Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Behavior of cellulose in NaOH/Urea aqueous solution characterized by light scattering and viscometry

Cellulose was dissolved in 6 wt % NaOH/4 wt % urea aqueous solution, which was proven by a ¹³C NMR spectrum to be a direct solvent of cellulose rather than a derivative aqueous solution system. Dilute solution behavior of cellulose in a NaOH/urea aqueous solution system was examined by laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 6 wt % NaOH/4 wt % urea aqueous solution at 25 °C was [η] = 2.45 × 10^?2 weight‐average molecular weight (M_w)^0.815 (mL g^?1) in the M_w region from 3.2 × 10⁴ to 12.9 × 10⁴. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were 6.0 nm, 350 nm^?1, and 20.9, respectively, which agreed with the Yamakawa–Fujii theory of the wormlike chain. The results indicated that the cellulose molecules exist as semiflexible chains in the aqueous solution and were more extended than in cadoxen. This work provided a novel, simple, and nonpollution solvent system that can be used to investigate the dilute solution properties and molecular weight of cellulose. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 347–353, 2004     

Relationship between the dynamic softening transition and wet sliding friction of elastomer compounds

For properly chosen elastomer compounds, thermorheological characterization is combined with an examination of the variation of the wet sliding friction with temperature. A conceptual argument leads to the assumption that the wet sliding friction should maximize at the energy dissipation peak associated with the dynamic softening transition at a characteristic frequency determined by the sliding speed and the effective smallest surface asperity scale. The dynamic softening transition is characterized with the peak in tan δ/G′ⁿ, where tan δ is the loss tangent, G′ is the elastic modulus, and n is a constant between 0 and 1. The William–Landel–Ferry transform is uncritically applied for extrapolating the position of the peak in tan δ/G′ⁿ at high frequencies. Even based on the criterion of tan δ, the results obtained on a concrete surface indicate that the effective smallest asperity scale is of order of 100 μm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2467–2478, 2004     

Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

NMR investigation of concentrated alumina and silica slurries

The longitudinal relaxation times (T₁) of water in concentrated silica and alumina slurries were measured as a function of solids content. It was shown that the results could be fit very well with a two-phase fast-exchange model between free and surface-bound water. As expected, values of T₁ for bound water were in the order of 20–2000 times lower than that for free water, indicating a higher effective viscosity of the surface-bound water. The strength of the interaction depended on the particular surface, and all of the aluminas examined interacted more strongly with water than the two silicas studied, which themselves differed considerably. The chemical mechanical polishing (CMP) removal rate of tantalum by silica slurries was shown to be directly correlated with the interaction parameters, derived from the NMR relation times rather than with total surface hydroxyl group concentration.     

A Novel Model for Protein Immobilization on Microspheres

The immobilization of proteins, especially receptor proteins commonly used in high through-put screening of drugs (HTS), have received great attention in recent years. There are many successful isothermal models for describing the adsorption of protein onto solid surface, such as Langmuir model, Bi-Langmuir model, Fowler model, Freundlich model, Freundlich-Langmuir model and Tekmin model etc. In all these models, Langmuir model was the most favorable one model accepted by many researchers, but the experimental results showed that it was not entirely fit to all adsorption behaviors. So new models were required for describing protein adsorption onto microspheres in different conditions.In our research, a novel isothermal model, including Langmuir and other adsorbing behaviors was presented basing on the holding degree of surface active sites and the interaction styles of protein immobilization. In Langmuir model, the adsorbing amount of protein was described as [PS] =Km[P]/1 + K[P], where [PS] was the concentration of adsorbed protein, [P] was the concentration of freeprotein at equilibrium state, and Km and K was constant. According to the interactions of protein and ligands, there were three patterns in the interactions of protein and ligands. On the similar assumption that the interaction of protein and microspheres were three styles, and based on the definition of the holding degree of surface active sites (Y), three adsorption behaviors could be described as Y K[ P ]φ/ K[P]φ+1 or ln K + φ ln[P] =ln(Y/1-Y) in which [P] was the concentration of free protein at equilibrium state, and φ and K was constant. Different scale of φ presented different adsorption behaviors, especially when φ was 1, the adsorption behavior was Langmuir adsorbing model. Figure I indicated the different adsorbing results in different adsorption behaviors (φ＞1, φ＜1,and φ=1).     

Baker＇s Yeast Mediated Reduction of Optically Active Diketone

Baker‘s yeast mediated reduction of optically active diketone is described. The two keto groups are efficiently differentiated and the ee value of the recovered material is considerably raised. It affords highly optically active key intermediates efficiently for the synthesis of natural polyhydroxylated agarofuran products.     

Galerkin method for optimal control of second‐order evolution equations

This paper presents the Galerkin approximation of the optimization problem of a system governed by non‐linear second‐order evolution equation where a non‐linear operator depends on derivative of the state of the system. The control is acting on a non‐linear equation. After giving some results on the existence of optimal control we shall prove the existence of the weak and strong condensation points of a set of solutions of the approximate optimization problems. Each of these points is a solution of the initial optimization problem. Finally we shall give a simple example using the obtained results. Copyright © 2004 John Wiley & Sons, Ltd.     

Modelling of an underground waste disposal site by upscaling

In this paper, we study the global behaviour of an underground waste disposal in order to have an accurate upscaled model suitable for the computations involved in safety assessment processes. We start from a detailed model describing the transport of pollutant leaking from a high number of units. Using the method of homogenization, going to the limit, we obtain first a macroscopic model where the sources are now appearing globally. Then we compute a first‐order matched asymptotic expansion and we give the error estimates for this approximation. Copyright © 2004 John Wiley & Sons, Ltd.     

Dynamic boundary stabilization of a Reissner–Mindlin plate with Timoshenko beam

This paper is concerned with well‐posedness results for a mathematical model for the transversal vibrations of a two‐dimensional hybrid elastic structure consisting of a rectangular Reissner–Mindlin plate with a Timoshenko beam attached to its free edge. The model incorporates linear dynamic feedback controls along the interface between the plate and the beam. Classical semigroup methods are employed to show the unique solvability of the coupled initial‐boundary‐value problem. We also show that the energy associated with the system exhibits the property of strong stability. Copyright © 2004 John Wiley & Sons, Ltd.