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org/journal/acsodf Article

Using Nanoindentation to Characterize the Mechanical and Creep

Properties of Shale: Load and Loading Strain Rate Effects
Jianfeng Wang, Chao Yang,* Yuke Liu, Yun Li, and Yongqiang Xiong

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ABSTRACT: The mechanical and creep properties of shale strongly influence artificial hydraulic fracturing, wellbore stability, and
the evaluation of reservoir performance in shale gas exploration. This study characterized these mechanical and creep properties at
the microscale through nanoindentation tests and evaluated their dependence on the indentation test parameters, specifically, the
indentation load and the loading strain rate. The mechanical parameters (the Young’s modulus and hardness) of shale were strongly
influenced by the magnitude of an indentation load (2−400 mN). Both parameters decreased sharply as the load increased from 2 to
200 mN; they then remained relatively stable at loads of 200−400 mN, suggesting that large indentation loads (200−400 mN) can
be used to detect the mechanical responses of bulk shale. In contrast, both parameters increased slightly as the loading strain rate
increased from 0.005 to 0.1 s−1. The indentation creep (CIT), related to creep behavior, and the creep strain rate sensitivity (m),
related to the creep mechanism of shale, both increased with increasing the indentation load, whereas they decreased with increasing
the loading strain rate. This demonstrates that increasing the load or decreasing the loading strain rate can increase creep
deformation in shale during nanoindentation creep testing. The values of m varied from 0.040 to 0.124 under different loading
conditions, suggesting that dislocation power-law creep may be the main mechanism controlling creep in shale. This study
standardizes the testing parameters for the characterization of the mechanical properties of shale by nanoindentation testing and also
advances our understanding of the deformation mechanisms of shale at the microscale.

■ INTRODUCTION
Shale gas is an important unconventional energy resource in
China. It is produced and stored in organic-rich shales that have
extremely low permeability and low porosity.1 Therefore,
artificial fracturing (mainly employing hydraulic power) must
be applied to extract the gas from the tight shale rock.2
Successful fracturing depends heavily on the reliable determi-
nation of the mechanical properties of a shale reservoir.3−5 A
further important consideration is the creep behavior of shale,
which can weaken the scale of artificially induced fractures after a
period of time.6 Therefore, the quantitative characterization of
the mechanical properties and creep behavior of shale should
greatly aid the planning and operation of hydraulic fracturing.
Conventional uniaxial/triaxial compression tests can reveal
the macroscopic mechanical properties and creep behavior of
shale.7−9 However, these tests are generally time-consuming and
© 2022 The Authors. Published by
American Chemical Society
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require high-quality samples comprising a large volume free
from fracture, which is generally difficult to obtain in field
sampling.10−12 Therefore, nanoindentation has been introduced
as an alternative technique to characterize the mechanical
properties of shale.13−17 This technique uses only small sample
volumes (cuttings are acceptable) and can quickly generate large
amounts of mechanical data. It therefore greatly aids the analysis
of the micromechanical properties of shale; examples include the
Received: February 28, 2022
Accepted: March 30, 2022
Published: April 14, 2022
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calculation of the mechanical parameters of individual phases in
shales, such as minerals16−19 and organic matter,14,15,20−23 the
relationships between mineralogy and bulk mechanics of
shale,14,15,24 the elastic anisotropy of shale,17,25,26 and the
methods for the prediction of the macromechanical properties
of shale.23,26,27 Besides, nanoindentation can also be used to
study shale creep.28 Wick reported that nanoindentation gave
results that were comparable with those of conventional uniaxial
compression testing for creep behavior; thus, they believed that
nanoindentation measurements were reliable in determining the
creep behavior of shales.29 Recent research has focused on the
effects of shale composition30−33 and temperature34 on its
nanoindentation creep behavior, creep models for shale,35 and
the relationship between the creep parameters obtained from
nanoindentation and triaxial creep tests.23,31,36 Nanoindentation
testing has proved useful for both the characterization of
mechanical properties and evaluating creep behavior.
Shale is highly heterogeneous, being composed of various
hard minerals (e.g., quartz, feldspar, pyrite, calcite, and
dolomite), soft clays, and organic matter, and containing many
pores and other defects.19,31,37,38 Its mechanical responses at
different indentation positions will therefore vary. As such, a
single indentation cannot provide sufficient information about
the whole (composite) mechanical properties of shale. To solve
this problem, previous researchers have taken the average value
of a large number of indentation data, which are usually obtained
by grid indentation to homogenize the mechanical parameters of
the shale.12,14−16,30,39 The principle used in testing is that when
the maximum indentation depth (hmax) produced by an
indentation load is much larger than the particle size of the
individual phases, the average mechanical properties of the
composite material can be obtained.40 However, there is no
standardized method for the nanoindentation testing of
materials with complex microstructures such as shale, especially
regarding the characteristic indentation load beyond which clay-
rich shale responds homogeneously.
Additionally, nanoindentation is essentially depth-sensitive:
the volume range acted on by the indenter at different depths
into the sample varies, potentially producing different
mechanical responses and different mechanical data. Previous
materials science studies have demonstrated the universality of
the indentation size effect (ISE), which is manifested as the
measured elastic modulus and hardness increasing with
decreasing load (or indentation depth).41,42 The measured
creep behavior of metals also shows significant ISE,43−50 as the
creep strain rate sensitivity (m) and hardness can become
smaller as the indentation displacement deepens,43−48,50
whereas some metallic films have exhibited the opposite
behavior.49 Furthermore, the mechanical and creep properties
of polymer materials were reported to depend strongly on the
indentation loading rate, with a higher loading strain rate
generally leading to higher values of hardness and lower creep
strain rate sensitivity.48 However, some exceptions show
opposite trends for hardness51 and creep strain rate sensitivity52
when indenting metallic materials. As for geological samples, Shi
et al. discussed the impact of the loading rate on the mechanical
properties of shale,12 but its effect on creep behavior was not
involved. In addition, a negative dependence on the indentation
size and the loading rate was found for the mechanical properties
of solid bitumen.12 Although much work has been done in metal
materials science, the effects of the load and the loading strain
rate on the mechanical properties and creep behavior of shale are
still not fully understood.
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In general, the main purpose of this study was to use
nanoindentation to explore the effects of the indentation load
and the loading strain rate on the mechanical properties and
creep behavior of shale at the microscale. We examine the creep
strain rate sensitivity through the characterization of the creep
behavior of shale under different indentation loads and loading
strain rates and discuss a potential deformation mechanism.
These results could aid understanding of the influence of loading
conditions on the mechanical properties and creep behavior of
shale, which is an important area of research in both field and
laboratory settings.
2. SAMPLE AND EXPERIMENTAL METHODS
2.1. Sampling and Sample Preparation. The shale
sample used for nanoindentation testing was collected from
the Lower Silurian Longmaxi Formation, Sichuan Basin, South
China (Figure 1). X-ray diffractometry analysis showed that it
was composed of quartz (34.4%), feldspar (13.6%), carbonates
(4.5%), pyrite (1.5%), and clay minerals (45.9%).
Figure 1. Figure 1. (a) The bulk Longmaxi shale core and (b) the
polished shale sample. (Taken by the author).
Nanoindentation testing requires the sample surface to be
quite flat53 and therefore carefully polished. The sample was first
cut to ∼10 mm length ×5 mm width ×5 mm height, and then
cast into a resin. The exposed surface of the shale was
perpendicular to the bedding plane. Various silicon carbide
abrasive papers (mesh numbers from 50 to 2000 grit) were used
sequentially to polish the sample. Furthermore, surface polishing
was performed using a series of alumina grit pads (9, 3, and 1
μm). Finally, an IM4000 argon ion mill operated at 4.0 kV and a
5° angle, which was produced by Hitachi High-Tech Global
Corporation, was used for polishing for 2 h to achieve a
completely flat surface. Atomic force microscopy (AFM) was
used to determine the mean roughness (root mean square
roughness, Rq) from two different areas (30 × 30 μm2) of the
shale surface, yielding a value of 67.9 ± 10.9 nm. Figure 2 shows
a tomographic AFM image of the sample (Dimension 3100,
Bruker Nano/Veeco, CA).
2.2. Mechanical Testing. 2.2.1. Introduction to Nano-
indentation. This study used a commercial nanoindentation
apparatus (NHT3 nanoindenter, Anton Paar Company)
equipped with a diamond Berkovich indenter. The stiffness
threshold was 500 N/m. The indenter applied loads of 0.1−500
mN as it was pressed into the sample surface.53 Before the
nanoindentation test, a standard fused silicon specimen was
employed to calibrate the tip shape. The stiffness threshold was
500 N/m and its spring compliance was 0.571 mm/N. The
resolutions of the load and displacement settings were 20 nN
and 0.01 nm, respectively.
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where Ei and νi are the Young’s modulus and Poisson’s ratio of

