Stability of vinylidene chloride copolymers containing 4-vinylpyridine units

Vinylidene chloride copolymers are prominent in the barrier plastic packaging industry. These materials display excellent barrier to the transport of oxygen (and other small molecules) as well as flavor and aroma molecules. However, they suffer from a propensity to undergo degradative dehydrochlorination at process temperatures. To scavenge hydrogen chloride formed and prevent its interaction with the metallic components of process equipment, a passive base is usually included as an additive prior to processing. The base is most often an inorganic oxide or salt. These may negatively impact the properties of the polymer, particularly as a film. An organic base that could be covalently incorporated into the copolymer might display better behavior. Accordingly, a series of copolymers containing low levels of 4-vinylpyridine (0.05–3 mole%) have been prepared, characterized, and examined by thermogravimetry to assess thermal stability. In all cases, polymers containing 4-vinylpyridine units are less stable than the polymer containing none of this comonomer. Clearly, the pyridine moiety is a sufficiently strong base to promote E2 elimination of hydrogen chloride to generate dichlormethylene units in the mainchain from which thermal degradation may be initiated.     

关于五阶非线性微分方程一致耗散解的一个结果

Criteria for the existence of uniformly dissipative solutions for a certain fifth order non-linear differential equation are given by means of the frequency domain method.     

Spectroscopic,conformational analysis,structural benchmarking,excited state dynamics,and the photovoltaic properties of Enalapril and Lisinopril

There have been numerous attempts to theoretically design a better photovoltaic property with much interest on how to improved absorption and emission parameters of most reactive compounds in respect to dye – sensitized solar cells (DSSCs). This is regardless of the promising futures of the photovoltaic properties. However, for such effective design, it is necessary to understand the electronic and photophysical properties of the dye systems. Herein detailed density functional theory (DFT) and time – dependent DFT (TD-DFT) investigation of the excited state characteristics and the influence of various solvents: water, acetone, ethanol and chloroform on the photophysical properties of enalapril and lisinopril were investigated along with the experimental spectral (UV–vis and FT-IR) analysis. The electronic structure calculations were conducted using the 6–311++G(d,p) basis set in combination with B3LYP, M06-2X, and ?B97XD DFT functionals for the structural benchmarking investigations of the studied compounds. Results of the excitation electronic analysis of enalapril was observed to have wavelength absorption in the order gas > chloroform > ethanol > water which correspond to 229.19, 228.81, 228.85, 229.03 nm respectively while Lisinopril have the order of chloroform > gas > water > ethanol which present ethanol have the highest transition energy. In all the studied structured, the transition assignment corresponds to π $\to$ π* all corresponding to the Frank -Condon local excitation. It can be inferred from the photovoltaic properties that among the studied compounds in four different phases enalapril have the highest oscillator strength, but the values of light-harvesting efficiency (LHE) varies and show greater stability in Lisinopril. Lisinopril was observed to have the highest value of $V_{OC}$ compared to Enalapril this further confirmed the result obtained from the frontier molecular orbitals.     

Prediction and optimization of the performance characteristics of CZTS thin film solar cell using band gap grading

The results of the numerical simulation of the performance characteristics of (Cu₂ZnSnS₄) CZTS thin film solar cell due to bandgap grading is presented in this work. The investigation of the performance of this solar cell was carried out using the Analysis of Microelectronics and Photonics software (AMPS-1D). A substrate cell structure FTO/CdS/CZTS/Mo(SLG) was used as the base model. An efficiency of 8.33% was obtained from the simulation with baseline parameters while an intentional grading of the device was carried out on the device both at the front and back interface of the absorber. Front grading was observed to degrade the device performance while significant improvement of the device performance was observed with back grading. An intentional double grading of the device further enhanced the efficiency up to 12.26%.     

Spherical cell approach for the effective viscosity of suspensions

In the present paper, the spherical cell approach is employed for addressing the effective viscosity of suspensions of spherical particles. The proposed derivation is based on the only assumption which constitutes the essence of the spherical cell approach: a representative part of the suspension is a spherical cell which contains a particle surrounded by the continuous phase. In contrast with the previous studies on this topic, no additional assumptions are used in the present analysis. The general method of derivation and the final result, which represents the effective viscosity as a function of the solid-phase volume fraction, are compared with earlier studies where the spherical cell approach was applied for describing the effective viscosity.     

