Experiments in Fluids 35 (2003) 159166 DOI 10.

1007/s00348-003-0641-x

Measurement of 3D pore-scale flow in index-matched porous media

hr, K. Roth, B. Ja hne M. Sto

159 solution would be unfeasible. However, applications like those mentioned above are generally not interested in this detailed information, but in averaged, macroscopic quantities. The aim of the research is to nd a suitable macroscopic model and to derive the parameters of this model from the properties of the underlying pore-scale model. Measurements of macroscopic quantities have been done since the middle of the 19th century for hydraulic conductivity (Darcy 1856) and about hundred years later for dispersion coefcients (as outlined e.g., in Fried and Combarnous 1971). The difculties in probing ow and transport on the pore scale, stemming from the opaqueness of the medium, can be overcome by the application of a transparent porous matrix and liquids with their refractive index matched to that of the matrix. Refractive 1 index matching methods were used for some decades to Introduction gain 3D optical access to liquid ow phenomena (for an The study of ow and transport in porous media is an overview see Budwig 1994), the application of these active eld of research which has applications in many disciplines, e.g., the forecast of spread and fate of pollu- methods to porous media was done by Burdett et al. (1981) tants in aquifers in hydrology, oil production in petroleum using a light absorption technique, Montemagno and Gray (1995) and Rashidi et al. 1996 using PLIF, and Peurrung engineering, heterogeneous catalysis in chemical engiet al. 1995 and Moroni and Cushman (2001) using particle neering and ow of blood and other body tissues in tracking velocimetry (PTV). In contrast to previous works, medicine. The scientic approach to the description of ow and the present planar laser-induced uorescence (PLIF) transport in porous media is based on the introduction of technique has a much higher spatial and temporal models and parameters on different scales. Although the resolution and is the rst to simultaneously visualize the model on the pore-scale, mainly the equations of Navier dynamics of two immiscible liquids. Stokes and molecular diffusion, is mostly well known, the exact boundary conditions can, in general, not be 2 measured and, even if they were available, the numerical Experimental setup In PLIF, a uorescent substance is excited by a planar laser sheet with its wavelength tuned to the absorption band of Received: 2 September 2002 / Accepted: 8 March 2003 the substance. The light is absorbed by the substance and Published online: 28 June 2003 re-emitted at characteristic wavelengths. A 2D image of the Springer-Verlag 2003 concentration distribution can be obtained by a CCD camera mounted with its optical axis perpendicular to the hr (&), K. Roth, B. Ja hne M. Sto laser sheet. Consecutive displacement of the laser plane in Institute for Environmental Physics, the out-of-plane direction results in a set of 2D images Im Neuenheimer Feld 229, 69120 Heidelberg, Germany E-mail: michael.stoehr@iwr.uni-heidelberg.de quantifying the 3D concentration distribution. This technique gives access to 3D information without any chal hr, B. Ja hne M. Sto Interdisciplinary Center for Scientic Computing, lenging tomographic reconstruction. The prerequisite for Im Neuenheimer Feld 368, 69120 Heidelberg, Germany this method to work accurately is that the refractive The authors gratefully acknowledge the nancial support of the indices of solid and liquids are precisely matched at the graduate program Modelling and Scientic Computing in dye emission wavelengths. Figure 1 shows the arrangeMathematics and Natural Sciences of the Interdisciplinary ment of the setup components, which are detailed in the Center for Scientic Computing. We should also like to thank Schott Glas, Molecular Probes Inc., and Dow Corning GmbH for following paragraphs. The light source for illumination is an argon ion laser their assistance, and two anonymous referees for their constructive reviews. operating at 488 nm with an output of 1.6 W. The beam is Abstract We present the experimental analysis of uid ow at the pore-scale of a transparent porous medium with matched refractive indices of the solid and liquid phases. The planar laser-induced uorescence (PLIF) technique described is the rst to simultaneously visualize the 3D pore-scale ow of two immiscible liquid phases in porous media. Through the application of a highly precise index matching method and the employment of up-to-date CCD imaging hardware, the system features a high spatial resolution and sampling rate. The method was used to study the dispersion of a tracer dye in singlephase ow and the displacement of oil by water in an imbibition process.