Figure 2. Three-dimensional topographic image of shale rock from
AFM (area 30 × 30 μm2, Rq = 60.1 nm).
Figure 3a outlines a schematic diagram of the nano-
indentation. Complete indentation included applying a loading
force to the sample surface and holding it for some time prior to
being unloaded. Figure 3b shows a typical P−h curve, which is
divided into three stages (i.e., loading, holding, and unloading).
By using a continuous mechanical model, the hardness (H)
and reduced Young’s modulus (Er) of the material can be
obtained from the P−h curve
P There are some specific requirements for grid nano-
H = max
Ac (1)
Er =
S π
2β Ac
where S is obtained from the initial slope of the unloading curve,
which represents the stiffness of the material, β is a constant that
depends on the geometry of the indenter (for a common
Berkovich indenter, β = 1.034), and Ac is the projected contact
area, which is calculated from the depth of contact (Hc).53,54
Furthermore, based on the reduced Young’s modulus and
Poisson’s ratio, the Young’s modulus of the material can be
defined as
1 1 − v2 1 − vi2
= +
Er E Ei
the diamond indenter, respectively. For the diamond indenter,
Ei = 1140 GPa and νi = 0.07. E and ν are the Young’s modulus
and Poisson’s ratio of the samples prepared for testing,
respectively. For the shale sample, the Poisson’s ratio is assumed
to be 0.30.26 Shale rock with a Poisson’s ratio between 0.05 and
0.30 would have an 8% uncertainty in the Young’s modulus
measured using nanoindentation.14
2.2.2. Procedure for Testing Mechanical Properties.
Constant load tests assessed the influence of the indentation
load on mechanical properties, and tests at the constant strain
rate explored the effect of the loading strain rate. Specifically,
constant load tests used loads of 2, 5, 10, 20, 50, 100, 200, 300,
and 400 mN, all at a loading strain rate of 0.05 s−1. The tests at
the constant strain rate applied strain rates of 0.005, 0.010,
0.030, 0.070, and 0.100 s−1 during the loading stage with a
maximum indentation load of 300 mN. The holding time for
studying the shale’s mechanical properties was 2 s. For all the
indentation tests, the indenter approached and was retracted
from the sample surface at a rate of 2000 nm/min within a
distance of 2000 nm of the sample surface.
As mentioned in the introduction, this work characterized the
mechanical properties of shale by averaging a large amount of
nanoindentation data. Obtaining the data relied on grid
indentation. Figure 4a shows the schematic diagram of grid
nanoindentation, and Figure 4b−d shows typical microscope
images of a matrix of 100 indents (at a load of 300 mN) on the
shale sample.
indentation, including the selection of the representative
elementary area (REA) of the shale matrix27 and the minimum
distance between neighboring indentations.55 The REA refers to
(2) the smallest area that can be analyzed to represent the bulk shale
in all respects. The minimum distance between neighboring
indentations should be at least 10 times the indentation depth in
order to avoid mechanical interference between adjacent
indentations.55 The minimum REA in shale is 250 μm × 250
μm,27 which provides a basis for selecting the minimum
indentation number. Therefore, grid indentation should apply at
least 200 individual indentations at loads of 2, 5, and 10 mN, and
at least 100 individual indentations for loads of 20, 50, 100, 200,
300, and 400 mN to cover the REA of the sample surface in each
case. The distances between neighboring indentations were 20
μm for loads of 2−10 mN, 50 μm for loads of 20−300 mN, and
(3) 60 μm for a load of 400 mN.

