Influence of Pore Structure on SIP Properties Deduced from Micro-scale Modelling

J. Volkmann, N. Klitzsch, E. Wiens and O. Mohnke

Applied Geophysics and Geothermal Energy, E.ON Energy Research Center, RWTH-Aachen

Introduction Model Properties System of Equations

The frequency dependent electrical impedance of porous media We model a three-dimensional system of alternating smaller and The governing equations for charge transport in pore space are ac-
and the corresponding geophysical method, Spectral Induced Po- larger pores filled with electrolyte, apply a sinusoidal voltage and cording to Marshall and Madden (1959) the continuity equations for
larization (SIP), are studied by modelling the charge transport in determine the current through the system in order to find its complex the concentrations of cations Cp and anions Cn (eq. 1,2) and Pois-
the electrolyte filled pore space and by corresponding laboratory resistivity at different frequencies. We use a reduced cation mobility son’s equation for the electric potential U (eq. 3). A time harmonic
experiments. inside the electrical double layer to account for the interaction of approach leads to frequency dependent equations for the complex
In the last two decades many empirical relations were proposed, these ions with the charged inner rock surface. The thickness of the amplitudes of the excess concentrations cp , cn and the potential u
which relate the frequency dependent electrical properties of water layer with reduced cation mobility is given by the Debye length and (eq. 7-9). They are valid for monovalent ions with equal equilibrium
saturated rocks to structural properties such as pore radius, and in- thus depends on the concentration of ions. concentrations C = cp0 = cn0 (e.g. NaCl solution).
ner surface area, or to hydraulic conductivity (Börner et al., 1996; . ∂ Cp = cp0 + cp ei𝜔t (4)
Binley et al., 2005). Unfortunately, these relations are not universal; Cp = Dp ΔCp + ∇ (𝜇p Cp ∇U) (1)
∂t
they apply only for specific rock types and water compositions. In ∂
Cn = Dn ΔCn − ∇ (𝜇n Cn ∇U) (2) and Cn = cn0 + cn ei𝜔t (5)
order to quantify the influence of inner rock structure (as well as of ∂t
electrochemical water and rock properties) on the frequency depen- F
ΔU = (Cn − Cp ) (3) U = uei𝜔t (6)
dent electrical properties, we model the charge transport processes 𝜀
at the pore space in the frequency range f = 10−3 Hz − 108 Hz.
We carried out corresponding experiments at samples with different
pore radius distributions and different conductivities of the pore wa-
( )
Figure 3: Simple axial i𝜔cp = Dp Δcp + ∇ 𝜇p cp0∇u (7)
ter. 2-point and 4-point measurement arrangements were used to symmetric model of a pore
cover the frequency range from 1 mHz to 10 MHz. system; colors indicate excess
concentrations
i𝜔cn = Dn Δcn − ∇ (𝜇n cn0∇u) (8)

Laboratory Experiments F( )
Figure 4: Section of the pore system Δu = cn − cp (9)
𝜀
We measured complex resistivity spectra for four samples P0,
√
▶ EDL region: thickness 𝜆D = 𝜀kT
P2, P4 and P5 characterised by different grain sizes (Figure 1). 2e2C
▶ EDL region: ion mobilities 𝜇p < 𝜇n 𝜇(p/n)kT
2-point measurements are made with respect to the ’high’ frequeny The Einstein relation D(p/n) = relates the diffusion coeffi-
▶ Free electrolyte: ion mobilities 𝜇n = 𝜇p e
range f > 104 Hz. The 4-point measurement arrangement allows cients D(p/n) and the mobilities 𝜇(p/n) of the different ions.
the characterisation of the ’low’ frequency range f < 104 Hz by
avoiding contact impedance effects. While the pore structure varies Resulting Spectra
Notation: Faraday’s constant F, temperature T, elementary charge
due to the use of the different samples the effect of the electrolyte e, Boltzmann’s constant k and permittivity 𝜀.
The resulting spectra show two different characteristic minima in the
concentration is studied by changing the pore fluid.
frequency range 10−3 Hz − 108 Hz. The effects of the fluid permit-
. Verification of the Modelling Approach
tivity are neglegted. We distinguish between the low (< 104 Hz)
.
and high frequency (> 104 Hz) region and study the influencing pa-
To verifiy our modelling concept, we compare the results of a one-
rameters on the amplitude 𝜙min and the position fmin of the phase
dimensional pore system - a sequence of active and passive zones -
minima.
to
1 the analytical solution according to Marshall and Madden (1959).
3D model and experimental results:
1D model results:
0 0

