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Comparison of fractal dimensions from nitrogen

adsorption data in shale via different models
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Cite this: RSC Adv., 2021, 11, 2298

Kouqi Liu, *a Mehdi Ostadhassan,*b Ho Won Jang, *c Natalia V. Zakharova a

and Mohammadreza Shokouhimehr *c

The roughness of pore surfaces in shale reservoirs can affect the fluid flow, which makes it necessary to be
characterized. Fractal dimension, a key component in fractal geometry, can be used to describe the surface
irregularities. In this paper, we evaluated and compared the fractal dimensions of several shale samples with
three major fractal models based on nitrogen adsorption isotherms. The results showed that Frenkel–
Halsey–Hill (FHH), Neimark, and Wang–Li models all can be applied for fractal dimension
characterization of shale samples. From theoretical thermodynamics, these three models should be
considered identical based on the FHH equation. However, the experimental data obtained from these
samples showed that the fractal dimensions that are derived from the Neimark model and Wang–Li
model are the same while a discrepancy was observed with the results from the FHH model. The
difference in the fractal dimensions in the experimental data among these three models was attributed
Received 23rd October 2020
Accepted 8th December 2020
to the micropore structures. It was found that as the micropore surface area or the micropore volume
increases in the samples, the difference in the fractal dimensions would increase as well. If the number
DOI: 10.1039/d0ra09052b
of micropores present in the samples is limited, all three models can become suitable for fractal
rsc.li/rsc-advances dimension calculation in shale samples, otherwise, the Neimark or Wang–Li model is preferred.

geometries that can overcome the limitations of traditional

1. Introduction methods. Avnir et al. (1984) found that at the molecular level,
Unconventional reservoir resources now play an important role the surface of most materials reects a fractal behavior with
in total energy consumption.1,2 For the unconventional reser- fractal dimension varying from 2 to 3, where 2 means a perfectly
voirs with low porosity and permeability, the surface roughness smooth surface and 3, signicantly rough and a disordered
of the pores in a porous media would impact uid ow and heat surface.6
transfer.3 During oil production in two-phase ow in the The fractal dimension of a solid surface can be determined
subsurface, the roughness of the pore surface can affect the with a variety of techniques such as porosimetry,7 electro-
phase distribution of ow regimes and lead to variations in chemical methods,8 small angle scattering,9 and adsorption
phase relative permeability.4 Knowing the surface roughness of isotherms.5 With some assumptions, adsorption isotherms
the pores can assist in understanding oil/gas ow which have been employed for the surface roughness characterization
requires characterization of pore surface precisely. Traditional in different materials such as carbon blacks,10 carbon bers,11
techniques to evaluate surface roughness are based on the and aerosol particles.12 Up to date, various fractal models based
concept of isolated deviations from a planar surface area. on the adsorption isotherms have been proposed and applied to
However, this method has the difficulty of identifying a small analyze the fractal dimension of the solid surface such as the
number of structural parameters that can describe the rough- fractal version of Frenkel–Halsey–Hill (FHH) model which is
ness for a variety of purposes that can accurately reect the pore based on the classical FHH theory,5,13 the thermodynamic
surface.5 Fractal dimensionality proposed by Avnir et al. (1984) model which was developed by Neimark14 and the Wang–Li
is an excellent method to characterize the complex surface model.15
Nitrogen adsorption nowadays has become a standard
technique for pore structure analysis in shale characteriza-
a
Department of Earth and Atmospheric Sciences, Central Michigan University, Mount
tion.16–21 In addition to its applicability for pore size distribu-
Pleasant, MI, 48859, USA. E-mail: [email protected]
b
tion, pore surface area and pore volume determination,
Key Laboratory of Continental Shale Hydrocarbon Accumulation and Efficient
Development, Ministry of Education, Northeast Petroleum University, Daqing, researchers have combined fractal dimension analysis with
163318, China. E-mail: [email protected] adsorption isotherms to obtain more information from the
c
Department of Materials Science and Engineering, Research Institute of Advanced pores.22–26 Based on the literature, nearly all the authors utilized
Materials, Seoul National University, Seoul 08826, Republic of Korea. E-mail: the FHH model solely to characterize fractal dimensions of
[email protected]; [email protected]