Figure 3. Schematic of a (a) nanoindenter,30 and (b) schematic of a typical nanoindentation curve, P: the applied load, Pmax: the peak load, S: the
contact stiffness, h: the indentation displacement, hmax: the maximum indentation displacement, We: elastic work, and Wp: plastic work.

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Figure 4. (a) Schematic of the nanoindentation grid. (b−d) Typical optical microscopy images of the shale sample with a matrix of 100 indentations
made at a load of 300 mN; the photography used an eyepiece with 40× magnification and objective lenses with (b) 5×, (c) 50×, and (d) 20×
magnification.

2.3. Creep Testing. 2.3.1. Creep Test Procedure. Shale where ε̇ and σ are the steady-state creep strain rate and the
creep can be investigated by measuring the displacement−time applied stress, respectively; A is a constant; R is the molar gas
curve during the holding stage, in which the applied load constant; Q is the activation energy for a thermally activated
remains constant and the indentation displacement increases. process; T is the temperature; and n is the power-law exponent
There are three stages in a macroscale creep test: transient (or (creep stress exponent). All the experiments were conducted at
primary), steady state (or secondary), and tertiary (or room temperature, which could be considered relatively
accelerating).56 Most nanoindentation cases show only the constant, allowing eq 1 to be described as
first two stages because the tertiary stage means that creep
deformation is accelerating to failure, which is difficult to ε ̇ = C1σ n (5)
observe.28,35
Similar to the mechanical characterization, indentations at the C1 = A exp( −Q /RT ) (6)
constant load and the constant strain rate were used to
investigate the effects of the load and the loading strain rate where C1 is a temperature-dependent material constant. For the
on the creep behavior of the shale. Dynamic mechanical analysis nanoindentation creep test via a Berkovich indenter, ε̇ and σ can
model testing was applied during the loading stage. This be calculated using their equations as follows57
involved small monochromatic oscillations modulating the
indenter load. The main difference between the investigation 1 dh
ε̇ =
of the mechanical properties and creep behavior was the h dt (7)
duration of the holding stage. Specifically, the creep tests used a
holding time of 1200 s. The selected dwell time was much P
greater than most of those previously reported, which helped to σ=
24.56h2 (8)
identify any possible change in the creep mechanism during
testing.57 where h and t are the instantaneous indentation depth and the
2.3.2. Calculation of Creep Strain Rate Sensitivity (m). indentation time, respectively, and P is the instantaneous applied
Creep strain rate sensitivity (m) is a power-law exponent indentation load.
reflecting the flow performance of a material and can indicate the Equation 2 can be rewritten as

i P yz
= C jjj
deformation mechanism.11,48,50,58 The smaller the m value, the
z
2z
n

k 24.56h {
more resistance to creep deformation. It is determined from the 1 dh
steady-state stage of the creep test. The following power-law h dt (9)
relationship is usually used to describe steady-state creep
behavior59 Therefore, the value of m can be calculated by taking the
logarithm on both sides of eq 1. Its value is the reciprocal of
ε ̇ = Aσ n exp( −Q/RT) (4) n:48,60
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Figure 5. Typical curves for (a) load versus displacement and (b) displacement versus load. Plots of (c)Young’s modulus and (d) hardness at
indentation loads of 2−400 mN at a loading strain rate of 0.05 s−1.

