Journal of Petroleum Science and Engineering 205 (2021) 108935

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Journal of Petroleum Science and Engineering

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Alteration in micro-mechanical characteristics of wellbore cement fracture

surfaces due to fluid exposure
Ishtiaque Anwar a, Mahya Hatambeigi a, Kirsten Chojnicki b, Mahmoud Reda Taha a,
John C. Stormont a, *
a
University of New Mexico, Albuquerque, NM, United States
b
Sandia National Laboratories, Albuquerque, NM, United States

A R T I C L E I N F O A B S T R A C T

Keywords: The stiffness of wellbore cement fracture surfaces was measured after exposing to the advective flow of nitrogen,
Nanoindentation silicone oil, and medium sweet dead crude oil for different exposure periods. The test specimens were extracted
Wellbore cement from fractured cement cylinders, where the cement fracture surfaces were exposed to the different fluids up to 15
Micro-mechanical properties
weeks. A nanoindenter with a Berkovich indenter tip was used to measure load-indentation depth data, which
Fluid exposure
was used to extract the elastic modulus (E) and nano-hardness (H) of the cement fracture surfaces. A reduction in
Crude oil
the elastic modulus compared with an unexposed specimen were observed in all the specimens. Both elastic
modulus and nano-hardness for the specimens exposed to silicone oil were lower than specimens exposed to
nitrogen gas and varied with the period of exposure. The elastic modulus and nano-hardness of the specimens
exposed to crude oil were the lowest with a significant decrement with the exposure period. The frequency
distribution of the nanoindentation measurements shows that the volume-fraction ratio of the two types of
cement hydrated nanocomposites for both the unexposed and test specimens is about 70:30%. Phase trans­
formation beneath the indenter is observed for all of the specimens, with more obvious plastic deformation in
specimens exposed to crude oil. Analytical measurements (SEM, EDS, FT-IR, and XRD) on exposed cement
fracture surfaces reveal different levels of physical and chemical alteration that are consistent with the reduction
in stiffness measured by nanoindentation. The study suggests that cement stiffness will decrease due to crude oil
exposure, and the fracture will be sensitive to stress and pore pressure with time.

1. Introduction
Wellbores are used to provide subsurface access for a wide range of
operations, including fluid storage (Miyazaki, 2009), CO2 sequestration
(Watson and Bachu, 2008; Zhang and Bachu, 2011), geothermal energy
development (Shadravan et al., 2015), waste disposal, and oil/gas
exploration and production (Davies et al., 2014). Wellbores typically
consist of steel casing surrounded by a seal in the annular space between
the host rock and the casing. API class G cement, commonly known as
oil-well or wellbore cement, is used as a seal in wellbores because of its
resistance to reaction with sulfates, ideal density and setting time.
However, after exposure to wellbore conditions fluid pathways are often
formed in cement which reduce or sometimes compromise the wellbore
seal. Within a wellbore system, several potential leakage pathways have
been identified, including cement fractures, microannuli from
de-bonding at the cement-casing and cement-formation interface (Celia
et al., 2005; Watson and Bachu, 2009), and the porous corrosion product
that may exist in between cement and steel casing (Anwar et al., 2019a).
In all the cases, the wellbore cement is exposed to the leaking fluid
(Fig. 1).
A primary concern of wellbores with flaws is upward fluid leakage
from the storage cavern or underground reservoir. One indication of
wellbore leakage is the build-up of fluid pressure in the cemented
annulus at the surface, referred to as sustained casing pressure. It is a
widespread concern of many gas and oil wells (Zhang and Bachu, 2011;
Davies et al., 2014). Leakage upward through the wellbore annulus can
contaminate water-bearing formations, create hazardous surface con­
ditions, and compromise the functionality of the wellbore. In addition to
the environmental concerns of wellbore leakage, there are also safety
concerns. A leaking wellbore may lead to the accumulation of hazardous
or toxic fluid in the vicinity of the wellbore system. Toxic gases, such as
methane from oil/gas wellbores, may accumulate to significant

* Corresponding author.
E-mail address: jcstorm@unm.edu (J.C. Stormont).

