The Crystallization and Melting Behaviors of PDLA-b-PBS-b-PDLA Tri-block Copolymers

In this study,the poly(D-lactide)-block-poly(butylene succinate)-block-poly(D-lactide)(PDLA-b-PBS-b-PDLA)triblock copolymers with a fixed length of PBS and various lengths of PDLA are synthesized,and the crystallization behaviors of the PDLA and PBS blocks are investigated.Although both the crystallization behaviors of PBS and PDLA blocks depend on composition,they exhibit different variations.For the PDLA block,its crystallization behaviors are mainly influenced by temperature and block length.The crystallization signals of PDLA block appear in the B-D 2-2 specimen,and these signals get enhanced with PDLA block length.The crystallization rates tend to decrease with increasing PDLA block lendth during crystallizing at 90 and 100°C.Crystallizing at higher temperature,the crystallization rates increase at first and then decrease with block length.The crystallization rates decrease as elevating the crystallization temperature.The melting temperatures of PDLA blocks increase with block lengths and crystallization temperatures.For the PBS block,its crystallization behaviors are mainly controlled by the nucleation and confinement from PDLA block.The crystallization and melting enthalpies as well as the crystallization and melting temperatures of PBS block reduce as a longer PDLA block has been copolymerized,while the crystallization rates of the PBS block exhibit unique component dependence,and the highest rate is observed in the B-D 2-2 specimen.The Avrami exponent of PBS crystallites is reduced as a longer PDLA block is incorporated or the sample is crystallized at higher temperature.This investigation provides a convenient route to tune the crystallization behavior of PBS and PLA.     

Is it worthwhile to go beyond the local-density approximation in subsystem density functional theory?

Frozen density embedding (FDE) theory is one of the major techniques aiming to bring modeling of extended chemical systems into the realm of high accuracy calculations. To improve its accuracy it is of interest to develop kinetic energy density functional approximations specifically for FDE applications. In the study reported here we focused on optimizing parameters of a generalized gradient approximation-like kinetic energy functional with the purpose of better describing electron excitation energies. We found that our optimized parametrizations, named excPBE and excPBE-3 (as these are derived from a Perdew-Burke-Ernzerhof-like parametrization), could not yield improvements over available functionals when applied on a test set of systems designed to probe solvatochromic shifts. Moreover, as several different functionals yielded very similar errors to the simple local-density approximation (LDA), it is questionable whether it is worthwhile to go beyond the LDA in this context.     

Nonlinear Mechanical Response of Polymer Matrix Composites: A Review

Abstract

The present article provides a review on the nonlinear mechanical behavior of polymer matrix composites (PMCs). Initially, essential mechanisms driving the nonlinear response of PMCs under different loading conditions are discussed. Rate-dependence, tension-compression asymmetry, viscous behavior, unloading characteristics, interaction between stress components and effects of environmental factors on mechanical properties are briefly reviewed. This is followed by a review of major approaches and constitutive models for predicting stress–strain behavior of PMCs. Following an increasing degree of complexity, models are categorized into four major classes: nonlinear elasticity models, elastic-plastic models, elastic-plastic-viscous models and Damage-Plasticity models. The vast number of existing models is mainly due to the anisotropy and inhomogeneity of PMCs. In brief, this review focuses on informing the reader of major frameworks, rather than addressing all the models in detail.     

Nanoparticles from vesicle polymerization: Characterization and kinetic study

The polymerization of isodecyl acrylate (ISODAC) in vesicles made from an anionic surfactant—sodium di-2-ethylhexyl phosphate (SEHP)—and from water is studied by ¹H-NMR, transmission electron microscopy, and quasielastic light scattering. High polymerization rates and high conversion rates are achieved with both water-soluble initiator, K₂S₂O₈ (potassium persulfate), and oil-soluble initiator, AIBN (azoisobisbutyronitrile). ISODAC is probably located inside the vesicle bilayer(s) because of its high hydrophobicity. Particles stable at room temperature with a mean diameter of about 50 nm are obtained. Kinetic orders of ISODAC polymerization are determined and the characterization of the resulting particles during and after polymerization are studied. © 1996 John Wiley & Sons, Inc.     

Characterization of the molecular deformation behavior of glassy epoxy resins by rheo-optical FTIR spectroscopy

Rheo-optical FTIR spectroscopy was used for the first time to monitor molecular orientation phenomena in highly crosslinked epoxies. After studying the orientation behavior of epoxy/amine networks during uniaxial deformation above their glass transition temperature in a preceding article, this article deals with the rheo-optical characterization of the deformation process of those epoxy systems below T_g. The orientation behavior is influenced by the different molecular structure of the constituents and the free volume entrapped in the resins. Yield strain and tensile modulus are correlated with the slope of the orientation function. The orientation function was found to show an abrupt change of its slope in the yield point region. This phenomenon is discussed with respect to the mechanism of plastic deformation. © 1996 John Wiley & Sons, Inc.     