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shale rocks without any strong basis. Thus, to date, the dimension DN can be calculated through the following
following questions have remained unanswered: is the FHH equation:14
model the most suitable one for fractal dimension analysis of
shale rocks? If not, which model would provide us with more ln S(r) ¼ k
(DN
2) ln r (5)
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accurate understanding of this complicated rock pore

structures? where k is a constant and S can be derived from the Kiselev
This study attempts to answer the above questions. In order equation as follows:
ð Ns ð
to do so, 19 shale samples from the Bakken Formation have RT Ns
S¼
mdN ¼ ð
lnðX ÞÞdN (6)
been collected and gas adsorption data has been acquired from NðX Þ s NðX Þ
these samples. In the next step, several mainstream fractal
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models were employed to analyze the adsorption isotherms. and r, the average radius of curvature of the meniscus at the
Based on the comparison of the results, some suggestions have interface between condensed adsorbate and gas, increases as
been made to select the best fractal model for analyzing the the relative pressure X increases following Kelvin's equation:
pore structure of shale samples in the future. 2sVL
r¼
(7)
RT ln X

2. Basic fractal theory of the gas where s, R, T, VL are the surface tension, universal gas constant,
the temperature, and the molar liquid adsorbate, respectively.
adsorption Ns is the adsorption quantity as the relative pressure X tends to
2.1. FHH fractal theory become 1.
In order to apply the classical Frenkel–Halsey–Hill (FHH) theory
on fractal materials, Pfeifer et al. (1989, 1984)5,13 assumed the 2.3. Wang–Li fractal theory
lm of the uid that is absorbed on the sample surface could be Considering the correlation between the area of the fractal
regarded as a number of spheres with radius z representing surface and the volume circumscribed by the surface that is
a monolayer. Thus, the volume of this absorbing lm is equal to proposed by Mandelbrot (1982),28 Wang and Li calculated the
the number n(z) of spheres multiplied by the sphere volume fractal dimension based on the following equation:15
(zz3). Therefore, the fractal dimension can be dened by
assuming that n(z) is proportional to z
D. Then the amount of S(r) ¼ k0DWLr2
DWLVDWL/3 (8)
uid that is adsorbed as a function of the lm thickness z on
a fractal surface is given by: where k0 is the factor relating surface area with the corre-
sponding volume. Thus, by assuming that the liquid cannot be
N f z3
D (1) compressed, V can be calculated as:

where D is the fractal dimension, and z is the radius. Based on V ¼ [Ns
N(X)]VL (9)
the condensation regime, the mean radius curvature of the
interface is: Combining eqn (5) and (7)–(9), the following expression can
be obtained:
z f [
ln X]
1 (2)
ln A(X) ¼ l + DWL ln B(X) (10)
where X ¼ P/P0, the relative pressure, P is the equilibrium
pressure on the sample while P0 is the saturation pressure of where l is a constant, A(X) and B(X) can be described as:
nitrogen at 77 K. Substituting eqn (2) into eqn (1), one obtains Ð Ns

NðX Þ
lnðX ÞdNðX Þ ½NS
NðX Þ1=3
the expression of the fractal surface prediction in the capillary AðX Þ ¼ ; BðX Þ ¼ (11)
r2 ðX Þ rðX Þ
condensation regime in a log–log format:27

ln N ¼ a + (D
3) ln(
ln X) (3)
3. Materials and methods
where a is a constant value. 19 shale aliquots were collected from the Bakken Formation
from the cores that are retrieved from several wells drilled in the
2.2. Neimark fractal theory Williston Basin, ND. These shale samples are mainly composed
Neimark took a thermodynamic approach to determine the of quartz and clay minerals. All samples were crushed into
surface fractal dimension of a porous solid (DN) which can be powders with grain size less than 250 mm (60 mesh). Data from
expressed by:28 samples #17, #18, and #19 were analyzed previously and pre-
sented in the study by Liu et al. (2017)26 and some of the other
S(r)  r2
DN (4) samples are studied by Abarghani et al. (2020) who focused
more on the organic chemistry.29 Prior to the adsorption
where S(r) is the surface area and r is the length of the yardstick measurements, all powders were degassed for 8 hours at 110  C
which is used to measure the surface area.14 Then the fractal to remove moisture and volatiles that may exist in the sample