https://doi.org/10.1016/j.petrol.2021.108935
Received 20 February 2021; Received in revised form 7 May 2021; Accepted 10 May 2021
Available online 19 May 2021
0920-4105/© 2021 Elsevier B.V. All rights reserved.
I. Anwar et al.
concentrations and cause both an asphyxiation and explosive hazards
(Armstrong and Mendoza, 2002).
For a leaky wellbore, the fluid transmissivity depends, in part, on the
stiffness of the flow path. A stiff path will retain asperities that preserve
the aperture geometry under stresses from the adjacent formation, from
within the casing or from pore pressures. An alteration in the cement
stiffness may alter the asperities and thereby significantly change the
fracture aperture and consequently the fracture permeability and the
leakage rate. As such, a better understanding of the alteration in stiffness
of the fracture walls adjacent to the fluid movement is essential.
Nanoindentation is well suited technique to characterize the micro-
mechanical properties, specifically stiffness, of cement fracture sur­
faces. The stiffness, the extent to which cement resists deformation in
response to an applied force, is related to the elastic modulus (E) of the
cement and cross-sectional area of the element experiencing the applied
force. If the area of the element experiencing the force remains constant,
then the wellbore cement stiffness depends only on E (Boresi et al.,
1993). In this paper we will use the cement stiffness and the elastic
modulus (E) interchangeably. The basic idea of nanoindentation is to
indent a sharp tip into a material surface and to measure the relevant
properties, E, from the response of the tip. Nanoindentation has been
previously used to characterize cementitious materials. The micro­
structural properties of cement paste at different water-to-cement paste
ratios determined from nanoindentation tests have been reported by
numerous authors (Domnich et al., 2000; Chen et al., 2010; Con­
stantinides et al., 2003; Constantinides and Ulm, 2004; Davydov et al.,
2011; Hughes and Trtik, 2004; Kim et al., 2013; Jones and Grasley,
2011) as water content is a known factor influencing cement stiffness.
The nanoindentation technique has been extended to evaluate
micro-mechanical characteristics of blended cement pastes such as
nanosillica, silica fume, fly ash, slag, and other cement-based materials
(Kim et al., 2013; Katsuki and Gutierrez, 2014; Griffin et al., 2014; Hu
et al., 2014; Zadeh and Bobko, 2013; He et al., 2013; Mondal et al.,
2010; Plassard et al., 2007). Nanoindentation was also used to identify
the micro-mechanical properties of the interfacial transition zone that
develops in between the aggregates/fiber reinforcement and bulk
cement paste (Xie et al., 2015; Wang et al., 2009; Moser et al., 2013;
Mondal et al., 2008, 2009; Allison et al., 2012).
Hydration is the totality of the complex chemical changes that occurs
when the anhydrous cement with necessary constituents is mixed with
water, resulting in hardened cement paste (Taylor, 1997). Most of the
previous major studies were focused on characterizing hardened cement
paste or understanding the significance of nanoparticles on cement
behavior. Investigations revealed that calcium-silicate-hydrate (C–S–H)
Fig. 1. A simplified diagram illustrating an example of oil-well or wellbore cement exposed to fluid in a leaky wellbore system.
2
Journal of Petroleum Science and Engineering 205 (2021) 108935
gel, the major hydration product of hardened cement paste (Larbi, 1993;
Jennings and Tennis, 1994), is present in cement surfaces as either a low
density (LD) or high density (HD) configuration, which are similar in
composition but different in packing density and thus stiffness (Con­
stantinides et al., 2003). The chemical alteration and permeability
variation of wellbore cement due to the presence of carbonated brines in
geologic CO2 storage sites has been reported by several researchers
(Walsh et al., 2013; Scherer et al., 2011; Duguid and Scherer, 2010;
Carey et al., 2007). Walsh (Walsh et al., 2014) incorporated the inves­
tigation on altered mechanical properties of reacted cement for nu­
merical modeling of permeability over time. However, none of the
studies were explicitly focused on quantifying the alteration in
micro-mechanical properties of cement due to fluids exposure in well­
bores storing liquid hydrocarbon. This information may be important for
understanding conditions in liquid hydrocarbon wells exhibiting behind
casing pressure. It may also inform future decisions around regulating
behind casing pressure in onshore liquid hydrocarbon wells, for which
there are no current regulatory requirements.
The objective of this study is to measure the stiffness of unexposed
and exposed specimens from cement fracture surfaces that have expe­
rienced advective fluid flow of different fluids which may be present in a
liquid hydrocarbon wellbore. To accomplish this objective, nano­
indentation measurements were made on cement fracture surface sam­
ples exposed to different fluids and for different periods. The measured
load-indentation depth data of the hydrated composites of the speci­
mens were used to extract the elastic modulus (E) and nano-hardness
(H). The hardness obtained will be termed as nano-hardness in the
rest of the paper, because H is measured here at the nano scale and may
differ from the conventional definition in which area is determined by
direct measurement of the hardness impression. Three different expo­
sure fluids were used: (a) nitrogen gas; (b) silicone oil as an inert fluid;
and (c) crude oil. To complement the nanoindentation measurements,
the physical and chemical alterations in the cement specimens due to
contact with the above fluids were identified using several analytical
measurements (SEM, EDS, FT-IR, and XRD).
2. Materials and methods
2.1. Specimen preparation
The cement paste consisted of API Class G Portland cement, silica
fume (BASF Rheomac SF100), plasticizer (BASF Glenium 3030), and
distilled water. The cement paste was mixed until a smooth and ho­
mogenous slurry was achieved with a water-cement ratio of 0.4. The mix
I. Anwar et al. Journal of Petroleum Science and Engineering 205 (2021) 108935

