Effect of LiClO4 on the radical polymerization of Di-2-[2-(2-methoxyethoxy)ethoxy]ethyl itaconate

The effect of LiClO₄ on the polymerization of di-2-[2-(2-methoxyethoxy)ethoxy]ethyl itaconate (DMEI) with dimethyl 2,2′-azobisisobutyrate (MAIB) was investigated in methyl ethyl ketone (MEK) kinetically and by ESR. The polymerization rate (R_p) at 50°C, where the concentrations of DMEI and MAIB were 1.00 and 5.00 × 10⁻² mol/L, increased with increasing [LiClO₄]. Marked acceleration was observed at higher [LiClO₄]s than 1.0 mol/L. The molecular weight of resulting polymer (ca. 10,000) was relatively insensitive to [LiClO₄], indicating occurrence of chain transfer. IR analysis of mixtures of LiClO₄/DMEI and LiClO₄/poly(DMEI) indicated complexation of LiClO₄ with DMEI and its polymer. The rate constants of propagation (k_p) and termination (k_t) were determined by ESR. k_p (1.7–10.5 L/mol s at 50°C) increased with [LiClO₄]. k_t (5.2–1.0 × 10⁴ L/mol s at 50°C) showed remarkable decrease at higher [LiClO₄]s than 1.0 mol/L. R_p of polymerization of equimolar complex of LiClO₄/DMEI with MAIB at 50°C in MEK was expressed by R_p = k[MAIB]^0.5[DMEI]^2.4. k_p increased and k_t decreased with [DMEI]. The activation energies of overall polymerization, propagation and termination were estimated to be 34.5, 8.0, and 59.4 kJ/mol. Copolymerization of DMEI with styrene was also profoundly affected by the presence of LiClO₄. Such large effects of LiClO₄ on the homo- and copolymerization of DMEI are explicable in term of association of LiClO₄-complexed DMEI monomers. © 1997 John Wiley & Sons, Inc.     

Collapse mechanisms and extreme deformation of particle-laden interfaces

Particle-laden interfaces are at the basis of many advanced materials, such as bijels and dry water. While the final properties of these materials can generally be controlled, their response to deformation during processing and use is still poorly understood. In particular, the dynamics of particle-laden interfaces in relevant flow conditions is receiving increasing attention. These conditions are typically highly dynamic and can involve unsteady flow or large deformations. This article gives an overview of the remarkable phenomena of particle-laden interfaces undergoing deformations of large amplitude and at high strain rate, in other words extreme deformation. Upon large-amplitude compression, a monolayer of particles can collapse by buckling or by expelling particles in the liquid. The criteria for buckling or expulsions, as well as recent experiments in highly dynamic conditions, are discussed, showing that these criteria can depend also on the rate of deformation. The emerging use of ultrasound-driven bubbles as an experimental platform for controlled deformation of particle-laden interfaces at high strain rate is also discussed. The ability to control the fate of particles at interfaces during dynamic deformation of droplets or bubbles ultimately underpins a variety of applications from controlled release to catalysis.     

人工神经网络光度法同时测定土壤中铅-镉-镍

研究了以4－（2－吡啶偶氮）－间苯二酚（PAR）为显色剂、十二烷基硫酸钠（SDS）为增敏剂、乙酸－乙酸钠为缓冲液，在水相中对铅、镉、镍进行同时测定。利用二次回归正交组合设计，对体系因子进行了优化。以苏州吴县水稻田土壤为研究对象，利用反向人工神经网络对其中铅、镉、镍的全量、有效态、活化态分别进行了同时测定，预测结果与AAS法所测结果基本一致。     

界面张力弛豫法研究不同分子量原油活性组分界面扩张粘弹性

采用界面张力弛豫法研究了不同分子量原油活性组分在正癸烷-水界面上的扩张粘弹性质,阐述了界面扩张模量的弹性和粘性随扩张频率的变化规律.研究发现,随着原油活性组分分子量的增大,极限扩张粘度明显增大,而极限扩张弹性逐渐增大;当分子量大于某一数值后,极限扩张弹性变化不明显.对界面张力弛豫实验结果进行拟合得到的参数表明,界面上和界面附近的微观弛豫过程的数目随原油活性组分分子量的增加而增加,弛豫过程的特征频率也呈规律性变化.不同原油活性组分的界面扩张粘弹性质可从其不同特征的微观弛豫过程得到解释.     