Kinetics of Phenolic Compounds Modification during Maize Flour Fermentation

This study aimed to investigate the kinetics of phenolic compound modification during the fermentation of maize flour at different times. Maize was spontaneously fermented into sourdough at varying times (24, 48, 72, 96, and 120 h) and, at each point, the pH, titratable acidity (TTA), total soluble solids (TSS), phenolic compounds (flavonoids such as apigenin, kaempferol, luteolin, quercetin, and taxifolin) and phenolic acids (caffeic, gallic, ferulic, p-coumaric, sinapic, and vanillic acids) were investigated. Three kinetic models (zero-, first-, and second-order equations) were used to determine the kinetics of phenolic modification during the fermentation. Results obtained showed that fermentation significantly reduced pH, with a corresponding increase in TTA and TSS. All the investigated flavonoids were significantly reduced after fermentation, while phenolic acids gradually increased during fermentation. Among the kinetic models adopted, first-order (R² = 0.45–0.96) and zero-order (R² = 0.20–0.82) equations best described the time-dependent modifications of free and bound flavonoids, respectively. On the other hand, first-order (R² = 0.46–0.69) and second-order (R² = 0.005–0.28) equations were best suited to explain the degradation of bound and free phenolic acids, respectively. This study shows that the modification of phenolic compounds during fermentation is compound-specific and that their rates of change may be largely dependent on their forms of existence in the fermented products.     

Measured turbulent entropy production with large eddy particle image velocimetry

In this paper, statistical post-processing of measured velocity, dissipation rate and turbulence data is performed to establish whole-field distributions of entropy production within a channel. Thermal irreversibilities arising from temperature variations were not included in the study, as the experiments were conducted between unheated plexiglass plates in an essentially isothermal water tunnel. Unlike velocity or temperature, the measurement of entropy cannot be performed directly, so entropy production is measured indirectly through spatial differencing of measured velocities in large eddy PIV. In contrast to single-point methods of anemometry, large eddy PIV enables whole-field, time-varying measurements of the velocity field, which can be post-processed to yield entire spatial variations of the entropy production rate. An uncertainty analysis is performed to estimate measurement uncertainties with the new experimental technique. The uncertainties are decomposed into systematic and random components, including a propagated uncertainty, due to spatial differencing of the velocity field. Close comparisons between measured results of turbulence dissipation and direct numerical simulations provide useful verification of the formulation, before post-processed results of dissipation rates are used to determine entropy production within a channel.     

Urea hard segment morphology in flexible polyurethane foam

A series of flexible polyurethane slabstock foam samples were prepared with varying water content and studied using transmission electron microscopy (TEM), video-enhanced optical microscopy (VEM), and small-angle X-ray scattering (SAXS). A new TEM sample preparation technique was developed in which the foam is impregnated with water, frozen, and microtomed, and the polyether soft segment is selectively degraded in the electron beam. Structures of two size scales were detected. A texture with grains (“urea aggregates”) 50–200 nm in size was imaged using both VEM and low-magnification TEM for foams with formulations containing more than 2 pphp water. For the first time, images of urea hard segment microdomains in polyurethane foam (approximately 5 nm in size) were obtained using high-magnification TEM. A microdomain spacing of approximately 6–8 nm was estimated from the SAXS scattering profiles. Glycerol was added to one of the formulations in order to modify the urea microphase separation and to give insight into morphology development in molded polyurethane foam systems. No structure was observed in low-magnification TEM images of the glycerol-modified foam, although smaller structures (hard segments) were detected at high magnification and by SAXS. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 573–581, 1998     

Microstructure of triblock copolymers in asphalt oligomers

A model asphalt has been separated into two parts, asphaltene and maltene, through solvent extraction by n-heptane. The interactions of asphaltene and maltene with the triblock copolymer poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) were investigated by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), dynamic mechanical analysis (DMA), and differential scanning calorimetry (DSC). Asphaltene was found to be essentially immiscible with both blocks of SEBS, while maltene was miscible with SEBS. An unusual sequence of morphological transformations of SEBS microstructure with respect to the addition of maltene was observed. The morphology transformed from hexagonal cylinder, to perforated layers, to lamellae and then back to the original hexagonal cylinder. The observed transformation reflects a limited solubility for both S and EB domains: at lower concentration maltene is a preferential additive for S domains, while increasing concentration the swelling of EB-rich microdomains by maltene becomes significant. The basic understanding of the interactions of the components of asphalt with SEBS gives a simple path to characterize and predict the microstructure of triblock copolymers in asphalt oligomers. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2857–2877, 1997