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Fig. 1 Gas adsorption isotherms of all the shale samples.

pores. Low-pressure nitrogen adsorption experiment was per- size distribution (PSD) while micropore volume and micropore
formed on a Micromeritics® Tristar II apparatus at 77 K. The surface area can be quantied using the Barrett–Joyner–
gas adsorption quantity was monitored and recorded as the Halenda (BJH) model.30
relative pressure increases from 0.01 to 1. The outcome will
provide us with the pore structure information such as the pore
Table 1 Summary of the fractal dimensions of the shale samples using
FHH theory

Samples DFHH P/P0 range scale R2

#1 2.519 0.085–0.961 0.997

#2 2.506 0.084–0.956 0.999
#3 2.529 0.056–0.953 0.998
#4 2.519 0.053–0.990 0.995
#5 2.491 0.092–0.959 0.998
#6 2.503 0.055–0.990 0.999
#7 2.506 0.055–0.959 0.998
#8 2.507 0.050–0.956 0.996
#9 2.506 0.084–0.957 0.996
#10 2.487 0.050–0.954 0.998
#11 2.534 0.055–0.991 0.996
#12 2.528 0.080–0.958 0.996
#13 2.498 0.048–0.958 0.995
#14 2.499 0.094–0.956 0.997
#15 2.565 0.084–0.959 0.992
#16 2.495 0.053–0.956 0.999
#17 2.435 0.113–0.883 0.984
#18 2.454 0.112–0.884 0.981
#19 2.522 0.071–0.935 0.990
Fig. 2 The FHH fractal analysis of sample #1 (adsorption branch).

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Fig. 3 The Neimark fractal analysis of sample #1 (adsorption branch).

Fig. 4 The Wang–Li fractal analysis of sample #1 (adsorption branch).

4. Results existence of mesopores. Based on the recommendations by the

4.1. Nitrogen adsorption isotherms International Union of Pure and Applied Chemistry,31 the shape
of these hysteresis loops show the major pores in these samples
Gas adsorption isotherms of all shale samples can be seen in
are slit shaped. The difference between the gas adsorption
Fig. 1. At extremely low relative pressures, the amount of
quantities at the same relative pressure of these samples
adsorbed gas will depend on the micro-pore volume. As the
explains that these samples have different pore structures, such
relative pressure increases, multilayer adsorption will be
as pore volume and pore surface area.
formed. Hence, the knee-bend shape of the adsorption
isotherms in the gure can indicate the transition from the
monolayer adsorption to the onset of the poly-molecular 4.2. FHH fractal model
adsorption. At the higher relative pressure, the gas in the The adsorption branch of the isotherms in these samples was
mesopores and macropores starts to condense. During the used for fractal dimension analysis. Fig. 2 displays the FHH
desorption stage, as the relative pressure decreases, the quan- fractal analysis of sample #1 as a representative of all samples.
tity of the gas adsorbed will decrease. Therefore, the desorption In a certain P/P0 range (0.0085–0.961) (mainly the poly-
curve will coincide with the adsorption curve which is caused by molecular adsorption region), linear correlations exist
the “tensile strength effect”, creating hysteresis loops. The between ln(
ln X) and ln N which demonstrate that eqn (3) can
hysteresis loops that is observed in all isotherms indicate the be applied for fractal dimension calculations and analysis.
Table 1 summarizes fractal dimensions of all samples with

Table 2 Summary of the fractal dimensions of the shale samples using Table 3Summary of the fractal dimensions of the shale samples using
Neimark fractal theory Wang–Li fractal theory