design was in accordance with ASTM C305-14. The cement mixes were
cured in a 55 ◦ C water bath for seven days and were stored until tested in
a 100% humidity curing room.
The hardened cement cylinders were prepared in the laboratory with
a nominal cured dimension of 152 mm in length and the outer diameter
of 75 mm. A single fracture was created using the Brazilian tensile test,
which divided the cylindrical cement samples longitudinally into two
equal halves. The samples were placed in a modified pressure vessel
(Anwar et al., 2019a) and subjected to a constant hydrostatic confining
stress while fluids flowed through the fracture. Radial stress was applied
to the specimen using hydraulic pressure behind a core holder sleeve,
integrated into the triaxial cell. Fluid flow tests were conducted at 25 ±
0.5 ◦ C under the confining stress of about 3.45 MPa, which corresponds
to the expected geostatic stress at a depth of about 175 m. The details of
the fluid flow tests are provided in supplemental section S1.
The test specimens for micro-mechanical characterization were then
extracted from the fractured surface of cement cylinders subjected to the
flow test, using a Buehler IsoMet low-speed cutting machine equipped
with diamond cut-off blade. The specimens were categorized as control
specimens or Blank with no fluid exposure; specimens group A, exposed
to nitrogen gas; specimens group B, exposed to silicon oil; and specimen
group C, exposed to crude oil. Table 1 lists all the specimens tested with
the type of fluid exposure, and fluid exposure period. The properties of
the liquids used are presented in supplemental section S2.
The specimens were first cast in acrylic to fit them into the nano­
indentation holder. The Buehler EcoMet 4 variable speed grinder-pol­
ishers with an AutoMet 2 powerhead, was used to metallographically
polish all of the specimens using a waterproofed diamond lapping film
pad. Pads of decreasing abrasiveness (125 μm, 70 μm, 30 μm, 9 μm, and
1 μm) were used in succession. The polishing of the specimen surfaces
was verified (up to 1 μm) using an automated surface profiler with a
contact-based stylus system (Anwar et al., 2021).
To obtain the mentioned fluid exposure period, specified in Table 1,
the specimens were stored in a sealable glass enclosure in the relevant
fluid under vacuum pressure right after the fluid flow test. Prior to
testing, all the specimens were cleaned using nitrogen gas to get rid of
any polishing debris and paste on the surface.
during the loading and unloading rate. The average specimen thickness
was approximately 0.8 mm, which is about 200 times the average
indentation depth (<4000 nm). As such, the measurements were ex­
pected to be free from substrate effect.
The test locations were positioned using a computer-controlled high
precision X–Y table with 0.01 nm resolution assisted by a microscopic
camera, and the entire series of required indentations were performed in
a single run using the InView computer program. Since the cement is a
heterogeneous material, measurements were performed on various lo­
cations of the specimen. Microscopic images of the indentation locations
were taken before and after the measurements in order to avoid any
existing or newly formed microcracks. The images were also helpful to
visually select uniform, polished and relatively less porous surfaces of
similar coloration, in order to minimize any abnormal variation in ob­
tained data. The selected regions are mostly a mixture of hydrated
phases with a presence of negligible unreacted clinker grains. The load-
indentation depth curve of every individual event was examined, and
any inadvertent indentation on porous material or pure un-hydrated
clinker grain was not incorporated in the results. Electron imaging
combined with energy dispersive spectrum analysis was used to choose
each of the indentation locations. The typical surface chosen for the
indentation is shown in Fig. 2. A total of 224 indentations were under­
taken on fourteen locations of each specimen with 4 × 4 = 16 mea­
surements on each location.
2.3. Load-indentation depth data interpretation
The principal outcome in the nanoindentation experiment is the
measurement of mechanical load and the indentation depth. The load-
indentation depth curve for the nanoindentation test of cement speci­
mens typically consists of a number of segments (Constantinides et al.,
2003; Schuh, 2006). The first is the approach segment, followed by a
constant loading rate segment. Subsequently, a short hold segment with
partial unloading may exist, followed by the unloading segment. All the
load-versus- indentation depth curve segments were observed in our
measurements and are graphically illustrated in Section 3.1. Any mea­
surement that encountered abnormal segments were discarded.