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Fig. 1. Experimental setup

coupled to an optical ber and then focused on the ow cell to a diameter between 0.5 and 1 mm. It is expanded to a vertical sheet by reection on the mirror of a galvanometer scanner oscillating at 50 Hz. A high resolution progressive scan camera (Basler A113P) is used to record the images. It employs a CCD sensor chip with a resolution of 1,3001,030 pixels, which provides features such as electronic exposure time control and partial scan. Thereby, the exposure time is adjusted continuously in steps of 20 ms (the scanning duration of the laser beam) to obtain maximum signalto-noise ratio, and the scan area on the CCD chip is adapted to the geometry of the ow cell. The accumulated charges on the CCD are digitized by the camera and transferred as an 8-bit video data stream to a FPGA framegrabber (Silicon Software microenable equipped with a Xilinx XC4085XLA). The data are received by

a PC via its PCI interface and stored to a hard disk. Optical bandpass lters (55020 nm and/or 60020 nm) are used to limit the imaging to these emission wavelengths of the uorescent dye, where the refractive indices are closely matched (see Sect. 5), and also to screen scattered light, e.g., from imbedded air bubbles. In two-phase ow, where two dyes with different emission wavelengths are used, a PC-controlled lter wheel is deployed to change between the two lters. The switch is done after each complete volume scan. Camera, bandpass lter and galvanometer scanner are mounted on a motorized translation stage in order to subsequently scan different parallel planes in the ow volume. In the present experiments, the increment between two adjacent planes was set to 0.4 mm. The accuracy of the measurement is limited by the camera noise and high-frequency oscillations of the laser light intensity to a signalto-noise ratio of approximately 20:1. The ow cells are rectangular parallelepipeds made of Plexiglass. The solid granulate material is clamped between two metal grids which adjoin liquid-lled inlet and outlet areas. A tubing pump conveys the uids through a tube from the outlet to the inlet. Two versions of the ow cells for horizontal and vertical ow direction are sketched in Fig. 2. The volumes of the porous matrix are 844 cm3 and 5105 cm3 respectively. In horizontal ow, a partial scan area of 1,300600 pixels is used, resulting in a resolution of about 70 lm in the x and y directions. The resolution in the z direction is given by the width of the laser beam (0.51 mm). The system is capable of recording 90 parallel planes every 30 s, corresponding to a data rate of about 2.3 MB/s. During the rst 14 s, the actual scanning and data aquisition take place, while the

Fig. 2. Flow cells for a horizontal and b vertical ow

remaining 16 s are used to drive back the translation stage and store the data to the hard disk.

3 Selection of solid and liquids 3.1 Solid matrix A transparent, rigid and inert material is required as the solid porous matrix. The refractive indices of plastics are in a range from 1.49 (acrylic, e.g., Plexiglass or Perspex) to 1.58 (polycarbonate, e.g., Lexan or Makrolon), those of optical glasses from 1.46 (fused silica) to 1.87 (Schott LaSFN9). Because the number of suitable liquids decreases rapidly with increasing refractive index, experiments were performed with fused silica (Schott Lithotec) and Plexiglass. The fused silica was crushed with a jaw crusher and sieved to sizes of 0.61.0 mm. The Plexiglass was obtained from the manufacturer in a granulation of 0.6 mm mean diameter. Since a large portion of these grains had air bubbles inside, they were separated in a NaCl solution with a density hardly smaller than that of Plexiglass. Whereas Plexiglass is only moderately acid resistant, fused silica is extremely resistant owing to the very strong siliconoxygen bonds. The physical and optical properties of these two materials are shown in Table 1 and Fig. 3. 3.2 Liquids The two immiscible and transparent liquids have to match the refractive index of the solids and are additionally required to be inert, nontoxic, nonvolatile, and nonammable. A group of Dow Corning silicone oils were used as non-aqueous phase liquids (NAPLs). They are all miscible with each other so that the refractive index of the mixture can be adjusted between 1.375 (DC 200) and 1.533 (DC 710). For the aqueous phase, a zinc chloride solution was used. Due to deprotonation of the hydrated zinc ions, the pH of a solution with a refractive index of 1.46 is around 2.0. It is therefore not compatible with Plexiglass and with many uorescent dyes. Though sodium iodide solutions have a signicantly higher pH, the number of compatible dyes is even lower due to reaction with iodide. Properties of silicone oil and pure water are shown in Table 2.
Table 1. Solid properties