−10
φρ /mrad

−20
L =1µm,L =1µm
1 2
−20 −500 −30
analytical solution
−40

φ / mrad
L =1.5µm,L =0.5µm
1 2
−50 analytical solution
L1=0.5µm,L2=1.5µm

ρ
−60
analytical solution
−70
−40 −1000
−2 0 2 4 6 8
log(f/Hz) −80
Figure 1: Computer tomography −90
pictures of the four rock samples Figure 2: Experimental setup for 2-point Figure 6: Experimental results: 2-point
Figure 5: Modelling result for pore −100

P0, P2, P4 and P5 used for SIP and 4-point measurements −3 −2 −1 0 1 2 3 4 5 6

lengths L1 = 10−5 m, L2 = 10−8 m, measurement at sample P0, fluid log(f)

measurements pore radii R1 = 1,4 ⋅ 10−7 m, conductivity 𝜎w = 12𝜇S/cm (green);

Figure 7: 1D Marshall-Madden model; simulated results and analytical solution
R2 = 1,4 ⋅ 10−8 m and concentration 4-point measurement at Oberkirchner
C = 1 mol m−3 sandstone (red)

Results for the phase minimum at f < 104 Hz Results for the phase minimum at f > 104 Hz

For high differences of the large and small pores a phase minimum at frequencies f < 104 Hz We obtain a second characteristic phase minimum in the frequency range 104 Hz − 108 Hz, caused by
can be found. While the dependence of the phase amplitude is not in agreement with the SNP or charge accumulation at the interface between regions with different electrical properties. Since we use
1D Marshall-Madden model (Figure 8), it is in agreement with these theories with respect to the the ion mobilities as the only decisive parameter, we present preliminary results in this section. For a
behaviour of the characteristic frequency (Figure 9). The difference in the absolute values of fmin is complete model in this frequency range the different permittivities in the free electrolyte and the EDL
an effect of the pore geometry (see Figure 11). Although the amplitudes do not agree with current would have to be considered as well as the permittivity of the sorrounding rocks. Nevertheless even
and classical theories, the simulation shows qualitative agreement with experiments (Figure 10). for this simple model we obtain spectra which confirm the concept of small pore throats responsible
The influence of pore geometry is associated with the length of the larger pores Llarge (Figure 11). for noticable phase values (Figures 16 and 17). The position of the minimal phase shift and the con-
The nearly quadratic dependence on geometric pore properties is known from experiments (Figure 12). centration dependence are in agreement with the classical Maxwell-Wagner theory (Maxwell, 1873;
Wagner, 1914) and experiments (Figure 15). Our simple model − although in this case in agreement
Influence of Concentration: with Maxwell-Wagner theory − does not predict any influence of pore geometry on relaxation times we
. see in experiments (Figure 15).
1 for model results r No influence of concentration
.∣𝜙min∣ ∼ C
∣𝜙 ∣ ∼ 1 for model results
model results on fmin min C Influence of Concentration:
0 6
.
.∣𝜙min∣ ∼ √1 for all models fmin ∼ C for all models
−5 5 C
φmin / mrad

/Hz)

−10 4
0 8.5
min

Simulation
SNP model
log(f

−15 8
|φ | ∼ C−1 Marshall−Madden model 3 −20
min

−20 7.5
log(fmin/Hz)

Simulation
/ mrad

2 −40
Maxwell model
7
−25 Maxwell−Wagner model
−1 −0.5 0 0.5 1 1.5 2 1 −60 f ∼C
−1 −0.5 0 0.5 1 1.5 2 6.5 min
min