Samples DN P/P0 range scale R2 Samples DWL P/P0 range scale R2

#1 2.702 0.010–0.961 0.994 #1 2.569 0.010–0.961 1.000

#2 2.631 0.010–0.956 0.997 #2 2.517 0.010–0.956 1.000
#3 2.619 0.010–0.953 0.996 #3 2.528 0.010–0.953 1.000
#4 2.498 0.010–0.953 0.989 #4 2.392 0.010–0.958 0.999
#5 2.696 0.010–0.959 0.993 #5 2.540 0.010–0.959 1.000
#6 2.495 0.055–0.959 0.991 #6 2.408 0.010–0.959 0.999
#7 2.680 0.010–0.991 0.995 #7 2.556 0.010–0.959 1.000
#8 2.702 0.010–0.956 0.995 #8 2.564 0.010–0.959 1.000
#9 2.718 0.010–0.957 0.994 #9 2.589 0.010–0.957 1.000
#10 2.743 0.053–0.921 0.993 #10 2.627 0.010–0.954 1.000
#11 2.591 0.010–0.959 0.996 #11 2.473 0.010–0.959 1.000
#12 2.742 0.010–0.958 0.993 #12 2.596 0.010–0.958 1.000
#13 2.747 0.011–0.958 0.990 #13 2.586 0.011–0.958 1.000
#14 2.687 0.010–0.956 0.995 #14 2.549 0.010–0.956 1.000
#15 2.804 0.010–0.959 0.992 #15 2.666 0.010–0.959 1.000
#16 2.539 0.010–0.956 0.994 #16 2.425 0.010–0.956 1.000
#17 2.866 0.011–0.832 0.988 #17 2.782 0.011–0.883 0.999
#18 2.898 0.010–0.883 0.994 #18 2.820 0.010–0.883 0.998
#19 2.882 0.011–0.884 0.986 #19 2.866 0.011–0.934 0.995

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0.961, linear correlations could exist between ln S and ln r,

indicating the suitability of the application of the Neimark
fractal model in the calculation of fractal dimension of the
samples. The Neimark fractal dimensions DN of all samples can
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be seen in Table 2. All fractal dimensions are also measured in

the reasonable interval (2–3) based on previous studies and
recommendation.4 The P/P0 range which can be utilized in
Neimark theory is very similar as the P/P0 range in the FHH
model. From Table 2, sample #18 was calculated with the largest
fractal value while sample # 6 had the smallest fractal dimen-
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sion value.

4.4. Wang–Li model

Fig. 4 shows the fractal analysis results of representative sample
#1 based on the Wang–Li fractal model. If the relative pressure
ranges from 0.010 to 0.961, linear correlations can be estab-
lished between the ln A(X) and ln B(X). The fractal dimension
values of all samples from this model also are found between 2
and 3 (Table 3), indicating that Wang–Li fractal model can also
be applied in the fractal dimension calculation of our shale
samples. Sample #4 and sample #6 have very close fractal
Fig. 5 Comparison of the fractal dimensions of shale samples using dimension values and sample #17, #18, #19 have larger fractal
different models. dimension values compared with other samples, and these
ndings follow the results that are obtained by the Neimark
corresponding relative pressure intervals. The fractal dimen- model.
sion of all samples was calculated between 2 and 3, meaning
those values are in a reasonable data range (2–3) based on the
literature. Sample #15 has the largest DFHH values while sample
5. Discussions
#17 the smallest value. The P/P0 range of these samples based Considering Tables 1–3, it is concluded that the fractal
on the FHH analysis varies between 0.10–0.88, showing that dimensions of samples would vary based on the model that is
most measured data points in the experiment can be utilized for used. It can be seen that the FHH fractal dimension varies
the FHH fractal analysis (Table 1). between 2.435 (sample #17) to 2.565 (sample#15) which is
within a smaller range compared to the Neimark model (2.495–
2.898) and the Wang–Li model (2.392–2.866). Furthermore,
4.3. Neimark fractal model comparing all shale samples in this study, the fractal dimension
Neimark fractal model was employed to estimate the fractal values of the samples are close based on the Neimark model
dimension of shale samples in this study as well. Fig. 3 shows and Wang–Li model which were not the case in the FHH model.
the analysis result of sample #1 as a general representation. If Overall, the results show that it'd necessary to compare all
relative pressure value is measured between the 0.010 and mainstream fractal dimension performance in pore structure

Fig. 6 The DFHH and DN of all the testing shale samples.

