Sulfur-Containing Vinyl Monomers. XV. Kinetic Study of Radical Polymerization of Vinyl Mercaptobenzothiazole and Its Copolymerization

A kinetic study of radical polymerization of vinyl mercaptobenzothiazole (VMBT) with α,α′-azobisisobutyonitrile (AIBN) at 60°C was carried out. The rate of polymerization (R_p) was found to be expressed by the rate equation: R_p = k[AIBN]^0.5 [VMBT]^1.0, indicating that the polymerization of this monomer proceeds via an ordinary radical mechanism. The apparent activation energy for overall polymerization was calculated to be 20.9 kcal/mole. Moreover, this monomer was copolymerized with methyl methacrylate, acrylonitrile, vinyl acetate, phenyl vinyl sulfide, maleic anhydride, and fumaronitrile at 60°C. From the results obtained, the copolymerization parameters were determined and discussed.     

Finite-stretching corrections to the Milner-Witten-Cates theory for polymer brushes

This paper investigates finite-stretching corrections to the classical Milner-Witten-Cates theory for semi-dilute polymer brushes in a good solvent. The dominant correction to the free energy originates from an entropic repulsion caused by the impenetrability of the grafting surface, which produces a depletion of segments extending a distance μ∝L^-1 from the substrate, where L is the classical brush height. The next most important correction is associated with the translational entropy of the chain ends, which creates the well-known tail where a small population of chains extend beyond the classical brush height by a distance ξ∝L^-1/3. The validity of these corrections is confirmed by quantitative comparison with numerical self-consistent field theory.     

不同取代位置的萘衍生两亲分子在气/液界面组装膜中的螺旋结构与圆偏振发光

Langmuir-Blodgett(LB)技术可在二维气/液界面上精确地控制分子之间的排列及堆积方式, 构建有序超薄膜及纳米组装体. 同时, 界面这一不对称环境也可有效放大组装体的手性信息, 实现超分子体系中的手性传递和手性放大. 本文研究了萘环取代位置不同的两种手性两亲分子——N,N′-双十八烷基-α-萘-L-氨基-谷氨酸二酰胺(1NLG)和N,N′-双十八烷基-β-萘-L-氨基-谷氨酸二酰胺(2NLG)在气/液界面的铺展及组装行为, 发现同分异构效应影响了两亲分子在界面的排列, 1NLG组装形成了均一的纳米带状结构, 而2NLG则形成了左手螺旋结构, 并且2NLG薄膜表现出圆偏振发光(CPL)性质, 其不对称因子(g_lum)比三维体相组装体(超分子凝胶)大23倍, 表明界面促进了超分子手性的放大.     

Techniques of aligning carbon nanotubes

This paper reviews major techniques of aligning carbon nanotubes, either during the growth or by the post-growth processing. A number of post-processing alignment techniques are discussed, which employ mechanical stretching, fracture, compression, friction, filtration, fiber drawing, gas flow, liquid crystals, Langmuir-Blodgett technique, acoustic, magnetic and electric fields. The suitability of those techniques to industrial applications is analyzed.      

Effects of confinement on static and dynamical properties of water

Molecular-dynamics results on water confined in a silica pore are reviewed and discussed in connection with experiments performed on water in Vycor and with studies of water in contact with proteins. The properties of confined water are studied as a function of both temperature and hydration level. The interaction of water in the film close to the substrate with the silica atoms induces a strong distortion of the hydrogen bond network. At high hydration levels a double dynamical regime is observed. At low hydration an anomalous diffusion is found upon supercooling with a transition from a Brownian to a non-Brownian regime on approaching the substrate in agreement with results found in studies of water in contact with globular proteins.Received: 1 January 2003, Published online: 14 October 2003PACS: 61.20.-p Structure of liquids - 61.20.Ja Computer simulation of liquid structure     

