Synthesis of PMMA‐b‐PBA block copolymer in homogeneous and miniemulsion systems by DPE controlled radical polymerization

In this research, poly(methyl methacrylate)‐b‐poly(butyl acrylate) (PMMA‐b‐PBA) block copolymers were prepared by 1,1‐diphenylethene (DPE) controlled radical polymerization in homogeneous and miniemulsion systems. First, monomer methyl methacrylate (MMA), initiator 2,2′‐azobisisobutyronitrile (AIBN) and a control agent DPE were bulk polymerized to form the DPE‐containing PMMA macroinitiator. Then the DPE‐containing PMMA was heated in the presence of a second monomer BA, the block copolymer was synthesized successfully. The effects of solvent and polymerization methods (homogeneous polymerization or miniemulsion polymerization) on the reaction rate, controlled living character, molecular weight (M_n) and molecular weight distribution (PDI) of polymers throughout the polymerization were studied and discussed. The results showed that, increasing the amounts of solvent reduced the reaction rate and viscosity of the polymerization system. It allowed more activation–deactivation cycles to occur at a given conversion thus better controlled living character and narrower molecular weight distribution of polymers were demonstrated throughout the polymerization. Furthermore, the polymerization carried out in miniemulsion system exhibited higher reaction rate and better controlled living character than those in homogeneous system. It was attributed to the compartmentalization of growing radicals and the enhanced deactivation reaction of DPE controlled radical polymerization in miniemulsified droplets. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4435–4445, 2009     

Multi-mode nonlinear vibration and postbuckling of antisymmetrically laminated imperfect angle-ply cylindrical panel with free straight edges

Summary A multi-mode solution to nonlinear vibration and postbuckling of the titled problem is presented for two straight edges free from forces and bending moments and the other edges subjected to identical variation of rotational stiffness and normal boundary forces. The dynamic Marguerre-type nonlinear equations are adopted. The transverse deflection and stress function are expanded into two series with timedependent coefficients. The Galerkin procedure furnishes an infinite system of ordinary differential equations for these time functions. The method of harmonic balance is used for a solution of a finite number of these equations. The postbuckling behavior is treated as a special case. Numerical results in nonlinear vibration and postbuckling of antisymmetrically laminated angle-ply panel are presented graphically for different panel parameters and also compared with available data.

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Nichtlineare Schwingung und Nachbeulen einer antisymmetrisch geschichteten, imperfekten zylindrischen Schale mit freien geraden Rändern

Übersicht Für das im Titel genannte Problem wird bei Normalkraftbelastung und Verdrehsteifigkeit der kreisbogenförmigen Ränder eine Lösung der dynamischen, nichtlinearen Marguerre-Gleichungen in Form verallgemeinerter Fourier-Reihen für die Durchbiegung und Spannungsfunktion mit zeitabhängigen Koeffizienten vorgestellt. Das Galerkin-Verfahren liefert ein System unendlich vieler gewöhnlicher Differentialgleichungen für diese Zeitfunktionen. Zur Lösung einer endlichen Zahl der Gleichungen wird die Methode der harmonischen Balance benutzt. Für verschiedene Schalenparameter werden numerische Resultate zur Schwingung und zum Nachbeulen in graphischer Form dargestellt und mit fremden Ergebnissen verglichen.

     

Biosynthesis and characterization of novel polyhydroxyalkanoate polymers with high elastic property by Cupriavidus necator PHB4 transformant

We attempted to synthesize novel polyhydroxyalkanoate (PHA) containing new 3-hydroxy-4-methylvalerate (3H4MV) monomer from the transformed strain of Cupriavidus necator PHB⁻4 harboring the PHA synthase gene of Chromobacterium sp. USM2 (phaC_Cs). Novel PHA containing SCL and MCL monomers were successfully synthesized from crude palm kernel oil (CPKO) and isocaproic acid. Results showed that P(3HB-co-1 mol% 3HV-co-3 mol% 3H4MV-co-18 mol% 3HHx) possessed higher thermal stability, higher elastomeric behavior at room temperature and higher ductility than the P(3HB-co-5 mol% 3HHx). The novel PHA film was found to possess an interesting rubber-like elasticity and flexibility property which has not been reported. The soil surface degradation study showed that the novel PHA film was degraded faster than the 3HB homopolymer and copolymer with 5 mol% of 3HHx.     

