Crystallization of Poly(ethylene adipate) within γ-Phase Poly(vinylidene fluoride) Matrix

The effects of PEA on the γ-phase PVDF crystal structure and the crystallization of PEA within the pre-existing γ-phase PVDF spherulites have been investigated by optical microscopy(OM), infrared spectroscopy(IR) and scanning electron microscopy(SEM). The results demonstrate that the γ-phase PVDF spherulites consist of the lamellae exhibiting a highly curved scroll-like morphology and develop preferentially in PEA-rich blend. With increasing PEA concentration, the scroll diameter increases and the scrolls are better separated from each other. PEA crystallizes first in the interspherulitic region and transcrystalline layer develops. Subsequently, the transcrystalline layer of PEA continues to grow within the γ-phase PVDF spherulites, e.g., in the region between the scrolls, until impinging on other PEA transcrystalline layers or spherulites. The crystallization kinetics results indicate that the growth rate of PEA crystals in the intraspherulitic region of γ-phase PVDF shows a positive correlation with content of PEA, but a negative one with the crystallization temperature of γ-phase PVDF.     

Study on the Relationship between Emulsion Properties and Interfacial Rheology of Sugar Beet Pectin Modified by Different Enzymes

The contribution of rheological properties and viscoelasticity of the interfacial adsorbed layer to the emulsification mechanism of enzymatic modified sugar beet pectin (SBP) was studied. The component content of each enzymatic modified pectin was lower than that of untreated SBP. Protein and ferulic acid decreased from 5.52% and 1.08% to 0.54% and 0.13%, respectively, resulting in a decrease in thermal stability, apparent viscosity, and molecular weight (Mw). The dynamic interfacial rheological properties showed that the interfacial pressure and modulus (E) decreased significantly with the decrease of functional groups (especially proteins), which also led to the bimodal distribution of particle size. These results indicated that the superior emulsification property of SBP is mainly determined by proteins, followed by ferulic acid, and the existence of other functional groups also promotes the emulsification property of SBP.     

Pulse radiolysis study of the initial steps of the polymerization of cyclohexyl acrylate and cyclohexyl methacrylate

Pulse radiolysis with kinetic spectroscopic detection was applied to study the kinetics of the first steps of radiation induced polymerization of cyclohexyl acrylate and cyclohexyl methacrylate in cyclohexane solvent. The reactions were initiated by cyclohexyl radicals produced in the radiolysis of the solvent. The transient absorption spectra of the -carboxyalkyl type radicals produced in addition reaction show maxima around 300 nm. This shifts to longer wavelength with time after the pulse. This phenomenon was explained by the oligomerization reaction. From the kinetic curves average rate coefficients of termination for the oligomer radicals (2k_t) were determined as a function of time elapsed after the electron pulse. The values obtained were compared with those calculated for other (acrylate and methacrylate type) monomers.     

烟气中Hg的氧化机理的研究

本文对Ｈｇ与Ｃｌ２在烟气中的氧化反应进行了热力平衡计算和动力学计算。平衡计算的结果表明有ＣＩ元索存在时Ｈｇ的氧化率为１００％，而在相同的条件下动力学计算纺果为Ｈｇ的氧化率在２０％～８０％之间变化，与实验结果吻合。实际的氧化反应是一种超平衡状态，不能达到理想的平衡状态。因此应采用动力学与热力平衡分析相结合的方法研究Ｈｇ在烟气中的反应机理。同时，计算结果显示Ｃｌ含量对Ｈｇ的氧化率的影响很大．     

New ligands for the Fe(III)‐mediated reverse atom transfer radical polymerization of methyl methacrylate

A series of (di)picolinic acids and their derivates are investigated as novel complexing tridentate or bidentate ligands in the iron‐mediated reverse atom transfer radical polymerization of methyl methacrylate in N,N‐dimethylformamide at 100 °C with 2,2′‐azobisisobutyrontrile as an initiator. The polymerization rates and polydispersity indices (1.32–1.8) of the resulting polymers are dependent on the structures of the ligands employed. Different iron complexes may be involved in iron‐mediated reverse atom transfer radical polymerization, depending on the type of acid used. ¹H NMR spectroscopy has been used to study the structure of the resulting polymers. Chain‐extension reactions have been performed to further confirm the living nature of this catalytic system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2912–2921, 2006     

Roles of SiH4 and SiF4 in growth and structural changes of poly-Si films

The structural properties of polycrystalline silicon films, prepared by plasma enhanced chemical vapor deposition system, with different flow rates of SiH₄/SiF₄ mixtures at 300 °C were investigated. This study indicates that the low hydrogen coverage on the growing surface, under optimum fluorine radicals, will be leaded to an improvement of crystallized area as compared with case of high hydrogen coverage surface. Moreover, the studies of the role of SiH₄ and SiF₄ radicals show that the SiH₄ radicals are important in the nucleation and growth of grains. However, SiF₄ radicals are effective in the structural change of grain boundaries regions and by this way, in the present system, establish the growth of grains under the dominant 〈1 1 0〉 direction. The stress investigation indicates that addition of high flow rate of SiF₄ in amorphous film, results in the nearly stress free films. Finally, we found that the changes in g-value reflect the changes in the intrinsic compressive and tensile stress in the both polycrystalline and amorphous silicon films.     

Monte Carlo study of interfacial silicon suboxide layers and oxidation kinetics

A simple simulation scheme that simultaneously describes the growth kinetics of SiO₂ films at the nanometer scale and the SiO_x/Si interface dynamics (its extent, and spatial/temporal evolution) is presented. The simulation successfully applies to experimental data in the region above and below 10 nm, reproduces the Deal and Grove linear-parabolic law and the oxide growth rate enhancement in the very thin film regime (the so-called anomalous region). According to the simulation, the oxidation is governed mainly by two processes: (a) the formation of a transition suboxide layer and (b) its subsequent drift towards the silicon bulk. We found that it is the superposition of these two processes that produces the crossover from the anomalous oxidation region behavior to the linear-parabolic law.     

Non-isothermal short-range-order kinetics of binary alloys as influenced by solute-vacancy complexes

A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach. The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures. An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use of DSC trace data. A value of 89.12±0.32 kJ mol^-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation energy corresponding to the ordering process as influenced by quenching temperature was also assessed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ultrasonic spectroscopic evaluation of the ring‐opening metathesis polymerization of dicyclopentadiene

An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol^?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003