间苯二酚-甲醛凝胶自发成膜技术研究

 以间苯二酚和甲醛为原料，对水相溶胶-凝胶聚合自发成膜技术获得间苯二酚-甲醛(RF)凝胶薄膜进行了研究。主要研究了溶胶-凝胶过程中冰醋酸（HAC）含量和反应温度对凝胶过程的影响，分析了RF有机凝胶自发成膜的形成机理。IR和SEM分析表明，所得到的凝胶膜具有典型的RF有机气凝胶结构，薄膜厚度大约为50 μm，膜由直径10 μm左右的粒子组成，没有观察到明显的孔洞结构。分析认为，在间苯二酚和甲醛占总溶液的质量分数为67％左右及控制pH值在一定的酸性范围，RF凝胶自发成膜过程和机理可以用RF凝胶的收缩机理加以解释，RF自发膜的表面形貌及形成机理与均匀泡沫的连续相分离机理类似。     

Growth of InN films and nanorods by H-MOVPE

InN films and nanorods were grown by hydride metalorganic vapor phase epitaxy (H-MOVPE) and the effects of growth temperature, and NH₃/TMIn and HCl/TMIn ratios on morphological dependences were studied. The growth habit of InN varied from thin film to microrod to nanorod to no deposition as the growth conditions were changed about transition from growth to etching conditions. The growth and etch regimes were also predicted by chemical equilibrium calculations of In–C–H–Cl–N-inert system. The optical properties of InN nanorods and columnar structured films were measured by room temperature PL and a maximum intensity was observed at 1.08 eV for both structures.     

Natural-based plasticizers and biopolymer films: A review

In recent years, much attention has been focused on research to replace petroleum-based commodity plastics, in a cost-effective manner, with biodegradable materials offering competitive mechanical properties. Biopolymers have been considered as the most promising materials for this purpose. However, they generally present poor mechanical properties regarding processability and end-use application, since the fragility and brittleness exhibited during thermoformation can limit their potential for application. In order to overcome this problem, plasticizers are added to provide the necessary workability to biopolymers. This class of products became more visible when biodegradable additives and plasticizers also became the focus of material scientists. The use of natural and/or biodegradable plasticizers, with low toxicity and good compatibility with several plastics, resins, rubber and elastomers in substitution of conventional plasticizers, such as phthalates and other synthetic conventional plasticizers attracted the market along with the increasing worldwide trend towards use of biopolymers. Here we discuss the main results and developments in natural plasticizer/synthetic and biopolymer-based films during the last decades.     

Selective area laser deposition of FCC beta silicon carbide

Silicon Carbide (SiC) has been deposited onto an alumina substrate by the thermal decomposition of the gaseous precursor tetramethylsilane (TMS). A 500 W ytterbium fibre laser was used to heat the surface of an alumina substrate locally, resulting in deposition of SiC at the sample surface. The SiC deposit was analysed using energy dispersive X‐ray spectroscopy and X‐ray diffraction (XRD). The deposit was confirmed to be silicon carbide and found to be face centre cubic (FCC) crystal structure. Raman spectroscopy was used to measure the stoichiometry of the deposit which initially was found to be carbon rich. Further analysis by Raman spectroscopy suggests the deposit may be more stoichiometric following a two hour thermal treatment of the sample at 600 degrees celcius in an atmosphere of air.     

Langmuir-Blodgett film of p-tert-butylthiacalix[4]arene modified glassy carbon electrode as voltammetric sensor for the determination of Hg(II)

The π-A isotherms and UV-vis spectra of the transferred films suggested that the monolayer of p-tert-butylthiacalix[4]arene can coordinate with Hg²⁺ at the air-water surface. From these observations, a glassy carbon electrode coated with Langmuir-Blodgett film of p-tert-butylthiacalix[4] arene as a new voltammetric sensor is designed for the determination of trace amounts of Hg²⁺. Compared with bare glassy carbon electrode and modified glassy carbon electrode using direct coating method, the Langmuir-Blodgett film-modified electrode can greatly improve the measuring sensitivity of Hg²⁺. Under the selected conditions, the Langmuir-Blodgett film-modified electrode in 0.1 mol L⁻¹ H₂SO₄ + 0.01 mol L⁻¹ KCl solution shows a linear voltammetric response for Hg²⁺ in the range of 5.0 × 10⁻¹⁰ to 1.5 × 10⁻⁷ mol L⁻¹, with a detection limit of 2.0 × 10⁻¹⁰ mol L⁻¹. The proposed method was also applied to determine Hg²⁺ in water samples (tap, lake and river water). In addition, the fabricated electrode exhibited a distinct advantage of simple preparation, non-toxicity, good reproducibility and good stability.