Dissipation Behavior and Acute Dietary Risk Assessment of Thiamethoxam and Its Metabolite Clothianidin on Spinach

Thiamethoxam and its metabolite clothianidin residues pose a potential threat to human health. This study aims to investigate the residue behavior and acute dietary risk assessment of thiamethoxam and clothianidin on spinach. Thiamethoxam and clothianidin were extracted using a quick, easy, cheap, effective, rugged, safe (QuEChERS) method and analyzed using liquid chromatography-tandem mass spectrometry (LC-MS/MS). At spike levels from 0.01 to 5 mg kg⁻¹, the average recoveries of both analytes were in the range of 94.5–105.5%, with relative standard deviations (RSDs) of 3.8–10.9%. The dissipation behavior of thiamethoxam followed first-order kinetics, with half-lives of ≤1.6 days. Clothianidin appeared readily as a plant metabolite with highest level exhibited during 3 to 5 days after application. Temperature and light may be two main factors for degradation of thiamethoxam. Besides, acute risk assessment of thiamethoxam and clothianidin was evaluated with risk quotients (RQs) <100%, which suggested a low health risk for all consumer groups of Chinese residents.     

A proposal for a convertible stadium roof structure derived from Watt-I linkage

In this paper, a novel convertible stadium roof structure is introduced, which has been derived from a special geometric configuration of Watt-I linkage, a 1-DoF mechanism used in robot technologies as anthropomorphic fingers. The proposed structure can offer a wide range of different shape configurations according to the environmental conditions and spatial needs, thus offering several aesthetic and functional advantages over existing solutions. This paper serves as a feasibility investigation of this concept, mainly from geometric and structural point of view. To that affect, first kinematic analysis and geometric design of this linkage are introduced. Then, structural analyses of the proposed structure with realistic dimensions and loading conditions are performed in three different geometric configurations, in order to discuss strength and stiffness limitations. Finally, potential cover materials and actuators are briefly discussed.     

Kinetics of batch production of single-cell protein from cheese whey

A kinetic model for single-cell protein batch fermentation was developed using the numerical simultaneous integration approach of the fourth-order Runge-Kutta method. The model takes into account the effect of substrate inhibtion, maintenance energy, and cell death on the cell growth and substrate utilization during the fermentation process. The theoretical results obtained from the model compared well with the experimental data. The model was used to study the effect of the initial substrate concentration on the lag period, fermentation time, specific growth rate, population size, and cell productivity of batch fermentation. Increasing the initial substrate concentration increased the lag period and fermentation time and decreased the specific growth rate and cell yield. The growth limiting substrate concentration was 2.9 g/L, whereas the growth inhibiting substrate concentration was 69.0 g/L. Increasing the initial substrate concentration above 150 g/L significantly decreased the yeast population size.     

Magnetically Enhanced 15 kHz Glow Discharge of Methane

This work deals with the luminous chemical vapour deposition (plasma polymerization) of hydrocarbon polymeric thin films in a magnetic field enhanced discharge of methane. The films were deposited on 4″ <111> single crystal silicon substrates. We investigated the influence of the different glow discharge parameters (e.g. pressure, flow rate, power input, etc.) on the deposition rate of methane and the refractive index of the resulting polymeric films, as well as the distribution of these parameters across the wafer. We used a Shinko Seiki Plasma Polymerization equipment with a bell jar reactor comprising two electrodes connected to a symmetric AC power supply of 15 kHz. Two magnetrons were formed by placing two circular shaped concentric magnetic poles behind each electrode. The substrates were attached on both sides of a rotating wheel held at a floating potential in the middle of the two electrodes. This equipment allowed us to vary a single parameter and keep the other parameters constant over the whole process. We measured the thickness and the refractive index and their distribution over the wafer. The effect of the system pressure, decoupled from the effect of flow rate, is explained by the characteristic nature of luminous gas phase and by the polymerization/deposition mechanism of luminous chemical vapour deposition.     

Mixed ligand complexes of AEE hexafluoroacetylacetonates with diglyme: Synthesis,crystal structure and thermal behavior

The novel mixed ligand complexes [Ca(hfa)₂(diglyme)(H₂O)] (I), [Sr(hfa)₂(diglyme)(H₂O)] (II) and [Ba(hfa)₂(diglyme)₂] (III) (Hhfa = 1,1,1,5,5,5-hexafluoropentane-2,4-dione, diglyme = 2,5,8-trioxanonane) were synthesized by the reactions of the alkaline earth element (AEE) carbonates in n-hexane with a mixture of Hhfa and diglyme, and they were characterized by elemental analysis, ¹H and ¹³C NMR, and FTIR spectroscopy. The crystal structures of I–III, consisting of mononuclear isolated molecules, have been determined. The thermal behavior and composition of the vapor phase have been studied for I–III by thermal analysis at low pressure and mass spectrometry using a Knudsen cell. The stability of the mixed ligand complexes [M(hfa)₂(diglyme)_n] to the removal of diglyme molecules under heating decreases in the row I > II ≈ III, and only I evaporates as the mixed ligand complex after water removal.