Fractal patterns of fluid domains for displacement processes in porous media

Percolation invasion displacement of a compressible defender is examined for two cases: when only the smallest accessible site is entered at each step and when all accessible sites less than the size given by a reducing back pressure are entered at each time step. Although the fractions of invading fluid are different, their scaling properties are equivalent. The effect of limited control of a back pressure in a real displacement and the effect of viscosity in a real time displacement are examined. In these cases the scaling properties of a percolation process at breakthrough are removed. As a result, one should expect that realistic displacement models will not have the singular properties usually attributed to percolation processes.     

Low-frequency velocity correlation spectrum of fluid in a porous media by modulated gradient spin echo.

In addition to the fast correlation for local stochastic motion, the molecular velocity correlation function in a fluid enclosed within the pore boundaries features a slow long time-tail decay. Here we present its study by the NMR modulated gradient spin-echo method (MGSE) [1] on a system of water trapped in the space between the closely packed polystyrene beads. With MGSE pulse sequence, a repetitive train of RF pulses with interspersed gradient pulses periodically modulates the spin phase. It gives the spin echo attenuation proportional to a value of the molecular velocity correlation spectrum at the modulation frequency. Covering the frequency range between Hz and MHz, it is a complement to the quasi-elastic neutron scattering, and so a suitable technique for the investigation of low frequency molecular dynamics in fluids. In our experiment, it enables to extract the low frequency correlation spectrum of water molecules confined in porous media. The function exhibits a negative long time-tail characteristic (a low frequency decay of the spectrum), which can be interpreted as a molecular back scattering on boundaries. The results can be well fitted with the spectrum calculated from the solution of the Langevin equation for restricted diffusion (which exhibits an exponential decay) [2] as well as with the spectrum obtained when simulating the hydrodynamics of molecular motion constrained by capillary walls (which gives an algebraic decay) [3]. Despite much work on theories and simulation, which predict slow negative long time tail of molecular velocity correlation dynamics in confined fluids, the obtained velocity correlation spectrum is the first experimental evidence to confirm these effects. The obtained dependence of spin echo attenuation on time, gradient strength and modulation frequency is also the first experimental verification of the recently developed approach to the spin echo in porous media, that uses the spin phase average with the cumulant expansion to get the attenuation as a discord of spin spatial coherence [4].     

Ageing of random porous media following fluid deterministic displacement, freezing, thawing

This paper introduces and investigates a simple model of random porous media degradation via several fluid displacing, freezing, and thawing cycles. The fluid transport is based on the deterministic method. The result shows that the topology and the geometry of porous media have a strong effect on displacement processes. The cluster size of the viscous fingering (VF) pattern in the percolation cluster increases with the increase of iteration parameter n. When iteration parameter , the VF pattern does not change with n. When and , the peak value of the distribution increases as n increases; is the normalized distribution of throat sizes after different displacement-damage but before the freezing. The distribution of throat size N(r) after displacement but before freezing damage, shows that the major change, after successive cycles, happens at r>0.9. The peak value of the distribution reaches a maximum when and r=1, where is the normalized distribution of the size of invaded throats for different iterations. This result is different from invasion percolation. The distribution of velocities normal to the interface of VF in the percolation cluster is also studied. When , the scaling function distribution is very sharp. The sweep efficiency E increases along with the increasing of iteration parameter n and decreases with the network size L. And E has a minimum as L increases to the maximum size of the lattice. The VF pattern in the percolation cluster has one frozen zone and one active zone. Received 30 March 1999 and Received in final form 8 August 1999     

Thermal conductivity of wet composite porous media

A model for the thermal conductivity of two-phase composite porous media, such as adsorbing desiccant bed with inert material, is presented. The unit cell model is extended to account for the inert materials and moisture sorbed in pores; and the effect of porosity, water content and presence of inert material is determined. The prediction of the effective thermal conductivity from this proposed model is compared with that given by other available models and experimental data and the proposed model is used to investigate the effect of porosity, water content and presence of inert material.     

Selective imaging of biofilms in porous media by NMR relaxation.

Nuclear magnetic resonance imaging (NMRI) techniques were employed to identify and selectively image biological films (biofilm) growing in aqueous systems. Biofilms are shown to affect both the longitudinal (T1) and transverse (T2) NMR relaxation time values of proximal water hydrogens. Results are shown for biofilm growth experiments performed in a transparent parallel-plate reactor. A comparison of biofilm distributions by both NMR and optical imaging yielded general agreement for both an open-flow system and an idealized porous system (the reactor without and with packed glass beads, respectively). The selective imaging of biofilm by relaxation NMRI is dependent upon the resolution of relaxation times for the fluid phases, dynamic range, and signal-to-noise ratio. For open-flow systems, the use of a rapid and quantitative T2-sorted NMRI technique was preferred. For porous systems where T2 values are generally more similar, a T1-weighted technique was preferred.     

