Atom-probe field ion microscopy

The atom probe field ion microscope (AP-FIM) is a combination of a field ion microscope and a time-of-flight mass spectrometer with a single ion detection sensivity. With the field ion microscope topology of a surface, surface reactions and surface modifications can be studied in atomic detail. By time-of-flight measurements surface layers and interface layers can be chemically analyzed atom by atom and atomic layer by atomic layer. Compositional variations according to surface or interface segregation, precipitations, or surface changes in corrosion or in electrochemical layer formation etc. can be studied quantitatively on a subnanometer scale. Some of our studies on related problems will be decribed briefly.     

Fundamental aspect and behavior of saturated fluorocarbons in glow discharge in absence of potential source of hydrogen

The glow discharge of a series of saturated fluorocarbons, C_nF_2n+2 (n = 1, 2, 4, 6, and 8), was studied with glass substrates which do not contain any hydrogen. It was found that the deposition rate was a function of the F/C ratio of the starting fluorocarbons. That is, fluorocarbons with higher F/C ratio, such as CF₄ and C₂F₆, hardly polymerized, while fluorocarbons with lower F/C ratio, such as C₈F₁₈, polymerized as well as C₂F₄. After plasma exposure, the surface of glass substrate was characterized by measurements of water contact angle, water droplet rolling-off angle, and ESCA. Although all saturated fluorocarbon plasmas could alter the surface more hydrophobic than before, the deposited materials from fluorocarbons with higher F/C were not stable. Also, in plasmas with high F/C fluorocarbons, i.e., CF₄ and C₂F₆, sputtering of the electrode material was observed. © 1992 John Wiley & Sons, Inc.     

Characterization of Heterogeneous Catalysts by use of Test Reactions

The following report gives an overview on work done in the Catalysis Laboratory of the Department of Chemistry, National University of Singapore over the last 15 years (1989–2004). Much of this work can be described as “characterization of catalytically active surfaces through test reactions”. The methods, systems studied and the reactions that we evaluated will be described. The review will mostly concentrate on work from the authors’ laboratory, but other relevant work will also be cited.     

Improving the efficiency and convergence of geometry optimization with the polarizable continuum model: new energy gradients and molecular surface tessellation

New equations are derived and implemented for efficient and accurate computation of solvation energy derivatives for the conductor-like polarizable continuum model (C-PCM) and the isotropic integral equation formalism polarizable continuum model (IEF-PCM). Two new molecular surface tessellation procedures GEPOL-RT and GEPOL-AS that generate near continuous potential energy surfaces are proposed for PCM geometry optimization. The combined use of these new techniques leads to efficient and convergent geometry optimizations with the PCMs.     

Effect of WO3 particle size on the type and concentration of surface oxygen

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Anomalous Density and Permittivity Effects on the Structure of Water

The relationship between the structural peculiarities of the hydrogen bond net and the anomalous behavior of density and dielectric permittivity of water is investigated. The degree of ordering in the network of hydrogen bonds is described in terms of the structural functions, among which the most important ones are tetrahedricity and the mean number of hydrogen bonds per molecule. The temperature dependence of the number of hydrogen bonds per molecule is discussed in terms of the analysis of the experimental temperature dependences of density and permittivity of water on the saturation line. The estimated density of hexagonal ice at the melting point is reproduced in terms of the concepts suggested for analysis; the estimate is rather close to the experimental value. Possible applications of the new approach are discussed.     

Surface modification of proteins by covalent binding of acrylic polymers

Surface modification of enzymes for a potential use in therapy was obtained with a new type of tailor-made copolymers ofNacryloylmorpholine andN-acryloxysuccinimide. The first monomer was designed to confer solubility on the polymer, whereas the second was used to give it reactivity toward protein amino groups. The reactivity of polymers of different composition towards amino acid derivatives and model proteins, such as catalase and ribonuclease-A, is described. Water soluble and catalytically active enzyme derivatives were obained using copolymers prepared with a mixture of N-acryloxysuccinimide andn-acryloylmorpholine in a 1:99 molar ratio. At increasing molar ratio (3:97, 10:90) extensive crosslinking between polymer and enzymes takes place, yielding insoluble adducts.     

非晶高聚物对聚(ε-己内酯)在其与苯乙烯-丙烯腈共聚物相容共混物中球晶生长速率的影响

本文研究了聚(ε-己内酯)(PCL)在其与苯乙烯-丙烯腈共聚物(SAN)的相容共混物中球晶生长速率与共混组成和结晶温度的关系.发现聚己内酯的球晶生长速率随着SAN的含量增加而下降.由于PCL与SAN是相容共混物,因此在用二次成核动力学方程描述PCL球晶生长速率时,我们引进了相互作用参数X.结果由共混体系的结晶动力学方程计算到的X值与由平衡熔点下降方法计算到的X_(23)值是相同的;而PCL晶体的折叠表面自由能则随着SAN含量的增加而下降.这些结果说明非晶高聚物SAN有碍于PCL球晶的生长.     

Benzamide species retained by DMSO composites at a kaolinite surface

The surface area of kaolinite-benzamide (K-Bz)6.62 m² g^–1, whichis noticeably lower than that of kaolinite-dimethyl sulphoxide (K-DMSO) 14.61m² g^–1, the co-perturbationof the inner-surface hydroxyl features at 3697 and 3650 cm^–1,and the increase of d(001) value by 7.44 Å are all related to the benzamidespecies inserted into the kaolinite structure through the replacement of theK-DMSO composites. Disappearance of the DMSO reflections and emergence ofwell-defined features at 6.04(2θ) and 11.16(2θ), 001 and 002 reflectionswith d values of 14.62 and 7.92 Å, respectively point out that the DMSOspecies were substituted efficiently by benzamide molecules. The thermal stabilityof the K-Bz derivative up to 300°C can be attributed to the slightly tiltedaromatic ring keying into the gibbsitic sheets via the –NH₂groups.     

Intrinsic infrared absorption for carbon–fluorine bonding in fluorinated nanodiamond

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