Reversible addition-fragmentation chain transfer polymerization of N-isopropylacrylamide: a comparison between a conventional and a fast initiator

The reversible addition-fragmentation chain transfer (RAFT) polymerization of N-isopropylacrylamide (NIPAM) was studied to determine the reasons for deviation of experimental molecular weights to lower molecular weight at high monomer conversion when S-1-dodecyl-S-(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAm) and S,S-bis(alpha,alpha'-dimethyl-alpha' '-acetic acid)trithiocarbonate (CTAd) were used as RAFT agents at 65 degrees C. For this purpose, experiments were performed in N,N'-dimethylformamide (DMF) at the NIPAM/CTA ratio of 200 with initiators capable of yielding fast and slow initiation, respectively by photochemical and thermal process, either at ambient temperature or at 65 degrees C. When the polymerization of NIPAM was conducted under these conditions with Irgacure-2959 (IRGC) as photoinitiator, a continuing supply of primary radicals by incremental initiator addition was required to achieve reasonably high conversion. This effect was also apparent by the loss of linearity of the first-order kinetic plot with a conventional initiator (4,4-azobis(4-cyanovaleric acid) (ACVA) as azo-initiator, 10h (t1/2) decomposition at 65 degrees C) indicating that steady-state concentration of the macroradical decreases significantly with the initiator consumption. Nevertheless, polymers with predictable number-average molecular weight Mn (i.e., based on [monomer]/([CTA] + [initiator]) ratio) and narrow polydispersities were obtained (PDIs < 1.2) with CTAm indicating that the process of chain growth was controlled. When CTAd was used, instead of CTAm, the polymers obtained were characterized by a larger polydispersity (1.2 < PDIs < 1.3). The so-called "living steady-state concentration" in chain equilibration together with the linear dependence of Mn vs conversion was observed only when the 200/1 NIPAM/CTA mixture in DMF was subjected to a permanent photoirradiation at 65 degrees C. With ACVA, the deviation of the experimentally measured molecular weights at high conversion was accounted for by the simultaneous self-initiated polymerization of NIPAM with the controlled process in the presence of CTA at 65 degrees C. Similar drift from the linear dependence Mn vs conversion was also observed at 65 degrees C when a significant number of low molecular weight polymer chains were generated intentionally by photodecomposition of IRGC.     

Comparison of homogeneous and heterogeneous Ga(III) catalysis in the cycloisomerization of 1,6-enynes

We describe a study of the gallium(III)-catalyzed 1,6-enynes cycloisomerization reaction in both homogeneous and heterogeneous conditions. With GaBr₃ in homogeneous conditions, some particularities were observed in terms of selectivity compared to reported GaCl₃-catalyzed reactions. The transfer of the reaction in heterogeneous conditions was realized by supporting Ga(III) salts onto montmorillonite. Both systems were compared based on reaction times, conversion, and selectivity and showed complementary activities.     

应用4变量精确平板理论分析FG复合板的自由振动

应用4变量的精确平板理论,对矩形功能梯度材料(FGM)复合板进行自由振动分析.与其它的理论不同,该理论的未知函数数量只有4个,而别的剪变形理论的未知函数为5个.提出的4变量精确平板理论,协调条件有了改变,与经典的薄板理论相比,许多方面有着惊人的相似,无需引入剪切修正因数——当横向剪应力越过板厚后,为了满足剪应力自由表面条件,出现抛物线状的改变,导致横向剪应力的变化.考虑了两种常见类型的FGM复合板,即,FGM表面层和各向同性夹芯层的复合板,以及各向同性表面层和FGM夹芯层的复合板.通过Hamilton原理,得到了FGM复合板的运动方程.得到闭式的Navier解,然后求解特征值问题,得到自由振动的基本频率.将该理论得到的结果,与经典理论,一阶的及其它更高阶的理论所得到的结果进行比较,检验了该理论的有效性.研究发现,该理论在求解FGM复合板自由振动性能方面,既精确又简单.     

On using the dynamic snap-through motion of MEMS initially curved microbeams for filtering applications

Numerical and experimental investigations of the dynamics of micromachined shallow arches (initially curved microbeams) and the possibility of using their dynamic snap-through motion for filtering purposes are presented. The considered MEMS arches are actuated by a DC electrostatic load along with an AC harmonic load. Their dynamics is examined numerically using a Galerkin-based reduced-order model when excited near both their first and third natural frequencies. Several simulation results are presented demonstrating interesting jumps and dynamic snap-through behavior of the MEMS arches and their attractive features for uses as band-pass filters, such as their sharp roll-off from pass-bands to stop-bands and their flat response. Experimental work is conducted to test arches realized of curved polysilicon microbeams when excited by DC and AC loads. Experimental data of the micromachined curved beams are shown for the softening and hardening behavior near the first and third natural frequencies, respectively, as well as dynamic snap-through motion.     

A two variable refined plate theory for the bending analysis of functionally graded plates

Bending analysis of functionally graded plates using the two variable refined plate theory is presented in this paper.The number of unknown functions involved is reduced to merely four,as against five in other shear deformation theories. The variationally consistent theory presented here has, in many respects,strong similarity to the classical plate theory. It does not require shear correction factors,and gives rise to such transverse shear stress variation that the transverse shear stresses vary parabolically across the thickness and satisfy shear stress free surface conditions.Material properties of the plate are assumed to be graded in the thickness direction with their distributions following a simple power-law in terms of the volume fractions of the constituents.Governing equations are derived from the principle of virtual displacements, and a closed-form solution is found for a simply supported rectangular plate subjected to sinusoidal loading by using the Navier method.Numerical results obtained by the present theory are compared with available solutions,from which it can be concluded that the proposed theory is accurate and simple in analyzing the static bending behavior of functionally graded plates.     

Local nonlinear dynamics of MEMS arches actuated by fringing-field electrostatic actuation

Nonlinear Dynamics - The nonlinear dynamic behavior of a resonant MEMS arch microbeam actuated by fringing electric actuation is investigated in this paper. The arch microbeam is loaded with DC and...     

Synthesis of α-Alkylidene-β-Ethoxycarbonyl Cyclopentanones and -γ-Butyrolactones

Synthesis of (E,Z)-α-Alkylidene-β-ethoxycarbonyl cyclopentanones 5 and (E,Z)-α-alkylidene-γ-butyrolactones 7 by condensing phosphonates 3 or 6 with a variety of aldehydes in the presence of aqueous potassium carbonate (6-10M) as base is reported.