Diffusion from sessile droplets through membranes

We analyze diffusion from a periodic array of hemispherical droplets through a membrane. We find that the multiple sources do not interact strongly, even when the droplets are closely spaced, so that the flux through the membrane appears nearly additive.     

Thermodynamic derivative properties and densities for hyperbaric gas condensates: SRK equation of state predictions versus Monte Carlo data

The ability of Soave–Redlich–Kwong cubic equation of state (SRK EoS) to predict densities and thermodynamic derivative properties such as thermal expansivity, isothermal compressibility, calorific capacity, and Joule–Thompson coefficients, for two gas condensates over a wide range of pressures (up to 110 MPa) was studied. The predictions of the EoS were compared to Monte Carlo simulation data obtained by Lagache et al. [M.H. Lagache, P. Ungerer, A. Boutin, Fluid Phase Equilibr. 220 (2004) 221]. Two completely different alpha functions for the SRK EoS attractive term were used and their respective effects on the predictions of such properties were analyzed. Also, two different forms of the crossed terms of the attractive parameter, a_ij, and three expressions of the crossed terms of the repulsive parameter, b_ij, were combined in different ways, and predictions were carried out. Little sensitivity of the properties on the chosen alpha function, except for the calorific capacities, was found in the systems studied. The most commonly used combination rules to model phase behavior of reservoir fluids, i.e. geometric and arithmetic forms of a_ij and b_ij, respectively, predicted very deficient results for these fluids at extreme conditions, specially for density calculations.     

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Some aspects of diffusion: fluctuations in reaction diffusion,and geometric influences in nonuniform media

Summary We deal with two diffusion problems: Space-integrated conserved entities characterizing very fast - diffusion - controlled reactions, such as time lags, etc. are universal. They are given by relationships which do not reflect the failure of the mean field hydrodynamic equations. We present another application which does not reflect this failure, for determining the surface flux via a diffusion controlled reaction producing a colored product. Another anomalous diffusion process we considered is transport through cellular materials whose cell sizes are highly nonuniform. We have analyzed the effects of extreme nonuniformity by considering fractal-like models of cellular solids. The diffusion current through these models can exhibit anomalous time-dependencies which are not predicted by the diffusion equation. In particular, it is shown that the initial diffusion current can be characterized by a power-law dependence on the time. Furthermore, the exponent of the power law is given in terms of the distribution of cell sizes in the fractal-like cellular solid.     

Excited states of porphyrin isomers and porphycene derivatives: a SAC-CI study

Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds.     

Graft copolymer of polymethyl methacrylate-g-polycarbonate urethane and the fully gelled grafted networks

We have synthesized and characterized the graft copolymer of polymethyl methacrylate (PMMA)-graft-polycarbonate urethane (PCU) (designated PMMA-g-PCU) and the fully gelled mutually crosslinked network composed of both PMMA and PCU (designated as PMMA-PCU-N). Unlike the previously synthesized one phase PCU/PMMA simultaneous interpenetrating polymer networks (IPN's), both of these new materials exhibited two distinct T_g's (from DSC and DMA studies) at all compositions which we have studied. The two-phase nature of the graft and network polymer was confirmed by TEM with domain sizes smaller than those found in the blends of the linear PCU and PMMA chains. In comparison with the corresponding IPN's, the PMMA-g-PCU and the PMMA-PCU-N were thermally less stable and had a lower ultimate strength. © 1992 John Wiley & Sons, Inc.