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analysis and make an informed decision for future studies as or

which model is truly representing the samples nature.  3
DFHH
2 DFHH
3 RT
Fig. 5 is a simple correlation between the fractal dimensions S r ¼K ð2VL ÞDFHH
2 r
DFHH (16)
DFHH
2 s
of these three models. Linear correlations exist between the DN
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and DWL (Fig. 5a) with the slope of the curve close to unity. This
is an indication that fractal dimensions from Neimark and Through transforming eqn (15) and (16) into the double log
Wang–Li model for these shale samples are almost similar. format, the following is obtained:
However, it can be seen that there isn't any meaningful corre- "  3
DFHH #
DFHH
3 RT DFHH
2
lation between DFHH and DN (Fig. 5b). ln S ¼ ln K ð2VL Þ
The fundamental dependence of FHH model is on the pore DFHH
2 s
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volume of the absorbing lm and its relationship with the pore
ðDFHH
2Þ ln r
radius (eqn (3)) while Neimark method foster to relate the
¼ constant
ðDFHH
2Þ ln r (17)
surface area of the absorbing lm to the pore radius.32
Considering the Wang–Li model, the fundamental dependence or
of the theory is to correlate the pore volume of the absorbing
lm, pore surface area and the pore radius altogether. FHH
model operates based on eqn (2) while Neimark and Wang–Li
models are based on eqn (6) in a condensation regime. It should
be note that both equations are very similar in their
mathematical/physical format thus all the three models are
based on Kelvin's equation.
In the condensation regime, concerning eqn (3), the FHH
model can be written as:

N ¼ K[(ln(P0/P)]
(3
DFHH) (12)

The partial differentiation of eqn (12) can will become:

dN ¼ K(DFHH
3)[ln(P0/P)]DFHH
4d[ln(P0/P)] (13)

Substituting dN in eqn (13) into eqn (6) ends in the following

expression:
RT
S ¼ KðDFHH
3Þ ðDFHH
2Þ
1 ½lnðP0 =PÞDFHH
2 (14)
s

In the next step, substituting r in eqn (7) to replace ln(P0/P),

the following equation will be derived:
 3
DFHH
DFHH
3 RT
S¼K ð2VL ÞDFHH
2 rð2
DFHH Þ (15)
DFHH
2 s

Fig. 8 The correlations between the micropore structures and (DN

Fig. 7 The correlations between the surface area and (DN
DFHH). DFHH).

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"  3
DFHH #
  2 DFHH
3 RT as well, correlations between the BET surface area on the x-axis
DFHH
2
ln S r ¼ ln K ð2VL Þ and the difference between the DN and DFHH (DN
DFHH) on the
DFHH
2 s
y-axis is plotted in Fig. 7. For the most samples, as the BET
1
þ DFHH ln surface area increases, the difference between the DN and DFHH
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r increases except sample #10 (the red point in Fig. 7). Therefore,
1
¼ constant þ DFHH ln (18) it can be concluded that BET theory and its relationship with
r
various outcomes by different fractal models that is proposed by
Sahouli et al. (1996)10 cannot fully explain the factors that may
Eqn (17) is representing the curve in Fig. 5 while the format cause the difference in fractal dimensions or at least fully
of eqn (18) is similar to eqn (10). These ndings conrm that explain such discrepancy on geomaterials.
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from a theoretical point of view, the fractal dimension calcula- We further correlated the micropore structures (micropore
tion equations provided by the Neimark and Wang–Li can be volume and micropore surface area) and the DN
DFHH value
derived by combining the Kelvin equation and the FHH fractal which can be seen in Fig. 8. As the micropore surface area or the
model. FHH model can also be viewed as a model with ther- micropore volume increases in the samples, the value of DN