2.2. Nanoindentation

An iNano nanoindenter from Nanomechanics, Inc. was used with a

Berkovich tip, the same type of tip used by others to investigate the
microstructural characteristics of similar materials (Griffin et al., 2014;
Ulm et al., 2007). The nanoindenter is capable of applying a small load
on the order of 3 nN to the Berkovich indenter tip having a half angle of
65.27◦ . The instrument, together with the enclosure, was suspended on a
pneumatic antivibration table in a temperature-controlled room at
24.5 ◦ C. A constant stiffness method with a grid nanoindentation mea­
surement protocol was used for all ten specimens.
The indentation depth can be measured as low as 0.02 nm from the
instrument. A computer connected to the apparatus was used to
constantly monitor the load as well as the loading rates continuously

Table 1
List of the specimens tested.
Specimen Type of fluid exposure Fluid exposure period (weeks)

Blank None –
A1 Nitrogen gas 8
A2 10
A3 15
B1 Silicone oil (PMX 200) 8
B2 10
B3 15
C1 Crude oil (medium, sweet) 8
C2 11
Fig. 2. Scanning electron microscopic image of a sample location on cement
C3 15
specimen A1.

3
I. Anwar et al.
For any load – depth sensing indentation method, including nano­
indentation, the reduced (combined) modulus of elasticity, Er can be
estimated using the following equation derived from the Hertzian theory
of contact mechanics (Timoshenko et al., 1951),
√̅̅̅̅
1 1 − ϑ2 1 − ϑ2i 2 A
= − = √̅̅̅ , (1)
Er E Ei S π
where E is the modulus of elasticity for the test specimen, ϑ is the
Poisson’s ratio of the test specimen, ϑi (= 0.07) is the Poisson’s ratio of
the indenter, A is the projected area of the indentation, S is the experi­
mentally measured stiffness (unloading stage), and Ei (= 1141 GPa) is
the modulus of elasticity for the indenter. The Poisson’s ratio (ϑ) of the
wellbore cement varies in between 0.15 and 0.20 (MohdZulkarnain,
2015). For the current measurements ϑ was assumed to be 0.2. It should
be noted that the effect of Poisson’s ratio on modulus of elasticity and
hardness of the test specimen, within such a small range, is negligible
(Hu and Hassan, 2019).
For the Berkovich indenter, the contact area of the indentation, A can
be calculated from the following expression,
√̅̅̅
A = 3 3h2c tan 2 θ , (2)
where angle, θ = 65.27⁰ (for the Berkovich indenter used in this
experimental study) and hc is the vertical depth along which contact is
made by the indenter.
The elastic deflection of the specimen surface at the contact point
(hs) at the maximum or peak indentation load (Pmax) is
Pmax
hs ​ = ε , (3)
S
where ε is a constant, which is 0.75 for the Berkovich indenter. Together
with the value of S, the vertical depth along which contact is made, hc =
hmax – hs, can be obtained for computing the contact area of the
indentation, A.
Elastic modulus (E).
The stiffness, S in Equation (1) is required for computing E following
the procedure described by Oliver and Farr (Oliver and Pharr, 1992),
where the initial 60% of the unloading curve is fit to the power function,
P = B(hmax − ​ hf )m to determine S (= dP/dh),
S=
dP
= mB(hmax − ​ hf )m− 1 , (4)
dh
where dP is the applied load, dh is the measured indentation depth, hf is
the imprint depth after complete unloading, and hmax is the total depth
of indentation at the maximum load (Pmax). The parameters are precisely
recorded by the instrument. B and m are coefficients which are found by
fitting the unloading curve data to Equation (3) using least square fitting
method by the InView computer program. As the unloading curves are
not linear, the manual measurements of S computed from linear fit of the
upper one-third of the unloading curve will introduce a substantial
error.
Nano-hardness (H).
The nanohardness is also calculated according to the Oliver and Farr
method (Oliver and Pharr, 1992). From definition, the value
nano-hardness can be calculated using the following equation (Brinell,
1901),
H = Pmax /A (5)
The maximum penetration depth in each test was hmax = 3–6 μm,
which indicates that the obtained cement characteristics in this study