Excited‐State Dynamics of the Metal String Complex Co3(dpa)4(NCS)2 from Femtosecond Transient Absorption Spectra

Transient absorption spectroscopy is used to study the excited‐state dynamics of Co₃(dpa)₄(NCS)₂, where dpa is the ligand di(2‐pyridyl)amido. The ππ*, charge‐transfer, and d–d transition states are excited upon irradiation at wavelengths of 330, 400 and 600 nm, respectively. Similar transient spectra are observed under the experimental temporal resolution and the transient species show weak absorption. We thus propose that a low‐lying metal‐centered d–d state is accessed immediately after excitation. Analyses of the experimental kinetic traces reveal rapid conversion from the ligand‐centered ππ* and the charge‐transfer states to this metal‐centered d‐d state within 100 fs. The excited molecule then crosses to a second d–d state within the ligand‐field manifold, with a time coefficient of 0.6–1.4 ps. Because the ground‐state bleaching band recovers with a time coefficient of 10–23 ps, we propose that an excited molecule crosses from the low‐lying d–d state either directly within the same spin system or with spin crossing via the state ²B to the ground state ²A₂ (symmetry group C₄). In this trimetal string complex, relaxation to the ground electronic surface after excitation is thus rapid.     

Long distance laser ultrasonic propagation imaging system for damage visualization

Wind turbine blade failure is the most prominent and common type of damage occurring in operating wind turbine systems. Conventional nondestructive testing systems are not available for in situ wind turbine blades. We propose a portable long distance ultrasonic propagation imaging (LUPI) system that uses a laser beam targeting and scanning system to excite, from a long distance, acoustic emission sensors installed in the blade. An examination of the beam collimation effect using geometric parameters of a commercial 2 MW wind turbine provided Lamb wave amplitude increases of 41.5 and 23.1 dB at a distance of 40 m for symmetrical and asymmetrical modes, respectively, in a 2 mm-thick stainless steel plate. With this improvement in signal-to-noise ratio, a feasibility study of damage detection was conducted with a 5 mm-thick composite leading edge specimen. To develop a reliable damage evaluation system, the excitation/sensing technology and the associated damage visualization algorithm are equally important. Hence, our results provide a new platform based on anomalous wave propagation imaging (AWPI) methods with adjacent wave subtraction, reference wave subtraction, reference image subtraction, and the variable time window amplitude mapping method. The advantages and disadvantages of AWPI algorithms are reported in terms of reference data requirements, signal-to-noise ratios, and damage evaluation accuracy. The compactness and portability of the proposed UPI system are also important for in-field applications at wind farms.     

Nonisothermal crystallization kinetics of poly(ε‐caprolactone) blocks in double crystalline triblock copolymers containing poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) and poly(ε‐caprolactone) units

The poly(3‐hydroxbutyrate‐co‐3‐hydroxyvalerate)/poly(ε‐caprolactone) block copolymers (PHCLs) with three different weight ratios of PCL blocks (38%, named PHCL‐38; 53%, named PHCL‐53; and 60%, named PHCL‐60) were synthesized by using PHBV with two hydroxyl end groups to initiate ring‐opening polymerization of ε‐caprolactone. During DSC cooling process, melt crystallization of PHCL‐53 at relatively high cooling rates (9, 12, and 15 °C min^?1) and PHCL‐60 at all the selected cooling rates corresponded to PCL blocks so that PHCL‐53 and PHCL‐60 were used to study the nonisothermal crystallization behaviors of PCL blocks. The kinetics of PCL blocks in PHCL‐53 and PHCL‐60 under nonisothermal crystallization conditions were analyzed by Mo equation. Mo equation was successful in describing the nonisothermal crystallization kinetics of PCL blocks in PHCLs. Crystallization activation energy were estimated using Kissinger's method. The results of kinetic parameters showed that both blocks crystallized more difficultly than corresponding homopolymers. With the increase of PCL content, the crystallization rate of PCL block increased gradually. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010