Table 1. Statistical Results for Nanoindentation Mechanical

1
m= =
d(log σ )
=
d log ( ( )) P
24.5h2 Properties Measured by Different Test Methodsa
n d(log ε)̇ d log ( ( )) 1 dh
h dt (10) hmax (nm)
hardness
(GPa)
Young’s modulus
(GPa)
loading
strain
3. RESULTS AND DISCUSSION Pmax rate
3.1. Mechanical Properties. 3.1.1. Mechanical Properties (mN) (s−1) ave. std. ave. std. ave. std.
at Various Loads. Figure 5a shows typical load−displacement 2 0.05 199.44 70.85 4.37 5.13 55.82 23.90
curves resulting from a series of tests with increasing loads (2, 5, 5 0.05 362.84 122.95 3.69 4.66 49.92 22.15
10, 20, 50, 100, 200, 300, and 400 mN). Indentation testing 10 0.05 526.72 151.76 3.00 3.10 47.91 14.90
comprises loading, holding, and unloading stages. The loads of 20 0.05 797.57 175.26 2.25 2.01 44.30 9.99
200−400 mN show similar curves for the different stages, 50 0.05 1338.85 240.43 1.86 1.82 40.91 8.22
suggesting consistent mechanical responses at these loads. 100 0.05 2032.31 275.40 1.33 0.94 37.22 5.74
Figure 5b shows the relationship between the indentation load 200 0.05 3095.08 347.72 1.08 0.34 33.15 4.48
and the resulting displacements. Specifically, the average 300 0.05 3850.71 390.53 1.04 0.28 32.10 3.94
displacement increased from 199.44 ± 70.85 nm at a load of 2 400 0.05 4507.66 388.73 0.98 0.20 31.39 3.54
mN to 4507.66 ± 388.73 nm at a load of 400 mN (Table 1). An 300 0.005 3945.21 365.62 0.96 0.23 30.91 3.56
increase in the indentation load results in an increase in the 300 0.01 3952.53 484.52 0.96 0.26 32.36 3.28
indentation depth. 300 0.03 3998.32 421.01 0.97 0.39 32.29 2.96
Figure 5c,d shows the load profiles of the mean Young’s 300 0.07 3649.10 263.51 1.13 0.21 35.03 3.61
modulus and hardness, respectively. The curves show two 300 0.1 3702.93 334.24 1.08 0.25 33.96 4.06
a
sections: a sharp decrease at loads of 2−200 mN and a relatively Pmax: maximum load and hmax: maximum indentation depth.
flat section at loads of 200−400 mN. Specifically, the mean
Young’s modulus varied from 55.82 GPa at a load of 2 mN to
33.15 GPa at a load of 200 mN, whereas hardness ranged from Alternatively, the large standard deviations at relatively low loads
4.37 to 1.08 GPa at these loads. At loads of 200−400 mN, the (2−10 mN) indicate that indentations penetrated only a single
mean Young’s modulus varied slightly between 33.15 and 31.39 mineral phase (quartz or clay minerals). Consequently,
GPa, whereas hardness ranged from 1.08 to 0.98 GPa (Table 1). averaging data from nanoindentations at low loads cannot
This indicates that with increasing load, the area and volume appropriately represent the whole shale sample.
acted on by the indentation increased continuously, so the 3.1.2. Accuracy of Estimates of Mechanical Properties.
indentation response gradually approached that of the whole Indentation testing in regions with predominantly hard or soft
shale. This result can also be derived from the decreasing minerals would give different mechanical properties. To better
standard deviations of mechanical data with the increasing understand the mechanical properties of shale at the microscale,
indentation load. Therefore, loads of 200−400 mN can be used we chose for detailed analysis two representative points (labeled
to characterize the mechanical properties of the bulk shale. a and b) from the grid indentations. Figure 6 shows hard
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Figure 6. Optical microscopy images of two representative indentation
points: a in mainly soft minerals and b in mainly hard minerals.
Indentation was at a strain rate of 0.05 s−1 with a maximum load of 400
mN.
minerals can be easily observed, while soft minerals, mainly clay,
are continuously distributed in the shale, acting as a framework
in which hard mineral grains are embedded.19 The optical
microscopy image of point a indicates that the residual
impression was in a region of mainly soft minerals, while point
b appeared to be mainly in hard minerals (Figure 6).
Figure 6 shows that the diameters of the two representative
indentations were >20 μm, which exceeds the size of most single
mineral phases. The size of the residual impression for the region
of soft minerals was larger than that for the region of hard
minerals. Point a had lower hardness (0.87 GPa) and Young’s
modulus (30.49 GPa) than point b (1.48 and 34.67 GPa,
Figure 7. Typical nanoindentation curves for various loads during nanoindentation testing of the Longmaxi Shale sample. (a) Normal P−h curve and
P−h curves with the “pop-in” phenomenon during the loading stage for loads of (b) 200, (c) 300, and (d) 400 mN.
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respectively). The mean hardness and Young’s modulus of the
grid nanoindentation were 1.04 ± 0.28 and 32.11 ± 3.94 GPa,
respectively. The mechanical parameters of the two regions are
comparable and very close to the mean values. Therefore, it is
acceptable to take the average value of a large number of
indentation data to derive mechanical parameters representative
of the whole shale.
A “pop-in” phenomenon was observed during the loading
stage of nanoindentation (Figure 7), characterized by a sudden
increase in displacement. This has been attributed to crack
propagation or microcracks and pores at the contacts among
minerals in the shale.61
To investigate the effects of the “pop-in” phenomenon on the
results of nanoindentation, the following power-law functions
were used to fit the loading and unloading curves61
P = Khn(loading stage) (11)
P = α(h − hf )m (unloading stage) (12)
where P, h, and hf are the applied load, displacement, and
residual displacement, respectively. K, n, α, and m are constants
derived from fitting the loading and unloading curves.
Table 2 lists curve fitting parameters for the loading and
unloading stages of typical nanoindentation curves. The results
indicate that the power-law functions fit both curves very well,
consistent with previous findings.61 This implies that the theory
of nanoindentation can be used to calculate the shale’s
mechanical parameters.
For indentation loads of 200−400 mN, 100 indentations were
used to give statistically accurate average values for the
mechanical parameters. Figure 8a,c shows the relationship
between the mean Young’s modulus and the number of
indentations at loads of 300 and 400 mN. It suggests that the
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Table 2. Curve Fitting Analysis for the Loading and Unloading Stages
loading stage
Pmax (mN) K n
a 200 0.000056 1.862
b 200 0.0011 1.4675
c 300 0.00016 1.743
d 400 0.0078 1.2792
Figure 8. Statistical analysis of the number of indentations: the mean Young’s modulus and standard deviation with respect to the number of
indentations at loads of (a) 300 and (c) 400 mN, and the error (|μn−μ100|/μ100) of the mean Young’s modulus with respect to the number of
indentations at loads of (b) 300 and (d) 400 mN. Note: μn represents the mean Young’s modulus for n indentations, and μ100 represents the mean
Young’s modulus for 100 indentations.
mean Young’s modulus and standard deviation changed slightly
when there were more than 30 indentations. For an allowed
error of 3% in the mean Young’s modulus, a matrix of 36
indentations (6 × 6 grid) is adequate to predict the mechanical
properties of the bulk shale sample (Figure 8b,d). Previous
studies have used less than 36 indentations to characterize the
mechanical properties of bulk shale,12,30,35,39 whereas few
studies have provided direct evidence supporting the choice of
the number of nanoindentations. Overall, the abovementioned
findings indicate that at least 36 indentations at loads of 200−
400 mN can be used to obtain the mechanical properties of
shale.
3.1.3. Mechanical Properties at Various Loading Strain
Rates. Given the abovementioned findings, a matrix of 36
indentations was used to obtain average mechanical data for
shale at each indentation loading strain rate with a constant load
of 300 mN. Figure 9a plots the corresponding typical load−
displacement curves, which are almost uniform in shape. Figure
9b shows the variation in indentation displacement for different
loading strain rates. Increasing the loading strain rate generally
decreases the average displacement. Specifically, it decreased
from 3945.21 ± 365.62 nm at a loading strain rate of 0.005 s−1 to
3702.93 ± 334.24 nm at a loading strain rate of 0.1 s−1. This
phenomenon has also been found in a previous study.12
Figure 9c,d shows a generally positive relationship between
the mean Young’s modulus and hardness with respect to loading
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unloading stage
R2 α m R2
0.9997 0.0026 1.7129 0.9901
0.9973 0.0035 1.6824 0.9892
0.9985 0.0261 1.4044 0.9805
0.9986 0.00039 1.9206 0.9885
strain rates (0.005−0.1 s−1). Specifically, the mean Young’s
modulus varied slightly between 30.91 ± 3.56 and 35.03 ± 3.61
GPa, and the mean hardness ranged from 0.96 ± 0.23 to 1.13 ±
0.25 GPa (Table 1). As the loading strain rate increased, it might
have produced a higher flow stress and a larger induced
compressive stress, which increased the deformation volume of
the material and expanded the plastic zone size.12 This accounts
for the high loading strain rate causing a reduction in surface
deformation displacement (Figure 9b). Consequently, pressure
hardening improved the contact hardness and the compressive
yield stress with an increasing loading strain rate.12
Notably, as the loading strain rate increased, the mean
Young’s modulus and hardness increased only by 9.8% and
12.5%, respectively. Compared with the variations seen under
different loads, altering the loading strain rate did not
substantially change the Young’s modulus or hardness,
suggesting that they were more sensitive to the indentation
load than to the loading strain rate under the considered
methodology and experimental conditions.
3.2. Creep Properties. Based on the results in Section 3.1.1,
the influence of the indentation load on shale creep was studied
using indentation loads of 200, 300, and 400 mN at a constant
loading strain rate of 0.05 s−1, and by applying loading strain
rates of 0.005, 0.010, 0.030, 0.070, and 0.100 s−1 at a constant
load of 300 mN. This could eliminate the effect of the load on
the bulk shale. The typical load−displacement curves and creep
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Figure 9. Typical curves for (a) load versus displacement and (b) displacement versus loading strain rate. Plots of (c) Young’s modulus and (d)
hardness at indentation loading strain rates of 0.005−0.1 s−1 and a load of 300 mN.

