Pore Network Analysis of Resistivity Index for Water-Wet Porous Media

Pore network analysis is used to investigate the effects of microscopic parameters of the pore structure such as pore geometry, pore-size distribution, pore space topology and fractal roughness porosity on resistivity index curves of strongly water-wet porous media. The pore structure is represented by a three-dimensional network of lamellar capillary tubes with fractal roughness features along their pore-walls. Oil-water drainage (conventional porous plate method) is simulated with a bond percolation-and-fractal roughness model without trapping of wetting fluid. The resistivity index, saturation exponent and capillary pressure are expressed as approximate functions of the pore network parameters by adopting some simplifying assumptions and using effective medium approximation, universal scaling laws of percolation theory and fractal geometry. Some new phenomenological models of resistivity index curves of porous media are derived. Finally, the eventual changes of resistivity index caused by the permanent entrapment of wetting fluid in the pore network are also studied.Resistivity index and saturation exponent are decreasing functions of the degree of correlation between pore volume and pore size as well as the width of the pore size distribution, whereas they are independent on the mean pore size. At low water saturations, the saturation exponent decreases or increases for pore systems of low or high fractal roughness porosity respectively, and obtains finite values only when the wetting fluid is not trapped in the pore network. The dependence of saturation exponent on water saturation weakens for strong correlation between pore volume and pore size, high network connectivity, medium pore-wall roughness porosity and medium width of the pore size distribution. The resistivity index can be described succesfully by generalized 3-parameter power functions of water saturation where the parameter values are related closely with the geometrical, topological and fractal properties of the pore structure.     

A Multi-Scale Approach to Model Two-Phase Flow in Heterogeneous Porous Media

The immiscible displacement of a wetting fluid by a non-wetting one in heterogeneous porous media is modeled using a multi-scale network-type analysis: (1) The pressure-controlled immiscible displacement of water by oil in pore-and-throat networks (1st length scale ~ 1?mm) is simulated as a capillary-driven process. (2) The pressure-controlled immiscible displacement in uncorrelated cubic lattices (2nd length scale ~ 1?cm) is simulated as a site percolation process governed by capillary and gravity forces. At this scale, each node represents a network of the previous scale. (3) The rate-controlled immiscible displacement of water by oil in cubic networks (3rd length scale ~ 10?cm), where each node represents a lattice of the previous scale, is simulated by accounting for capillary, gravity, and viscous forces. The multi-scale approach along with the information concerning the pore structure properties of the porous medium can be employed to determine the transient responses of the pressure drop and axial distribution of water saturation, and estimate the effective (up-scaled) relative permeability functions. The method is demonstrated with application to data of highly heterogeneous soils.     

Statistical Synthesis of Imaging and Porosimetry Data for the Characterization of Microstructure and Transport Properties of Sandstones

The microstructure of a suite of sandstone samples is quantitatively analyzed using a method which combines information from thin section micrographs of the pore space with mercury injection porosimetry in a statistical framework. This method enables the determination of a continuous distribution of pore sizes ranging from few nanometre to several hundred micrometre. The data obtained unify fractal and Euclidean aspects of the void space geometry, yield estimates of the pore-to-throat aspect ratio and challenge the ability of commonly used network models to describe fluid percolation in multiscale porous media. Application of critical path analysis to the prediction of flow permeability and electrical conductivity of sandstone core samples using the new information produces results comparable to those obtained by the classical approach—a fact attributed to the presence of macroscopic heterogeneity at the scale of several millimetres.     

UTILIZATION OF TOOLS FOR SUCCESSFUL. TROUBLESHOOTING OF STRUCTURAL PROBLEMS

A structural failure problem was solved using an integrated and iterative program of testing and analysis. The steps taken in solving the problem were: analytical calculations; operational testing; qualifications of analytical results; problem identification; design of corrective action; and confirmatory testing.     

Experimental study of the immiscible displacement of shear-thinning fluids in pore networks

The pore scale mechanisms and network scale transient pattern of the immiscible displacement of a shear-thinning nonwetting oil phase (NWP) by a Newtonian wetting aqueous phase (WP) are investigated. Visualization imbibition experiments are performed on transparent glass-etched pore networks at a constant unfavorable viscosity ratio and varying values of the capillary number (Ca), and equilibrium contact angle (theta(e)). Dispersions of ozokerite in paraffin oil are used as the shear-thinning NWP, and aqueous solutions of PEG colored with methylene blue are used as the Newtonian WP. At high Ca values, the tip splitting and lateral spreading of WP viscous fingers are suppressed; at intermediate Ca values, the primary viscous fingers expand laterally with the growth of smaller capillary fingers; at low Ca values, network spanning clusters of capillary fingers separated by hydraulically conductive noninvaded zones of NWP arise. The spatial distribution of the mobility of shear-thinning NWP over the pore network is very broad. Pore network regions of low NWP mobility are invaded through a precursor advancement/swelling mechanism even at relatively high Ca and theta(e) values; this mechanism leads to irregular interfacial configurations and retention of a substantial amount of NWP along pore walls; it becomes the dominant mechanism in displacements performed at low Ca and theta(e) values. The residual NWP saturation increases and the end WP relative permeability decreases as Ca increases and both become more sensitive to this parameter as the shear-thinning behavior strengthens. The shear-thinning NWP is primarily entrapped in individual pores of the network rather than in clusters of pores bypassed by the WP. At relatively high flow rates, the amplitude of the variations of pressure drop, caused by fluid redistribution in the pore network, increase with shear-thinning strengthening, whereas at low flow rates, the motion of stable and unstable menisci in pores is reflected in strong pressure drop fluctuations.     