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Fig. 3. Refractive index versus wavelength for fused silica (Schott Lithotec AG 2001), Plexiglass (Waxler et al. 1979), silicone oil (Cargille Laboratories Inc. 1999) and NaI solution (Narrow et al. 2000)

Figure 3 represents the refractive indices of silicone oil and an aqueous solution as a function of wavelength. Due to the lack of data for zinc chloride solutions, the latter is exemplied by the model for sodium iodide solutions given in Narrow et al. 2000. The weight proportions of the silicone oils were 84% DC 550 and 16% DC 556 for the experiments with Plexiglass and 98% DC 556 and 2% DC 200 with fused silica. A zinc chloride solution of 58 wt% was used with fused silica. The liquids were rst prepared with these approximate proportions, which were then ne tuned as described in Sect. 5. The densities and viscosities of the index matched liquids are shown in Table 3.

4 Fluorescent dye characteristics To allow the distinction between solid, non-aqueous, and aqueous phases, two uorescent dyes are needed which are each soluble in only one liquid phase. Also they should have a high absorption at 488 nm and a signicantly different Stokes shift, i.e., different emission spectra to permit a clear separation of the two liquid phases. For the

Solid

Refractive index n

dn/dT (C)1) 0.1210)4 )1.0510)4

Density p (g/cm3) 2.2 1.19

Water/air contact angle (Adamson 1999) %0 59.3

Mean diameter d (mm) 0.8 0.6

Fused silica 1.46 Plexiglass 1.49

Table 2. Pure liquid properties

Liquid DC 200 DC 550 DC 556 DC 710 Water

Refractive index n 1.375 1.4935 1.46 1.533 1.333

dn/dT (C)1) ) )3.9710)4 ) ) )0.9910)4

Density p (g/cm3) 0.761 1.068 0.98 1.11 0.997

Viscosity v (mm2/s) 0.65 125 22.5 500 0.893

Surface tension r (mN/m) 15.9 24.5 ) 28.5 72

Table 3. Properties of index matched liquids and corresponding dyes

Liquid

Refractive index n

Density p (g/cm3) 1.05 0.97 1.70

Viscosity v (mm2/s) 95 21 4

Molecular diffusivity Dm (mm2/s) 510)5 (Nile red) 210)4 (Nile red) 210)5 (Alexa Fluor 488)

Schmidt number Sc=v/Dm 2106 (Nile red) 9104 (Nile red) 2105 (Alexa Fluor 488)

84 wt% DC 1.49 550+16 wt% DC 556 98 wt% DC 1.46 556+2 wt% DC 200 58 wt% ZnCl2 solution 1.46

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aqueous phase, the uorescein substitute Alexa Fluor 488 (Molecular Probes) was used, which exhibits high absorbance and quantum yields as well as low sensitivity to pH, which makes it applicable in zinc chloride solutions. For the silicone oils, the phenoxazine dye Nile Red was employed. In Fig. 4, the absorption and emission spectra of these dyes given in Haugland (2001) are plotted, together with the laser excitation wavelength and the transmittance curves of the optical bandpass lters (55020 nm and 60020 nm). The lters were chosen to be each selective to one dye and to admit of optimal signalto-noise ratio and spatial accuracy (see Sect. 5). As noted in Haugland (2001), the emission spectrum of Nile Red

shown in Fig. 4b undergoes blue shifts in nonpolar environments. This explains why the maximum uorescence in the present case was found to be around 600 nm. Figure 4 also shows that the emission spectrum of Alexa Fluor 488 and the absorption spectrum of Nile Red overlap. This will increase the uorescence intensity of a Nile Red solution in the vicinity of a uorescent Alexa Fluor 488 solution (see Sect. 7). For the index-matched liquids, the coefcients of molecular diffusion Dm and Schmidt numbers Sc were estimated from the dispersion of the dyes in the porous medium with the uid at rest D0 and a tortuosity factor s, taking into account the increased pathlength due to pore geometry: D0 D m s : 1

The obtained values for Dm and Sc are given in Table 3.