Pt(hkl) surface charge and reactivity

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聚碳酸酯合成工艺开发的新进展

本文从工艺开发的角度，简要评介了目前聚碳酸酯两大工业生产工艺，即光气化界面缩聚工艺和熔融酯交换缩聚工艺的研究开发新动向。     

Structural effects in electron transfer reactions: comparative interfacial electrochemical kinetics for cis- versus trans-dioxorhenium(V)(bi)pyridine oxidation

The comparative interfacial oxidation kinetics of the approximate structural isomers trans-(O)₂Re^V(py)⁺₄ and cis-(O)₂Re^V(bpy)(py)⁺₂ (py, pyridine; bpy, 2,2′-bipyridine) have been assessed in aqueous solution via conventional cyclic voltammetry at a highly ordered pyrolytic graphite (HOPG) electrode. HOPG was employed because of its known propensity to diminish interfacial electron transfer (ET) rates (by ca. three to four orders of magnitude) and because of a probable lack of importance of kinetic work terms (diffuse double-layer corrections). Measured rates for the trans complex exceed those for the cis by about a factor of 3. Expressed as an effective activation Gibbs energy difference ΔG^*, this corresponds to a cis-trans difference of ca. 3 kJ mol⁻¹. The actual vibrational barriers to ET have determined from a combination of published X-ray structural results (trans complex) and new resonance Raman results (cis complex). The values are 0.6 kJ mol ⁻¹ for the trans oxidation and 4.4 kJ mol⁻¹ for the cis oxidation (i.e. close to the barrier difference inferred from rate measurements). Further analysis shows that most of the barrier difference is associated with displacement of a (predominantly) Re-N(bpy) stretching mode found only in the cis system. Differences in metal-oxo displacements (cis > trans) are also implicated.     

Entropy studies in interface science: An ageless tool

It is possible to obtain (excess) interfacial entropies from the temperature dependence of some characteristic surface parameter. Such excess entropies contain much valuable information. Their studies lead to deeper insight into the interfacial properties. In some cases, quite unexpected results are obtained. In the present paper, we shall consider three illustrations: (1) the surface excess entropy of the electrical double layer on silver iodide, (2) the surface excess entropy of the interface between air and electrolyte solutions and (3) the surface excess entropy of Langmuir polymeric monolayers. Their analysis starts with defining this characteristic parameter and measuring its temperature dependence, followed by a brief thermodynamic analysis to obtain the sought entropy.Given the generality of this methodology, its applicability is likely to be extended to a variety of other interfacial properties, in particular when competition between electric and non-electric forces plays a role as in self-assembly, hydrophobic bonding and polyelectrolytes.     

Wave Propagation in Rotating Functionally Graded Microbeams Reinforced by Graphene Nanoplatelets

This paper presents a study on wave propagation in rotating functionally graded (FG) microbeams reinforced by graphene nanoplatelets (GPLs). The graphene nanoplatelets (GPLs) are considered to distribute in the diameter direction of the micro-beam in a gradient pattern, which leads to the functionally graded structure. By using the Halpin-Tsai micromechanics model and the rule of mixture, the effective material properties of the microbeam are determined. According to the Euler-Bernoulli beam theory and nonlocal elasticity theory, the rotating microbeams are modeled. A comprehensive parametric study is conducted to examine the effects of rotating speed, GPL distribution pattern, GPL length-to-thickness ratio, GPL length-to-width ratio, and nonlocal scale on the wavenumber, phase speed and group speed of the microbeam. The research findings can play an important role on the design of rotating graphene nanoplatelet (GPL) reinforced microbeams for better structural performance.     

蒸汽相转化法原位诱导沸石化制备Y-ZSM-5双沸石复合物

针对Y型沸石在ZSM-5沸石干胶制备及晶化过程中易于溶解、坍塌的问题,采用葡萄糖在水热处理条件下对Y沸石进行包膜处理,提高了Y沸石在高温、高碱度环境中的稳定性,并采用蒸汽相转化法制备了同时含有Y和ZSM-5的双沸石复合物。对影响沸石复合物形成的因素如Y沸石表面碳包膜改性、凝胶碱度、晶化时间等进行了详细讨论。采用X射线衍射（XRD）、扫描电子显微镜（SEM）、傅立叶变换红外（FT-IR）、N₂吸附-脱附,能谱（EDS）以及NH₃-TPD等手段对制备的材料进行了表征。结果表明通过蒸汽相转化法能获得Y和ZSM-5两相共存的双沸石复合物,产物中的ZSM-5沸石相前驱体随蒸汽处理时间的延长逐渐从蠕虫状无定型向纳米多晶ZSM-5沸石转变,纳米多晶聚集体与Y型沸石晶粒之间紧密相连,相互包埋。在异丙苯催化裂化反应中,合成的沸石复合物的活性和稳定性介于Y和ZSM-5之间,优于对应的机械混合物。