Figure 10. Typical curves for (a) load versus displacement and (b) creep displacement versus time. Plots of (c) We/Wt and (d) CIT at indentation loads
of 200, 300, and 400 mN at a loading strain rate of 0.05 s−1.

displacement−time curves for the different indentation loads
and different loading strain rates are shown in Figures 10a,b and
11a,b, respectively. The corresponding measured parameters of
the ratio of elastic work to total work (We/Wt) and the
indentation creep rate (CIT) are displayed in Figures 10c,d and
11c,d. The We/Wt ratio represents the elastic part of indentation
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work; a higher value indicates a greater contribution of elastic
deformation. CIT was calculated by dividing the maximum
displacement during the loading stage by the creep displacement
during the holding stage. A higher CIT value indicates greater
creep deformation. Statistical results for these parameters are
provided in Table 3.
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Figure 11. Typical curves for (a) load versus displacement and (b) creep displacement versus time. Plots of (c) We/Wt and (d) CIT at loading strain
rates of 0.005, 0.01, 0.03, 0.05, 0.07, and 0.1 s−1 at a load of 300 mN.

Table 3. Statistical Results for Nanoindentation Creep Tests by Different Methodologiesa

creep strain rate
hmax (nm) CIT (%) We (pJ) Wt (pJ) Wp (pJ) We/Wt (%) sensitivity (m)
Pmax loading strain
(mN) rate (s−1) ave. std. ave. std. ave. std. ave. std. ave. std. ave. std. ave. std.
200 0.05 3070 239 13.06 2.72 56846 7541 265663 32277 208817 32908 21.7 3.7 0.047 0.025
300 0.05 4344 240 14.17 3.28 113178 11356 572566 64135 459388 58208 19.9 1.8 0.052 0.037
400 0.05 4726 357 17.62 2.43 157460 14813 850639 77591 693179 72922 18.6 2.0 0.066 0.036
300 0.005 4595 329 17.17 3.77 118686 12888 683686 69586 565000 65218 17.4 1.9 0.124 0.030
300 0.01 4527 424 17.86 4.78 118422 15122 640071 80872 521649 71521 18.6 1.8 0.070 0.034
300 0.03 4414 408 15.14 5.67 117789 15483 579884 71959 462095 69494 20.5 2.9 0.067 0.041
300 0.07 4567 424 12.57 1.94 105585 7847 566893 64458 461308 59696 18.8 1.6 0.040 0.020
300 0.1 4563 332 12.61 2.56 113571 10018 579341 59630 465770 56956 19.8 2.2 0.041 0.022
a
Pmax: the maximum load; hmax: the maximum indentation depth; CIT: the ratio of creep displacement during the holding stage to the maximum
displacement during the loading stage; We: elastic work; Wp: plastic work; and Wt: total work.

