ferroelectric liquid crystal in situ, a requisite starting point for understanding the liquid crystal-solid interface at the molecular level. The results are also important in the context of developing a model for the molecular. origins of the contrast observed in STM images of organic monolayers on conductor surfaces. The data and analysis provide strong evidence that neither frontier orbital alone (highest occupied or lowest unoccupied molecular orbital) is sufficient to describe the observed tunneling efficiency.     

Modified phases of diamond formed under shock compression and rapid quenching

Two modified forms of carbon were quenched by a rapid-cooling technique from graphite sheets shock-compressed to 65 gigapascals and 3700 K. One form, ;;n-diamond," which was obtained from the most rapidly cooled part, has a crystal structure close to that of cubic diamond. The other form, found in the relatively slow-cooled part, was comparable to an i-carbon prepared by an ion-beam technique. The n-diamond is interpreted as a metastable form, the same as hexagonal diamond, converted from graphite through a martensitic transition, for which either the region or the path may be different from that of hexagonal diamond. The second form was found to be produced through reconstruction.     

Atomic Control of the SrTiO3 Crystal Surface

The atomically smooth SrTiO(3) (100) with steps one unit cell in height was obtained by treating the crystal surface with a pH-controlled NH(4)F-HF solution. The homoepitaxy of SrTiO(3) film on the crystal surface proceeds in a perfect layer-by-layer mode as verified by reflection high-energy electron diffraction and atomic force microscopy. Ion scattering spectroscopy revealed that the TiO(2) atomic plane terminated the as-treated clean surface and that the terminating atomic layer could be tuned to the SrO atomic plane by homooepitaxial growth. This technology provides a well-defined substrate surface for atomically regulated epitaxial growth of such perovskite oxide films as YBa(2)Cu(3)O(7-delta).     

Phase transformations in carbon fullerenes at high shock pressures

C(60) powders were shock-compressed quasi-isentropically and quenched from pressures in the range 10 to 110 GPa (0.1 to 1.1 Mbar). Recovered specimens were analyzed by Raman spectroscopy and optical microscopy. C(60) fullerenes are stable into the 13- to 17-GPa pressure range. The onset of a fast ( approximately 0.5 micros) reconstructive transformation to graphite occurs near 17 GPa. The graphite recovered from 27 GPa and about 600 degrees C is relatively well ordered with crystal planar domain size of about 100 A. Above 50 GPa a continuous transformation to an amorphous state is observed in recovered specimens. The fast transformation to graphite is proposed to occur by pi-electron rehybridization which initiates breakup of the ball structure and formation of the graphite structure at high density.     

Atomic force microscopy of the electrochemical nucleation and growth of molecular crystals

In situ atomic force microscopy reveals the morphology, surface topography, and growth and dissolution characteristics of microscopic single crystals of the low-dimensional organic conductor (tetrathiafulvalene)Br(0.76)' which are grown by electrocrystallization on a highly oriented pyrolytic graphite electrode in an atomic force microscope liquid cell. The growth modes and the distribution and orientation of topographic features on specific crystal faces, whose identity was determined by "atomic force microscope goniometry," can be correlated with the strength and direction of anisotropic solid-state intermolecular bonding. Growth on the (011) face of (tetrathiafulvalene)Br(0.76) crystals involves the formation of oriented self-similar triangular islands ranging in size from 200 to 5000 angstroms along a side. These nuclei eventually transform into rectangular rafts at larger length scales, where bulk intermolecular bonding interactions and surface energies dominate over nuclei-substrate interactions.     

Carbon-based supercapacitors produced by activation of graphene

Supercapacitors, also called ultracapacitors or electrochemical capacitors, store electrical charge on high-surface-area conducting materials. Their widespread use is limited by their low energy storage density and relatively high effective series resistance. Using chemical activation of exfoliated graphite oxide, we synthesized a porous carbon with a Brunauer-Emmett-Teller surface area of up to 3100 square meters per gram, a high electrical conductivity, and a low oxygen and hydrogen content. This sp(2)-bonded carbon has a continuous three-dimensional network of highly curved, atom-thick walls that form primarily 0.6- to 5-nanometer-width pores. Two-electrode supercapacitor cells constructed with this carbon yielded high values of gravimetric capacitance and energy density with organic and ionic liquid electrolytes. The processes used to make this carbon are readily scalable to industrial levels.     

斜拉索PE保护层表面伤痕检测算法设计

提出了一种检测斜拉索PE保护层表面伤痕算法的设计。首先,在图像的预处理阶段,对原始图像进行灰度化和滤波处理;其次,运用边缘检测、边界跟踪及Hough变换获得了拉索轮廓的连续边界;然后,利用原始的灰度图像和基于拉索轮廓的掩模板,获得了无背景的拉索表面图像;最后,通过基于图像间空间差分的伤痕检测算法,获得斜拉桥拉索表面伤痕的图像,结果表明该算法能有效地从爬升机器人采集的图像中提取出斜拉索PE保护层表面伤痕的图像。     

Phosphorus: an elemental catalyst for diamond synthesis and growth

As diamond-producing catalysts, 12 transition metals such as iron, cobalt, and nickel were first reported by General Electric researchers more than 30 years ago. Since then, no additional elemental catalyst has been reported. An investigation of the catalytic action of group V elements is of great interest from the viewpoint of producing an n-type semiconducting diamond crystal. In the present study, diamond was synthesized from graphite in the presence of elemental phosphorus at high pressure and temperature (7.7 gigapascals and 1800 degrees C). Furthermore, single-crystal diamond was grown on a diamond seed crystal.     