modynamics basis. From the thermodynamics viewpoint, these DFHH increases which ts the logarithmic law. This infers that
three models should be identical in the applicability of the FHH in the shale samples, micropore structures could be responsible
equation.33 for the difference in fractal dimensions from these two different
However, the discrepancy that is observed in the experi- models.
mental data from these shale samples from each model does
exist. In order to nd the answer to this important question, one
should reconsider factors that introduce the difference in the
6. Model selection
data between among these models. Since the results from DN Considering the shale samples in this study, fractal dimensions
and DWL are very close, it was decided to only compare DN and from Wang–Li and Neimark model found to be similar and
DFHH in this study. Fig. 6 illustrates the histogram of fractal different from the FHH model results. As a result, Neimark and
dimensions of from DN and DFHH of these shale samples. This FHH models are compared in this section for further verica-
gure explains that the DFHH and DN values from some of the tions. Based on the discussion earlier, both FHH and Neimark
samples are very close, for example, samples #4, #6, though the models are based on thermodynamics theories. Jaroniec et al.
DFHH and DN values of samples # 17, sample #18 are notably (1990)34 studied the gas adsorption behavior on fractal surfaces
different. in heterogeneous microporous solids from the thermody-
Sahouli et al. (1996)10 acquired FHH and Neimark model to namics viewpoint and concluded that microstructures could
study the fractal dimensions of commercial rubber grade affect the fractal dimensions outcome. The correlations
carbon blacks. They found that the BET surface area can be used between the DFHH, DN and the micropore surface area and
to explain the difference between the fractal dimensions that micropore volume can be seen in Fig. 9 and 10, respectively. It
are calculated from different models. They argued if the BET can be seen that there isn't any clear correlation between the
surface area is large, the difference between the fractal dimen- micropore surface area, micropore volume and DFHH (Fig. 9)
sions would become signicant. On the contrary, if the BET while positive relationships can be established between the
surface area is measured smaller, the fractal dimensions from micropore structures and DN (Fig. 10). Collectively, this means
these two methods will get closer to one another. In order to that the DN would not only reect the fractal dimension in the
verify whether this theory is applicable to geomaterial samples capillary condensation regime but also infers to the micropore

Fig. 9 The correlations between the micropore structures and DFHH.

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Fig. 10 The correlations between the micropore structures and DN.

information of geomaterials. This is found beyond the ability of (4) Ultimately, DN (or DWL) do not denote only the capillary
FHH model. condensation process in the pores but also infer to the micro-
Based on the above discussion, it can be said, if micropores pore information which makes them preferred models to be
in the shale samples are not abundant, then either of the three used when micropores are abundant in the sample compare to
models can be used and they will generate similar results. DFHH.
However, if shale sample or any geomaterial that has a fractal
behavior has abundant micropores, the whole gas adsorption
process will be a mixture of the poly-molecular and capillary
Conflicts of interest
condensation, thus DN and DWL which are affected by the There are no conicts to declare.
micropores and the capillary condensation are preferred. Based
on our previous studies, the micopores in the Bakken shale are
mainly existing in the organic matter and clay minerals.29 If the
Acknowledgements
Bakken shale samples have abundant organic matter and clay The authors appreciate ND Core Library, Jeff Bader – the
minerals, the DFHH will not be suitable for the characterization director and state geologist – as well as Kent Holland – library
of pore structure. However, if the Bakken is free from huge technician – for providing us with the samples. This research
quantities of clay minerals and organic matter, these three was supported by the National Research Foundation of Korea
models can all be appropriate for analysis. (NRF) funded by the Ministry of Science and ICT
(2020M2D8A206983011). Furthermore, the nancial supports
of the Basic Science Research Program (2017R1A2B3009135)
7. Conclusions through the National 18 Research Foundation of Korea is
In this study, 19 shale samples were selected from the Bakken appreciated.
Formation and N2 adsorption experiments were performed to
analyze their pore structures. Three different models (FHH References
model, Neimark model, and Wang–Li model) were employed to
study and compare the fractal dimensions in these shale 1 B. Liu, Y. Yang, J. Li, Y. Chi, J. Li and X. Fu, Stress sensitivity
samples. The following few conclusions can be derived from of tight reservoirs and its effect on oil saturation: a case study
this study: of lower cretaceous tight clastic reservoirs in the Hailar
(1) The FHH, Neimark model and Wang–Li model all can be Basin, Northeast China, J. Pet. Sci. Eng., 2020, 184, 106484.
applied for fractal dimension analysis of shale samples. The 2 B. Liu, Y. Song, K. Zhu, P. Su, X. Ye and W. Zhao, Mineralogy
fractal dimensions obtained from the Neimark and Wang–Li and element geochemistry of salinized lacustrine organic-
model are similar while the results are different from the fractal rich shale in the middle Permian Santanghu Basin:
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