3.2.1. Variation in Creep Behavior with Indentation Load.
Figure 10a shows the load−displacement curves at each stage for
various loads. Figure 10b shows creep displacement with respect
to creep time (for 1200 s), showing two main stages: an initial
transient stage (the first ∼600 s) and a subsequent steady-state
stage (the following 600 s). During the transient period, creep
displacement increased with gradually decreasing acceleration,
and the variation in the creep rate (the slope of the curve) is
large.30 During the steady-state stage, the creep displacement
increased linearly with the creep time, and the slope of the curve
for a large indentation load appears relatively steep, while the
creep rate remains nearly constant.30 The We/Wt ratio decreased
with increasing indentation load (Figure 10c), dropping from
21.7% at 200 mN to 18.6% at 400 mN. The CIT was positively
correlated with the indentation load (Figure 10d), increasing
from 13.06% at 200 mN to 17.62% at 400 mN, suggesting that
the creep of shale increases with an increasing load.
14325
3.2.2. Creep Behaviors with Respect to Loading Strain
Rate. Figure 11a,b shows typical load−displacement curves and
creep time−displacement curves for different loading strain rates
(0.005, 0.010, 0.030, 0.070, and 0.100 s−1) and a total creep time
of 1200 s. A lower loading strain rate led to greater creep
displacement for a given holding time. According to the
variation in creep displacement in Figure 11b, the creep−time
curves also show a two-stage upward trend: an initial rapid rise
within the first ∼600 s, followed by a slow linear increase. This
variation conforms to established creep stages identified in
previous studies.30
The We/Wt ratio increased as the strain rate increased up to
0.05 s−1 (Figure 11c), after which it slightly decreased. Overall,
the generally positive trend for the We/Wt ratio shows that the
shale may have undergone more elastic deformation with an
increasing loading strain rate. The CIT value was negatively
related to the loading strain rate, decreasing from 17.17% at a
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Figure 12. (a) Displacement−time, (b) creep strain rate−time, (c) stress−time, and (d) logarithmic stress versus logarithmic creep strain rate curves
during the creep stage at a loading strain rate of 0.01 s−1 and a load of 300 mN. The holding time was 1200 s during the creep stage.

Table 4. Summary of the Indentation Settings and Mechanical and Creep Properties for Two Points
points Pmax (mN) loading strain rate (s−1) hmax (nm) hardness (GPa) Young’s modulus (GPa) creep displacement (nm) m
point 1 300 0.05 4619.7 0.66 25.77 461.1 0.066
point 2 300 0.05 3129.5 1.71 31.89 417.4 0.046

Figure 13. Optical microscopy images of points (a) 1 and (b) 2. Curves of (c) load versus displacement and (d) creep displacement versus creep time
during the creep stage for both points at the strain rate of 0.05 s−1 and a maximum load of 300 mN.