Laser scribing of high-performance and flexible graphene-based electrochemical capacitors

Although electrochemical capacitors (ECs), also known as supercapacitors or ultracapacitors, charge and discharge faster than batteries, they are still limited by low energy densities and slow rate capabilities. We used a standard LightScribe DVD optical drive to do the direct laser reduction of graphite oxide films to graphene. The produced films are mechanically robust, show high electrical conductivity (1738 siemens per meter) and specific surface area (1520 square meters per gram), and can thus be used directly as EC electrodes without the need for binders or current collectors, as is the case for conventional ECs. Devices made with these electrodes exhibit ultrahigh energy density values in different electrolytes while maintaining the high power density and excellent cycle stability of ECs. Moreover, these ECs maintain excellent electrochemical attributes under high mechanical stress and thus hold promise for high-power, flexible electronics.     

Melting of two-dimensional solids

Recent theoretical predictions indicate that melting of a two-dimensional solid may be caused by spontaneous creation of dislocations. The theory predicts that melting occurs by a two-step process involving an intermediate phase, called the hexatic phase, in which there is order in the local crystalline axes but not in the positions of atoms. These ideas are being tested by numerical simulations and by experiments on electrons on liquid helium, liquid crystal films, and rare gas layers adsorbed on graphite. Experiments on liquid crystal films indicate that the three-dimensional analog of the hexatic phase exists, and xenon on graphite exhibits a melting transition close to the form predicted.     

反应氮弧熔覆Ti(CN)/Fe复合涂层组织及耐磨性

采用TXⅡ500型TIG焊机,以Ti粉和石墨粉为原料,以工业纯氮为反应气体和保护气体,利用反应氮弧熔覆技术在Q235试件表面制备了Ti(CN)/Fe金属陶瓷复合涂层。利用扫描电镜、XRD射线衍射仪、显微硬度计、摩擦试验机分析了涂层组织结构、物相组成、显微硬度及涂层的耐磨性。结果表明:涂层成形良好,无裂纹、气孔等缺陷;涂层主要由原位反应形成的TiC0.51N0.12相、Fe相及少量的TiO2相组成;Ti(CN)/Fe涂层的显微硬度高达1 100HV0.5,约是基体金属的3倍;涂层磨损失重约是基体金属的1/8,涂层具有较好的耐磨性。     

Titanium carbide nanocrystals in circumstellar environments

Meteorites contain micrometer-sized graphite grains with embedded titanium carbide grains. Although isotopic analysis identifies asymptotic giant branch stars as the birth sites of these grains, there is no direct observational identification of these grains in astronomical sources. We report that infrared wavelength spectra of gas-phase titanium carbide nanocrystals derived in the laboratory show a prominent feature at a wavelength of 20.1 micrometers, which compares well to a similar feature in observed spectra of postasymptotic giant branch stars. It is concluded that titanium carbide forms during a short (approximately 100 years) phase of catastrophic mass loss (>0.001 solar masses per year) in dying, low-mass stars.     

Molybdenum nanowires by electrodeposition

Metallic molybdenum (Mo(o)) wires with diameters ranging from 15 nanometers to 1.0 micrometers and lengths of up to 500 micrometers (0.5 millimeters) were prepared in a two-step procedure. Molybdenum oxide wires were electrodeposited selectively at step edges and then reduced in hydrogen gas at 500 degrees C to yield Mo(o). The hemicylindrical wires prepared by this technique were self-uniform, and the wires prepared in a particular electrodeposition (in batches of 10(5) to 10(7)) were narrowly distributed in diameter. Wires were obtained size selectively because the mean wire diameter was directly proportional to the square root of the electrolysis time. The metal nanowires could be embedded in a polystyrene film and lifted off the graphite electrode surface. The conductivity and mechanical resiliency of individual embedded wires were similar to those of bulk molybdenum.     

Scanning tunneling microscopy and atomic force microscopy: application to biology and technology

The scanning tunneling microscope (STM) and the atomic force microscope (AFM) are scanning probe microscopes capable of resolving surface detail down to the atomic level. The potential of these microscopes for revealing subtle details of structure is illustrated by atomic resolution images including graphite, an organic conductor, an insulating layered compound, and individual adsorbed oxygen atoms on a semiconductor. Application of the STM for imaging biological materials directly has been hampered by the poor electron conductivity of most biological samples. The use of thin conductive metal coatings and replicas has made it possible to image some biological samples, as indicated by recently obtained images of a recA-DNA complex, a phospholipid bilayer, and an enzyme crystal. The potential of the AFM, which does not require a conductive sample, is shown with molecular resolution images of a nonconducting organic monolayer and an amino acid crystal that reveals individual methyl groups on the ends of the amino acids. Applications of these new microscopes to technology are demonstrated with images of an optical disk stamper, a diffraction grating, a thin-film magnetic recording head, and a diamond cutting tool. The STM has even been used to improve the quality of diffraction gratings and magnetic recording heads.     

钼在石墨炉内石墨探针表面上的原子化机理研究

本文报道了应用Ｘ－射线衍射分析及其它一些实验手段，研究钼在石墨炉内石墨探针表面上的原子化机理。结果表明：钼的原子化源于它的碳化物的热离解。