5 Method for precise index matching The spatial precision of the measured data is mainly determined by the amount of refraction caused by mismatched refractive indices of solid and liquid(s). Due to the differences in optical dispersion of each phase (see Fig. 3), the refractive indices can be matched at only one wavelength. Light with a different wavelength is refracted at the solidliquid interfaces, with the angle of refraction growing with distance from the matching wavelength. The qualitative behavior of a white light beam passing through a porous medium is illustrated in Fig. 5. The refractive indices are matched for green light. The multiplied effect of a single sphere sketched in Fig. 5a leads to a wavelength dependent broadening of a light beam in porous media. In Fig. 5b, the qualitative behavior of a white light beam passing through a porous medium is outlined. A photograph of a porous medium consisting of Plexiglass and silicone oil, matched at 550 nm, taken with this conguration is shown in Fig. 5c. The broadening of the red and blue portion of the light beam is obvious. As described in Sect. 2, an optical bandpass lter is used to screen the refracted parts of the spectrum and constrict imaging to a small area around the matched wavelength. Because the lter reduces the recorded light intensity, the choice of the lter bandwidth is a compromise between spatial accuracy and signal-to-noise ratio. To obtain the optimal spatial accuracy, a method has to be found to match the refractive indices at the center wavelength of the bandpass lter. Therefore an HP 8453 spectrophotometer was used as shown in Fig. 6. As the broadening of the light beam increases, the screening Fig. 4. Normalized absorption and emission spectra of Alexa Fluor 488 and Nile Red (from Haugland 2001) and transmittance effect of the slit leads to a decrease in light intensity on the photodiode array. Thus, the phenomena described above curves of optical bandpass lters

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Fig. 5. Qualitative behavior of a white light beam passing through a a sphere and b a porous medium. The refractive indices of the medium are matched at 550 nm. The photograph c is recorded with the setup in b

Fig. 7. Transmittance curves obtained for a porous medium matched at 550 nm and a bandpass lter with center wavelength 550 nm

behaves as an optical bandpass lter has been noted in the literature for over a hundred years under the name christiansen lter (Hense 1987). For the present application, this offers the possibility of easily matching the refractive indices with an accuracy of 1 nm. This corresponds to a difference in the refractive index of the liquid phase of about 510)5. Due to the different dn/dT of the liquids (Table 2) and solids (Table 1), changes in temperature during the experiment must be avoided. Therefore the refractive index matching was done directly before the experiments, with all components of the ow Fig. 6. Optical system of the HP 8453 spectrophotometer used cell being in equilibrium at room temperature (T%25C). for the determination of the matched wavelength Although no temperature control was performed, no signicant changes in the transmittance curve were found and shown in Fig. 5 result in transmittance curves with a after the experiments. maximum at the matched wavelength. As an example, the curve for a porous medium consisting of Plexiglass and 6 silicone oil is shown in Fig. 7 together with the curve for Image data preprocessing the corresponding optical lter. The fact that a transparent For the accuracy of subsequent quantitative evaluations solid powder immersed in an index-matched liquid of ow parameters, it is necessary to perform a radio-

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metric calibration, i.e., a correction of the image data for non-uniform illumination, and a geometric calibration to nd the relation between image coordinates and real world positions. Finally, the concentration time series at every voxel were corrected for the scanning time shift. For the radiometric calibration, advantage was taken of the fact that sources of scattered light inside the medium, e.g,. air bubbles, can never be completely avoided. Under the assumption that they are uniformly distributed, the amount of scattered light gives an approximation of the local illumination s(x,y,z). Therefore, the optical lter, which is used to screen the scattered light in the actual experiment, was removed beforehand, and a 3D image was taken. Then the parameters a1a9 of a quadratic model for each coordinate, Fig. 8. Isosurface plot of the dye concentrations after 20, 195, sx; y; z a1 x2 a2 x a3 a4 y2 a5 y a6 and 370 min 2 a7 z2 a8 z a9 were obtained by a least squares method. Because it is not practicable to insert a calibration target into the porous medium, the geometric calibration was also done using the scattered light image. Since the domain containing the porous medium is surrounded by Plexiglass and pure liquid areas where no scattering occurs, the signicant decrease in scattered light was used to detect the borders of this domain in x and y direction for every 2D image. Due to the increase in optical path length, these borders diverged with increasing z. The individual images were therefore stretched so that the borders coincided again. The z coordinates of the 2D images are given by the positions of the translation stage. For further evaluation, it is desirable that all data of a volume scan are related to the same time. Since the volume slices are recorded subsequently, as described in Sect. 2, the measurement time t(z) grows linearly with z: z t z t 0 3 vscan with the scanning velocity vscan=4 cm/14 s%0.29 cm/s. In order to relate all measurements to the same time t(0), the time series at each voxel were appropriately smoothed for z noise reduction and then shifted by Dt vscan using cubic smoothing splines (Green and Silverman 1994).