Anomalous fluid transport in porous media induced by biofilm growth

Magnetic resonance measurements of the transition from normal to anomalous hydrodynamic dispersion in porous media due to biological activity are presented. Fractional advection-diffusion equations are shown to provide models for the measured impact of biofilm growth on porous media transport dynamics.     

Electron spin relaxation of triarylmethyl radicals in fluid solution

Electron spin relaxation times of a Nycomed triarylmethyl radical (sym-trityl) in water, 1:1 water:glycerol, and 1:9 water:glycerol were measured at L-band, S-band, and X-band by pulsed EPR methods. In H(2)O solution, T(1) is 17+/-1 micros at X-band at ambient temperature, is nearly independent of microwave frequency, and exhibits little dependence on viscosity. The temperature dependence of T(1) in 1:1 water:glycerol is characteristic of domination by a Raman process between 20 and 80 K. The increased spin-lattice relaxation rates at higher temperatures, including room temperature, are attributed to a local vibrational mode that modulates spin-orbit coupling. In H(2)O solution, T(2) is 11+/-1 micros at X-band, increasing to 13+/-1 micros at L-band. For more viscous solvent mixtures, T(2) is much shorter than T(1) and weakly frequency dependent, which indicates that incomplete motional averaging of hyperfine anisotropy makes a significant contribution to T(2). In water and 1:1 water:glycerol solutions continuous wave EPR linewidths are not relaxation determined, but become relaxation determined in the higher viscosity 1:9 water:glycerol solutions. The Lorentzian component of the 250-MHz linewidths as a function of viscosity is in good agreement with T(2)-determined contributions to the linewidths at higher frequencies.     

2D relaxation/diffusion correlations in porous media

2D correlations between NMR relaxation and/or diffusion have been used to investigate water and oil dynamics in food and micro-emulsion systems. In the case of Mozzarella and Gouda cheese samples, a significant change in D/T2 correlation is appearing with cheese aging. In the case of a water/toluene micro-emulsion, some evidence for coalescence effects is suggested by D/D exchange spectra.     

The modulation of coupled relaxation in porous media.

This work investigates the effects of modulation of the transverse and longitudinal relaxation of the surface-fluid/pore-fluid spin system in porous media. Important new NMR well logging applications identify pore fluids by varying the CPMG T(2) pulse spacing to discriminate on the basis of fluid diffusivities in applied and local static magnetic field gradients. However, anomalous laboratory CPMG T(2) results have been reported repeatedly over 25 years for various porous media filled with a single fluid. In relatively large pores, at near bulk conditions, the transverse relaxation of diffusing molecular spins should be proportional to the square of the CPMG pulse spacing tau, the susceptibility contrast at the pore wall and the applied gradient. Observed is a markedly linear tau dependence that saturates at a plateau for large tau. The effect is not quadratic in applied gradient or susceptibility. For large pores, the tau dependence and the saturation value are proportional to the surface-to-volume ratio of the pores. This is in distinct contrast to the behavior observed by Borgia, Brown and Fantazzini for systems with much smaller pores at higher magnetic fields. The large-pore anomalous behaviors can be explained as a modulation of the exchange between surface-fluid and pore-fluid spins, such as observed by Luz and Meiboom in 1963 for water enriched with quadrupolar 17O. Scalar coupling of the solid-surface spins to the fluid-surface spins was postulated by Kleinberg, Kenyon and Mitra as a dominant relaxation mechanism for the surface fluid. The CPMG tau effect can be described as the modulation of the exchange coupling by the CPMG pi pulses, which mix the magnetizations between the exchanging, strongly coupled spin systems of the pore-fluid and the surface-fluid, which is, in turn, weakly coupled by scalar or pseudo-scalar interactions to the fast-relaxing solid surface.     

Magnetic susceptibility contrast induced field gradients in porous media.

Using a two-component composite theory, we compute the internal field gradient of a periodic porous medium induced by the magnetic susceptibility contrasts. The magnetization of such a system is computed by using the diffusion eigenstates in Fourier representation. We show that the volume averaged field gradient, when used in the formula for free diffusion, significantly overestimates the magnetization decay rate. We also establish bounds for such a periodic system within which the Gaussian approximation is valid for diffusion of spins in the pore space.     

Paramagnetic effects of iron(III) species on nuclear magnetic relaxation of fluid protons in porous media

The (1)H NMR spin-lattice relaxation time, T(1), of saturated sands depended on the chemistry of the pore fluid, pore size distribution, and relaxivity of the surface. In the absence of paramagnetic impurities, surface relaxivities of quartz sand and silica gel samples of known porosity and surface area at any pH were lower than any previously reported values. Relaxation rate of the bulk pore fluid increased linearly with increasing Fe(III) concentration and varied with speciation of the ion. With only 0.01% of the silica surface sites occupied by sorbed Fe(III) ions, surface relaxivity increased by an order of magnitude. In addition, low concentrations of Fe(III)-bearing solid phases present as surface coatings or as separate mineral grains increased surface relaxation as much as two orders of magnitude. We believe that observations of relatively constant surface relaxivity in rocks by previous researchers were the result of consistently high surface concentrations of paramagnetic materials.