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Figure 14. Creep strain rate sensitivity, m, (a) at different indentation loads with a loading strain rate of 0.05 s−1 and (b) with respect to the loading
strain rate at a load of 300 mN. Mean values with error bars (one standard deviation) are plotted.
loading strain rate of 0.005 s−1 to 12.61% at a rate of 0.1 s−1,
suggesting that the creep capability of the shale weakened with
an increasing loading strain rate.
It is noted that the accurate measurement of mechanical
parameters only needs several seconds of holding time.62 The
mean mechanical parameters (hardness and Young’s modulus)
for a holding time of 1200 s were less than those for a holding
time of 2 s. For example, the mean hardness varied from 1.04 ±
0.28 GPa to 0.77 ± 0.10 GPa, and the mean Young’s modulus
decreased from 32.10 ± 3.94 GPa to 25.92 ± 2.37 GPa with an
increasing holding time. That is, both parameters decreased as
the creep time increased. Creep was possibly responsible for the
decrease (consistent with previous findings35,63) owing to an
increase in the creep time producing greater displacement,
which would result in lower measured mechanical parameters.
3.3. Creep Mechanism of Shale. 3.3.1. Calculation of the
Creep Strain Rate Sensitivity (m) of Shale. The empirical
formula was used here to fit the creep displacement−time
curves50,64,65
h = c(t − d)e + a + bt
where h is the creep displacement and t is the creep time.
Parameters a, b, c, d, and e are constants obtained by fitting
nanoindentation creep data sets. Representative plots of
experimental creep displacement versus time and the corre-
sponding curves fitted using this equation (loading strain rate =
0.01 s−1, Pmax = 300 mN) are shown in Figure 12a. The values of
ε̇ and σ, calculated by eqs 4 and 5, are plotted with respect to
creep time in Figure 12b,c. The former decreased significantly
from 6.31 × 10−4 to 5.71 × 10−5 s−1 during the first ∼600 s, and
then remained relatively invariable at around the 10−5 order of
magnitude during the later steady-state stage during the last 600
s (Figure 12b). In comparison, σ gradually decreased during the
first ∼600 s before declining linearly. Therefore, the creep strain
rate sensitivity (m) was taken from the steady-state stage. A
logarithmic plot of the creep strain rate (ε̇) and stress (σ) based
on eq 6 (Figure 12d) gave the value of m. During the steady-state
stage of creep, the logarithmic value of ε̇ and σ decreased
correspondingly from the upper right corner to the lower left
with a good linear relationship (Figure 12d). The red triangle in
Figure 12d represents the fitting region and the data used to
calculate m as 0.070.
For further nanoscale investigation of the creep behavior of
bulk shale, we chose two representative indentations (labeled
points 1 and 2) from the grid for detailed analysis. Table 4 lists
information about both indentations. Point 1 was indented into
Article
mainly soft minerals, as demonstrated by the low hardness and
Young’s modulus, and high hmax and creep displacement. In
contrast, the optical microscopy image indicates that point 2 was
in mainly hard minerals; the hardness and Young’s modulus
were high, and hmax and creep displacement were low (Figure 13;
Table 4).
The m value of point 1 was a little larger than that of point 2
(Table 4), which suggests that the region rich in soft minerals
was more likely to creep. However, the small difference in m
values indicates that taking an average value from many points
can give a representative characterization of the shale’s creep
behavior.
3.3.2. Effects of Indentation Load and Loading Rate on
Creep Strain Rate Sensitivity. Figure 14 shows the creep
behavior of shale to be positively correlated with the indentation
load but negatively correlated with the loading strain rate. The
calculated m value was not fixed, but changed with the load and
the loading strain rate. With the increasing indentation load, it
increased slightly from 0.047 at a load of 200 mN to 0.066 at 400
mN (Table 3; Figure 14a). A generally slight positive
(13)
dependence of m on the indentation load is commonly observed
for metals and bitumen, which can be interpreted using a “shear
transformation zone” (STZ) or “free volume” model.44,66−68 In
the STZ model, the atomic-scale STZs consist of a large free
volume site with adjacent atoms, and they are considered to be
the basic shear units. They collectively deform under applied
shear stress, resulting in shear bands, which may further induce
the local softening of the material. It is generally considered that
with an increasing indentation load, the STZ or “free volume”
will continue to increase, the power to resist creep deformation
will reduce, and the creep strain rate sensitivity will increase.44,66
In contrast to the slight increase of m with the increasing load,
its value fell from 0.124 to 0.040 with the increasing loading
strain rate (Table 2). The generally small variation in m suggests
only a weak negative dependence on the loading strain rate
(Figure 14b), which is consistent with the variation of CIT
(Figure 11d). This suggests that a lower loading strain rate leads
to proportionally stronger creep behavior of the shale. Similar
results have also been found for metals at room temperature.48,69
A possible explanation of this result is that a higher loading strain
rate can lead to higher hardness (as observed in Figure 6) and
hence smaller m.48 Another possible reason is that a higher
loading strain rate can cause more heterogeneous grain
structures and higher local stress during the loading period,
which can effectively inhibit the absorption and emission of
dislocations at grain boundaries during the subsequent creep
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Table 5. Comparison of m Values From Previous Works
reference rock or its components
Brantut et al. 2012 granite, basalt, and sandstone
Rybacki et al. 2017 Posidonia shale
Naumann et al. 2007 Opalinus Clay
Gupta et al. 2018 Woodford, Wolfcamp, and Eagle Ford shale
Ma et al., 2021 quartz in granite
Ma et al., 2021 feldspar and mica in granite
Liu et al., 2019 solid bitumen
this work Longmaxi shale
period. This finally leads to a lower m at the steady-state stage of
the creep.48
3.3.3. Creep Mechanism Predicted from Creep Strain Rate
Sensitivity. Possible creep mechanisms during the nano-
indentation creep experiments have been established: dis-
location power-law creep, diffusional creep, and grain boundary
sliding.48,64,70,71 The m values of 0.040−0.124 observed here for
Longmaxi shale are relatively small, and are therefore not
attributed to grain-boundary sliding. Given the high creep strain
rate and deep holding depth, grain boundary diffusion and tip−
sample atomic diffusion can also be eliminated.64 Previous
studies have indicated that when m = 1, the creep is dominated
by the diffusion of atoms via lattice diffusion or Coble creep,48
when m = 0.5, the creep is mainly controlled by grain boundary
sliding,70 and when m < 0.33, dislocation power-law creep is the
dominant creep mechanism.64,71 Therefore, the small values of
m seen here suggest dislocation power-law creep as the
dominant creep mechanism for shale. As such, due to the high
load (200−400 mN) and shear stress, the sample surface
subjected to the indenter underwent strong shear flow, and
gliding dislocations met obstacles such as precipitates and lattice
atoms, and attempted to cut through or bypass them.72 This
dislocation movement may have dominated the deformation
behavior of the shale. Ma et al. found that the creep stress
exponent (n = 1/m) for quartz, feldspar, and mica in granite was
above 3, and suggested that dislocation creep was the dominant
deformation mechanism for these minerals in granite at low
temperatures and high strain rates.73 The m value observed here
is very close to those previously reported for Eagle Ford,
Wolfcamp, and Woodford marine shales,30 suggesting a
consistent creep mechanism for different shales.
Furthermore, the comparison of the m value for the shale with
that of other rocks or their components could provide useful
results. Table 5 summarizes m values for different rocks and rock
components as reported in the literature.
The results were obtained primarily via macroscopic creep
testing (i.e., triaxial compression testing)74−76 and nano-
indentation creep tests.11,30,73 None of the studies provided a
value of m above 0.33. The lowest was 0.0008−0.0123 for solid
bitumen, and the highest was 0.21 for Posidonia shale; therefore,
dislocation creep may be the dominant mechanism in all these
cases. The m values of shales from nanoindentation creep tests
are very close to those of Posidonia shale from triaxial creep
testing, which suggests that nanoindentation testing is useful for
predicting the macroscopic creep behavior of shale. Further
research should compare the creep behavior during nano-
indentation and traditional triaxial testing.
Shale is a complex multiphase Earth material, and explaining
its physical deformation mechanism remains challenging.