7 Results In the rst experiment, the technique was used to measure the transport of a uorescent tracer dye in a medium composed of silicone oil and Plexiglass (see Sect. 3). A small pulse of silicone oil with dissolved Nile Red was injected into the horizontal ow cell and a constant ow with a mean velocity in the liquid phase of 0.0017 mm/s was applied. The dye concentration was chosen to be low enough to minimize the variation in light intensity inside the cell caused by absorption but high enough to get an adequate signal-to-noise ratio. Since no absolute concentration values are measured, the image data g(x,y,z) are scaled to 0 g 1. Figure 8 shows the superimposed concentration distributions after 20, 195, and 370 min, corresponding to displacements of 2, 20, and 38 mm referring to the center of the plume, plotted as the halfmaximum iso-concentration surfaces. The effect of hydrodynamic dispersion, i.e., the temporally increasing variance of the concentration distribution is illustrated by the according x distributions  and their  mean values " hxi and variances r2 x " x x2 shown in Fig. 9. Figure 10 shows a volume subset of 25025050 voxels (181820 mm3) of the same experiment with the tracer dye concentration after a displacement of 31 mm. The second experiment was performed to visualize the displacement of oil by water. At the beginning, the vertical

Fig. 9. X distributions of the dye concentrations added up over the YZ plane after 20, 195, and 370 min. The mean values x and variances r2 are estimated from the least squares ts of a Gaussian distribution

Fig. 10. Tracer dye concentration inside a volume of

181820 mm3

ow cell was completely lled with fused silica and silicone oil. Then a zinc chloride solution, which has a much higher density than the silicone oil (see Table 3), was injected from the bottom with a mean velocity in the liquid phase of 0.0023 mm/s. Both the oil and aqueous phase were uniformly dyed with Nile Red and Alexa Fluor 488 respectively. For this experiment, the respective liquid phase saturations not the dye concentrations (which remained constant in each liquid for all times) were of interest, i.e., the assignment of the voxels to the solid, oil, or water phase. Figure 11 shows volume subsets (25025050 voxels =181820 mm3) of six volume data sets recorded successively with the two optical bandpass lters at three different times with the image data scaled to 0 g 1. Due to the uniform dye concentrations in each uid, the image data represent the volumetric contents of the oil (Fig. 11a, c,

165

Fig. 11. Volume subsets (181820 mm3) of a two-phase displace-

ment experiment recorded with lters 60020 nm for the oil phase (a, c, e) and 55020 nm for the water phase (b, d, f) at three different times with the image data scaled to 0 g 1 (see colorbar of gure 10) as an indication for the respective phase saturation

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e) and aqueous phase (Fig. 11b, d, f). In Fig. 11b, d and f, the separation between the lower region, where the aqueous phase has nearly completely displaced the oil, and the upper region, which is still completely lled with oil, is visible. Figure 11a, c and e rst shows the residual oil saturation, which consists of little disconnected "blobs" that have been trapped during the inow of the aqueous solution in the lower regions. Secondly, the parts of the oil-lled upper regions which adjoin water-lled areas are visible, whereas the oil at the top of the volume is only weakly uorescing. This is an effect of the overlapping absorption and emission spectra of the two dyes, as mentioned in Sect. 4. Since we are not interested in measuring dye concentrations, this does not interfere with further evaluations.

References
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8 Summary and conclusions We presented a PLIF method for the 3D measurement of ow and transport at the pore scale of porous media. Through the employment of appropriate solids, liquids, and uorescent dyes, this method is the rst high-resolution matching-index technique to visualize the ow of two immiscible liquids at the same time. The very high spatial and temporal resolution could be accomplished by the use of high-performance imaging hardware in combination with a method for highly precise refractive index matching of solid and liquids. This method, which has already been used for a long time in materials science for the characterization of the homogeneity of glass, was successfully adapted for the present application. The results exhibited demonstrate the methods applicability to studying ow and transport on multiple scales simultaneously. It provides the opportunity to vary ow parameters such as Peclet number or phase saturation and to construct heterogeneities in order to examine their inuence on microscopic ow and on the parameters of upscaled macroscopic ow models such as dispersion tensor and hydraulic conductivity.