Effect of pressure on oxygen enrichment of liquid crystalline cellulose ether membranes at elevated temperature

Cholesteric liquid crystalline triheptyl cellulose (THC)/ethyl cellulose binary blend membranes were prepared and the effect of pressure on their oxygen enrichment at elevated temperature was investigated using a constant pressure-variable volume method. The oxygen enrichment increased with the increase of transmembrane pressure difference or with slight increase of the THC content in the blend membranes. The oxygen concentration through the membranes increased linearly with decreasing pressure ratio. Air was directly separated through a 17 m-thick THC/EC(1.5/98.5) membrane to prepare an oxygen-enriched air containing 39.5% oxygen at the flux of 6.99×10^–4 cm³ (STP)/s.cm² at the pressure difference of 0.43 MPa and 85 °C.     

A thermodynamic framework to model thixotropic materials

Thixotropic materials are widely used in a variety of industrial applications. The constitutive relations to describe these materials are based on one-dimensional experiments in which the material is subjected to a shear motion and there is no unique methodology to obtain proper three-dimensional models. The path towards generalization to a three-dimensional framework is invariably carried out in a ad hoc manner. Here we propose a three-dimensional model that stems from a general thermodynamic framework that has proved to be quite robust in the development of constitutive relations, namely the application of the second law of thermodynamics together with the maximization of the entropy production. This leads to a constitutive equation that has the same form of a generalized Upper Convected Maxwell equation, if we require that changes of microstructure due to the deformation of each Maxwell element that comprises the model are reversible. Changes in microstructure are governed by a potential that is a measure of the difference between the current structure and the equilibrium structure associated with it. The equilibrium structure associated with the current structure is determined by the current value of stress, considered the main break up agent. We assume that the state of equilibrium would be achieved in a Motion With Constant Stress History, starting from the current stress state, until a steady state where the kinematics is not changing.     

Nuclear quantum effect and temperature dependency on the hydrogen‐bonded structure of base pairs

The structure of Watson–Crick‐type adenine‐thymine and guanine‐cytosine pairs has been studied by hybrid Monte Carlo (HMC) and path integral hybrid Monte Carlo (PIHMC) simulations with the use of semiempirical PM6‐DH+ method in the gas phase. We elucidated the nuclear quantum effect and temperature dependency on the hydrogen‐bonded moiety of base pairs. It was shown that the contribution of nuclear quantum effect on the hydrogen‐bonded structure is significant not only at low temperature 150 K but also at temperature as high as 450 K. The relative position of hydrogen‐bonded proton between two heavy atoms and the nuclear quantum nature of the proton are also shown. Furthermore, we have applied principal component analysis to HMC and PIHMC simulations to analyze the nuclear quantum effect on intermolecular motions. We found that the ratio of Buckle mode (lowest vibrational mode from normal mode analysis) decreases due to the nuclear quantum effect, whereas that of Propeller mode (second lowest vibrational mode) increases. In addition, nonplanar structures of base pairs were found to become stable due to the nuclear quantum effect from two‐dimensional free energy landscape along Buckle and Propeller modes. © 2013 Wiley Periodicals, Inc.     

Performance of a parallel viscoelastic-viscoplastic model for a microcellular thermoplastic foam on wide temperature range

This paper is concerned with the experimental testing and the constitutive modelling of a thermoplastic microcellular polyethylene-terephthalate (MC-PET) foam on the temperature range of 21–210 °C in order to investigate the temperature-dependent performance of the applied parallel viscoelastic-viscoplastic material model. By means of carefully designed uniaxial mechanical tests in temperature chamber, the viscous, elastic and yielding behaviours of the investigated material are identified, which are then applied for selecting suitable viscoelastic-viscoplastic constitutive models. The material characterization process is conducted using finite-element-based fitting method, including also the analysis of the applied numerical optimization algorithm. The fitting results are used to analyse the parameter sensitivity and to propose closed-form analytical relations for the temperature dependency of the material parameters. Finally, the utilisation of the analytical temperature functions for speeding up the parameter-fitting process is also demonstrated.     

Effect of working temperature on the interfacial behavior of overmolded hybrid fiber reinforced polypropylene composites

In the present study, the interfacial behavior of overmolded hybrid fiber reinforced polypropylene composites (hybrid composites) in the working temperature range from 23 °C to 90 °C was studied by experimental and constitutive methods. Monotonic and cycle loading-unloading single-lap-shear tests were employed to determine the interfacial properties of hybrid composites. The experimental results show that both interfacial shear strength and shear stiffness decrease with increasing working temperature. A regression function was adopted to evaluate the decaying degree of interfacial properties with increasing working temperature. The shear stress-displacement relationship under monotonic loading exhibits nonlinear behavior after an initial elastic region. The envelope lines of shear stress-displacement of hybrid composites under cyclic loading indicate that the nonlinearity in the curve is caused by the plastic deformation of polypropylene in the interphase region. A constitutive model was built to describe the nonlinear shear stress-displacement relation of hybrid composites at different working temperatures. A full suite of temperature-dependent plastic parameters in the model was obtained from cyclic loading-unloading tensile tests. The predicted shear stress–displacement curves agreed well with experimental results from different working temperatures. In addition, the failure mode of hybrid composites varied with working temperature.     