Traditional macroscopic tests have suggested that a range of
mechanisms may drive creep in shale, including subcritical crack
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n m test technique
5.5∼34 0.03−0.18 Triaxial creep tests
∼4.8 ∼0.21
∼5 ∼0.2
5.6−6.9 0.14−0.17 nanoindentation creep tests
10.5−13.5 0.07−0.10
>3 <0.33
81−1250 0.0008−0.0123
10−30 0.040−0.124
growth, pressure solution, frictional slip, internal grain
deformation, grain compaction and rearrangement, grain sliding,
and the collapse of clay floccules.31 The present nano-
indentation test results indicate that dislocation creep may be
the dominant deformation mechanism for shale. However,
dislocations here may have been produced by the compaction
and rearrangement of grains and their motion through frictional
sliding. As dislocations are too small to be directly observable by
optical microscopy, future observation by high-resolution
transmission electron microscopy should provide direct
evidence at the nanoscale, as it can examine the variation of
fine textures in shale before and after indentation, including the
boundaries of dislocations. Overall, the present findings provide
quantitative guidance for revealing the micromechanism of shale
creep behavior and may provide a baseline to investigate the
creep behavior of other rocks at elevated temperatures.
3.4. Limitations and Suggestions for Further Work.
Although the effects of the indentation load and the loading
strain rate on m have been described above, the large standard
deviation of its values, especially for different indentation loads,
does not indicate that the conclusions are highly reliable. The
variations in m observed in the present study may have been due
to the following reasons:
1) The holding time of the indentation experiment was a
major factor owing to the limited thermal stability of the
nanoindenter: the relatively short duration of most
indentation tests (minutes rather than days or months)
typically used to assess tensile creep might have
influenced the results.57
2) Primary creep might have significantly affected the
observed creep behavior.31
3) Using a heterogeneous and anisotropic sample (i.e., shale)
during the test might have induced complex creep
behavior. The creep curve with the “pop-in” phenomenon
and/or data with a relatively large thermal drift must be
discarded.33,57
Shale is a type of fine-grained sedimentary rock composed of a
variety of minerals (clay, quartz, feldspar, pyrite, and carbonate)
and organic matter. Each component has its own creep behavior.
Of these components, organic matter and clay minerals are
highly flexible and thus susceptible to creep deformation. A
nanoscale investigation of the creep behavior of shale can help
elucidate its creep deformation at a larger scale. Therefore, our
objective for forthcoming work is to determine the dominant
mechanism controlling the creep deformation of shale at a fine
scale.
Furthermore, the influences of fluid, pressure, and temper-
ature were not considered here. Therefore, the determined
mechanical properties and creep behavior of shale do not fully
represent those in the subsurface. It is reported that the friction
coefficient between clay minerals and organic matter would
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increase with increasing temperature, thus altering the creep
behavior of shales.34 In addition, during the hydraulic fracturing
procedure of a shale gas formation, the interaction between
fracturing fluids and shale rock may affect its creep behavior.
Considering the millimeter size of shale and the relatively short
test duration, our creep test was carried out without involving
the effects of fluids. Details of in situ shale reservoir conditions
(i.e., temperature and fluids) should be considered in a future
study.
Finally, although previous research has shown that the elastic
modulus determined by indentation testing is similar to that
obtained from traditional triaxial compression testing, nano-
indentation technology is quite different from macroscale
compression testing in terms of boundary conditions and
loading geometry.31 Moreover, for heterogeneous shale, the
Young’s modulus from the upscaling model by mineral fraction
is close to that obtained by uniaxial compressive testing,26,39
whereas there have been inconsistencies among values from
averaged nanoindentation data, the upscaling model by
deconvolution analysis and macroscale methods.14,27,39 In
addition, creep behavior measured by microindentation can
predict that measured by the macroscopic uniaxial compressive
testing of similar composite materials such as concrete.77
However, creep behaviors from triaxial testing and micro-
mechanic-based homogenization schemes from nanoindenta-
tion experiments show some discrepancies, which may be
attributed to the differences in creep strain values and spatial
scales for the heterogeneous shale between these two
methods.31,36 At present, it remains unclear whether nano-
indentation results are comparable with those from traditional
triaxial testing. Therefore, the relationship between the results
obtained from these two methods should be explored.
4. CONCLUSIONS
This study evaluated the mechanical parameters (the Young’s
modulus and hardness) and creep behavior of Longmaxi shale
via nanoindentation testing and investigated their sensitivities to
the indentation load and the loading strain rate.
(1) Nanoindentation tests using indentation loads of 2−400
mN obtained information on the mechanical properties of
bulk shale. The mechanical properties significantly
decreased as load increased from 2 to 200 mN, but
remained relatively stable at 200−400 mN, suggesting
that the applied methodology and experimental con-
ditions can influence the measured mechanical properties
of bulk shale.
(2) The mechanical properties were more sensitive to the
indentation load than to the loading strain rate. Increasing
the indentation load (from 2 to 400 mN) initially
decreased the Young’s modulus and hardness. In contrast,
both parameters increased slightly as the loading strain
rate increased from 0.005 to 0.100 s−1.
(3) Both the indentation creep (CIT) and the creep strain rate
sensitivity (m) were positively dependent on the
indentation load, whereas they were negatively dependent
on the loading strain rate.
(4) Values of m varied from 0.040 to 0.124, suggesting that
dislocation power-law creep is the main mechanism
controlling deformation of the shale.
In summary, optimizing the indentation testing method for
shale will provide fundamental experimental data for better
understanding and predicting shale mechanical deformation and
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fracturing performance. However, because of the heterogeneity
and anisotropy of shale, the mechanism controlling its creep
deformation remains unclear. Further experimental and
theoretical research in the field is still required to understand
the various factors influencing the creep mechanism, including
the mineral compositions of the shale and in situ reservoir
conditions (i.e., temperature and fluid).
■ AUTHOR INFORMATION
Corresponding Author
Chao Yang − Key Laboratory of Natural Gas Hydrate,
Guangzhou Institute of Energy Conversion, Chinese Academy
of Sciences, Guangzhou 510640, China; orcid.org/0000-
0002-9716-900X; Email: yangchao@ms.giec.ac.cn
Authors
Jianfeng Wang − State Key Laboratory of Organic
Geochemistry, Guangzhou Institute of Geochemistry, Chinese
Academy of Sciences, Guangzhou 510640, China; University
of Chinese Academy of Sciences, Beijing 100049, China
Yuke Liu − Research Institute of Petroleum Exploration &
Development, Beijing 100083, China
Yun Li − State Key Laboratory of Organic Geochemistry,
Guangzhou Institute of Geochemistry, Chinese Academy of
Sciences, Guangzhou 510640, China; CAS Center for
Excellence in Deep Earth Science, Guangzhou 510640, China
Yongqiang Xiong − State Key Laboratory of Organic
Geochemistry, Guangzhou Institute of Geochemistry, Chinese
Academy of Sciences, Guangzhou 510640, China; CAS Center
for Excellence in Deep Earth Science, Guangzhou 510640,
China; orcid.org/0000-0003-1483-4498
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsomega.2c01190
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the Special Fund for
Strategic Priority Research Program of the Chinese Academy of
Sciences (grant no. XDA14010102), the National Natural
Science Foundation of China (grant nos. 41802165 and
42002158), the Natural Science Foundation of Guangdong
Province (grant no. 2018A030313234), and the State Key
Laboratory of Organic Geochemistry, GIGCAS (grant no.
SKLOG202012). We would like to express our gratitude to Dr.
Yangcheng Zheng for his help with the scripts written in Python
for fitting creep curves. We also appreciate Editor Dr. Mohamed
Mahmoud and anonymous reviewers for their constructive
comments and suggestions that significantly improved this
manuscript. This is contribution No. IS-3166 from GIGCAS.
■
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