Theoretical elucidation of a classic reaction: protonation of the quadruple bond of the octachlorodimolybdate(II,II) [Mo2Cl8]4- anion

The protonation reaction of the unbridged quadruple metal-metal bond of [Mo(2)Cl(8)](4-) anion producing the triply bonded hydride [Mo(2)(μ-H)(μ-Cl)(2)Cl(6)](3-) is studied by accurate Density Functional Theory computations. The reactant, product, stable intermediates, and transition states are located on the potential energy surface. The water solvent is explicitly included in the calculations. Full reaction profiles are calculated and compared to experimental data. The mechanism of the reaction is fully elucidated. This involves two steps. The first is a proton transfer from an oxonium ion to the quadruple bond, being rate determining. The second, involves the internal rearrangement of chlorine atoms and is much faster. Activation energies with a mean value of 19 kcal/mol are calculated, in excellent agreement with experimental values.     

Liposomal drugs dispersed in hydrogels. Effect of liposome, drug and gel properties on drug release kinetics

Release of calcein and griseofulvin (GRF) from control (gels in which solutes are dissolved in) and liposomal gels was studied using agarose-assisted immobilization as a technique to separate gels from drug-receptor compartments. Liposomes composed of phosphatidylcholine (PC) or distearoyl-glycero-PC and cholesterol (DSPC/Chol), and incorporating calcein or GRF were prepared by thin film hydration. After cleaning the liposomes they were dispersed in different hydrogels (carbopol 974 [1, 1.5 or 2% (w/w)], hydroxylethyl-cellulose (HEC) [4% (w/w)], or a mixture of the two), and release of calcein or GRF was followed by fluorescence or photometric technique, respectively. Results show that calcein release from liposomal gels is slower compared to control gels, and can be further retarded by using rigid-membrane liposomes (faster release from PC-liposome compared to DSPC/Chol-liposome gels). Additionally, calcein release is not affected by the lipid amount loaded (in the range from 2 to 8 mg/ml), therefore solute loading can be controlled according to needs.

Oppositely, GRF release from liposomal gels is determined by drug loading. At high drug loading levels (compared to GRF aqueous solubility), GRF is released with constant rate from liposomal gels irrespective of liposome type (PC or DSPC/Chol). Thereby, for amphiphilic/lipophilic drugs, drug properties (solubility, log P) determine the system behavior.

Calcein and GRF release from control carbopol gels is faster compared to HEC and mixture gels. The same is true for calcein in liposomal gels. Carbopol gel rheological properties were found to be significantly different (compared to the other gels), implying that these characteristics are important for drug diffusion from gels.     

Vortex lattice transitions in YNi2B2C

We have performed extensive small-angle neutron scattering (SANS) diffraction studies of the vortex lattice in single crystal YNi₂B₂C for B‖c. High-resolution SANS, combined with a field-oscillation vortex lattice preparation technique, allows us to separate Bragg scattered intensities from two orthogonal domains and accurately determine the unit cell angle, β. The data suggest that upon increasing field there is a finite transition width where both low- and high-field distorted hexagonal vortex lattice phases, mutually rotated by 45°, coexist. The smooth variation of diffracted intensity from each phase through the transition corresponds to a redistribution of populations between the two types of domains.     

Metachromatic effects and photodegradation of basic blue on nanocrystalline titania films

Titania nanocrystalline films have been deposited on solid substrates by a sol-gel procedure carried out in Triton X-100 reverse micelles. When the dye Basic Blue is adsorbed on these films, it demonstrates a strong metachromatic effect; that is, it aggregates, resulting in a blue shift of its absorption spectrum. Metachromasy in this system is related to the hydrophilicity of the film surface and to the humidity of the film environment. Films composed of 67% titania and 33% silica gave an intense and reversible metachromatic effect that can be exploited to make a handy humidity sensor. Photodegradation of Basic Blue on titania films is faster in humid environments than in dry environments, and this goes in parallel with metachromatic effects.