Nonlinear free vibrations of porous composite microplates incorporating various microstructural-dependent strain gradient tensors

The main objective of the present numerical analysis is to predict the nonlinear frequency ratios associated with the nonlinear free vibration response of porous composite plates at microscale in the presence of different microstructural gradient tensors. To achieve this end, by taking cubic-type elements into account, isogeometric models of porous composite microplates are obtained with and without a central cutout and relevant to various porosity patterns of distribution along the plate thickness. The established unconventional models have the capability to capture the effects of various unconventional gradient tensors continuity on the basis of a refined shear deformable plate formulation. For the simply supported microsized uniform porous functionally graded material (U-PFGM) plate having the oscillation amplitude equal to the plate thickness, it is revealed that the rotation gradient tensor causes to reduce the frequency ratio about 0.73%, the dilatation gradient tensor causes to reduce it about 1.93%, and the deviatoric stretch gradient tensor leads to a decrease of it about 5.19%. On the other hand, for the clamped microsized U-PFGM plate having the oscillation amplitude equal to the plate thickness, these percentages are equal to 0.62%, 1.64%, and 4.40%, respectively. Accordingly, it is found that by changing the boundary conditions from clamped to simply supported, the effect of microsize on the reduction of frequency ratio decreases a bit.

     

Predicting the tautomeric equilibrium of acetylacetone in solution. I. The right answer for the wrong reason?

This study investigates how the various components (method, basis set, and treatment of solvent effects) of a theoretical approach influence the relative energies between keto and enol forms of acetylacetone, which is an important model system to study the solvent effects on chemical equilibria from experiment and theory. The computations show that the most popular density functional theory (DFT) approaches, such as B3LYP overestimate the stability of the enol form with respect to the keto form by ～10 kJ mol^?1, whereas the very promising SCS‐MP2 approach is underestimating it. MP2 calculations indicate that in particular the basis set size is crucial. The Dunning Huzinaga double ζ basis (D95z(d,p)) used in previous studies overestimates the stability of the keto form considerably as does the popular split‐valence plus polarization (SVP) basis. Bulk properties of the solvent included by continuum approaches strongly stabilize the keto form, but they are not sufficient to reproduce the reversal in stabilities measured by low‐temperature nuclear magnetic resonance experiments in freonic solvents. Enthalpic and entropic effects further stabilize the keto form, however, the reversal is only obtained if also molecular effects are taken into account. Such molecular effects seem to influence only the energy difference between the keto and the enol forms. Trends arising due to variation in the dielectric constant of the solvent result from bulk properties of the solvent, i.e., are already nicely described by continuum approaches. As such this study delivers a deep insight into the abilities of various approaches to describe solvent effects on chemical equilibria. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Cut sharing for multistage stochastic linear programs with interstage dependency

Multistage stochastic programs with interstage independent random parameters have recourse functions that do not depend on the state of the system. Decomposition-based algorithms can exploit this structure by sharing cuts (outer-linearizations of the recourse function) among different scenario subproblems at the same stage. The ability to share cuts is necessary in practical implementations of algorithms that incorporate Monte Carlo sampling within the decomposition scheme. In this paper, we provide methodology for sharing cuts in decomposition algorithms for stochastic programs that satisfy certain interstage dependency models. These techniques enable sampling-based algorithms to handle a richer class of multistage problems, and may also be used to accelerate the convergence of exact decomposition algorithms. Research leading to this work was partially supported by the Department of Energy Contract DE-FG03-92ER25116-A002; the Office of Naval Research Contract N00014-89-J-1659; the National Science Foundation Grants ECS-8906260, DMS-8913089; and the Electric Power Research Institute Contract RP 8010-09, CSA-4O05335. This author's work was supported in part by the National Research Council under a Research Associateship at the Naval Postgraduate School, Monterey, California.     

基于非局部塑性模型的应变局部化理论分析及数值模拟

通过求解一个第二类Fredholm方程,得到了基于非局部塑性软化模型的应变局部化问题理论解,结果表明,只有在当采用过非局部修正形式的非局部塑性软化模型才能得到应变局部化解,且得到的塑性应变分布和荷载响应依赖于所引入的特征长度及过非局部权参数。通过一维应变局部化有限元数值解,验证了非局部理论的引入能克服计算结果的网格敏感...     

Study of glassy microporous filters in the sodium borosilicate glasses with appropriate carriers

Summary DúThe aim of this work is to prepare a porous filter composed of two porous layers: macro-porous carrier and micro-porous sodium borosilicate (NBS) glass with TiO₂ additive (NBST glass), a Vycor-type glass. In the present work we prepared the macroporous support from the same material (NBST glass) as the upper microporous layer and then by sintering both parts to produce the required composite. This work introduces the results of experiments in the preparation of micro-porous filter on NBST glass base, laid on macro-porous carrier. After sintering of scrap NBST glass, porous samples were prepared to be used as carriers for micro-porous samples of phase-separated NBST glass. In other cases, the following carrier materials were used: a) frita SIMAX, b) Al₂O₃. The properties of the NBST glass and the changes in the glass structure with temperature were studied in order to determine the optimal sintering temperature of the prepared glasses. For the development of the sintered glasses, valuable information was obtained from heating microscopy (HM) and scanning electron microscopy (SEM) studies. The combination of the HM and SEM results with the measurements of the micro-hardness and density directed to the further study of the phase separated NBST glasses.