−3
log(C/mol⋅m ) −3
|∼C
−1/2
log(C/mol⋅m ) −80 |φ
φ

min
6
Figure 8: Dependence of the minimal Figure 9: Dependence of the Figure 10: Experimental results (absolute −100 5.5
phase shift on electrolyte frequency of the minimum on values); Data from Breede and Weller −120 5
−1 −0.5 0 0.5 1 1.5 2 −1 −0.5 0 0.5 1 1.5 2
concentration electrolyte concentration (2006) log(C/mol⋅m ) −3
log(C/mol⋅m ) −3

Influence of Pore Size: Figure 13: Dependence of the minimal Figure 14: Dependence of the
. phase shift on the concentration frequency of the minimum on the Figure 15: Experimental results for the
−1,7 −1,8 concentration different samples; relaxation time
. fmin ∼ L1 and fmin ∼ L1 𝜏 ∼ 1/fmin , resistivity 𝜌 ∼ 1/C; pore radii
for model results decrease from P0 to P5
6 Influence of Pore Size:
5 .
. ∣𝜙min∣ → 0 for Rlarge → Rsmall ∣𝜙min∣ → 0 for Rsmall → Rsmall
)/Hz)

Rlarge > 10−6 m → saturation

−3

Rlarge > 10−6 m → saturation

Simulation (C=0.1 mol m )
min

3 Simulation (C=1 mol m−3)

log(f

SNP model
2 Marshall−Madden model

0 0
1
−50
0
−6 −5.5 −5 −4.5 −10
/ mrad

log(Llarge/m) −100
/ mrad

Simulation
−20 Maxwell model −150
Figure 11: Dependence of fmin on the Maxwell−Wagner model
min
min

−200
larger pore length Llarge ; crosses:
φ
φ

−30
C = 1 mol m−3, points: C = 0,1 mol m−3 Figure 12: Experimental Results for the
−250

dependence of the relaxation time −40

−7 −6.5 −6 −5.5 −5
−300
−8 −7.5 −7 −6.5 −6
log(Rlarge/m) log(R /m)
𝜏 ∼ 1/fmin on the dominant pore throat small

diameter; Data from Kruschwitz (2007) Figure 17: Dependence of the minimal
Figure 16: Dependence of the minimal
phase shift on the larger pore radius phase shift on the smaller pore radius
Rlarge Rsmall
Conclusion and Outlook
We developed a simple three-dimensional pore system model which produces phase spectra in quali- References
tative agreement with experimental results, partially confirmed by classical theories, partially extending Binley, A., Slater, L.D., Fukes, M. and Cassiani, G. 2005. Relationship between spectral induced polarization and hydraulic properties of saturated and unsaturated sandstone. Water Resources Research 41, W12417.
Doi:10.1029/2005WR004202.
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Börner, F.D., Schopper, J.R. and Weller, A. 1996. Evaluation of transport and storage properties an the soil and groundwater zone from induced polarization measurements. Geophysical Prospecting 44: 583–601.
In the future more realistic geometries will be modelled, based on CT or SEM pictures. Furthermore, Kruschwitz, S. 2007. Assessment of the complex resistivity behavior of salt affected building materials. Dissertation, Fakultät VI - Planen Bauen Umwelt der Technischen Universität Berlin.
Marshall, D.J. and Madden, T.K. 1959. Induced polarization, a study of its causes. Geophysics 24 (4): 790–816.
we aim at the up-scaling from pore scale to sample scale, using network models or Lattice Boltzmann Maxwell, J.C. 1873. A Treatise on Electricity and Magnetism, Volume I. Clarendon Press. Oxford.

methods in order to deduce an interpretation sheme for broadband SIP measurements. Wagner, K.W. 1914. Erklärung der dielektrischen Nachwirkunsvorgänge auf Grund Maxwellscher Vorstellungen. Archiv für Elektrotechnik 2 (9): 371–387.

Institute of Applied Geophysics and Geothermal Energy – E.ON Energy Research Center – RWTH Aachen University – Aachen, Germany Mail: j.volkmann@geophysik.rwth-aachen.de Web: http://www.geophysik.rwth-aachen.de/