are representative of a microscale length of the cement material.
2.4. Additional analytical tests
Scanning electron microscope imaging, energy-dispersive X-ray
4
Journal of Petroleum Science and Engineering 205 (2021) 108935
spectroscopy, Fourier transform infrared spectroscopy, and X-ray
diffraction measurements were made on the exposed specimens for
further characterization and to better understand the nanoindentation
test results. The analytical measurements were undertaken without any
confining stress and at ambient temperature. We have compared the
results from the analytical measurements with the results of the same
test on unexposed or Blank specimens available in existing literature.
Brief descriptions of the selected methods are presented below.
Scanning electron microscope SEM images of the cement speci­
mens were taken for identifying the locations before and post nano­
indentation. Images were used to verify the existence of any anomalies
in the nanoindentation test spots and the post-test phase transformation.
This technique has been used to study cement structures by numerous
researchers (Feng et al., 2004; Stutzman, 2004; Kjellsen and Jennings,
1996). A Tescan Vega III SEM was used to create images of specimens.
The images were taken in a low vacuum system. The stage holding the
specimens was controlled using a computer. To increase the detection
sensitivity, Low-energy backscatter (LE-BSE) SEM detection was used
during imaging of the specimens.
Energy-dispersive X-ray spectroscopy The EDS technique detects
x-rays emitted from the exposed specimens during SEM imaging to
characterize the elemental composition. An energy-dispersive detector
was used to separate the X-rays of different elements into an energy
spectrum, which was then analyzed using a specialized computer pro­
gram. In the present study, energy dispersive spectroscopy (EDS) is used
as a known useful tool in unveiling the elemental composition of
cement. Researchers have used the same technique successfully for the
elemental analysis of different types of cement (Lin et al., 1997; Cocke
et al., 1992).
After the nanoindentation, the specimens were nano-coated with
carbon and examined with a Tescan Vega III SEM outfitted with EDS
sensors. Backscattered electron (BSE) imaging in conjunction with EDS
analysis was used to identify the compositions of the specimen surfaces
in which indents were formed. Conditions used were a working distance
of 15 mm and an accelerating voltage of between 10 and 15 kV for BSE
imaging. A low vacuum technique was used for SEM imaging to avoid
the need for specimen coating. The EDS analysis was undertaken on all
three specimen categories.
Fourier Transform Infrared Spectroscopy This technique mea­
sures the absorption of infrared radiation by the test specimen. The
produced infrared absorption bands are sensitive to individual chemical
bonding and can be used as a fingerprint to help recognize the molecular
bonds and thus identify the chemical components in the specimen. The
FT-IR data were obtained using a Nicolet 6700 spectrometer (Thermo
Fisher Scientific Inc.). It was equipped with a deuterated triglycine
sulfate (DTGS) detector and was controlled by OMNIC software. The
equipment was calibrated using the internal calibration routine, and the
corrections were applied to the detector output. The background spec­
trum was collected at an ambient atmosphere prior to the analysis of
each specimen. The spectra of hardened specimens were corrected with
a linear baseline. The spectra obtained for the mid-infrared region (both
functional group and fingerprint region) includes the range of wave­
numbers from 4000 cm− 1 to 400 cm− 1. Most of the bands of the clinker
minerals are within 1100–500 cm− 1. Attenuated total reflectance or
ATR FT-IR were conducted for three types of specimens – A1, B1, and C1
(of the same age).
X-ray diffraction This technique has been used to study the alter­
ations of crystalline phases (Lin et al., 1997). The analysis provides a
measurement of the angles and intensities of the diffracted X-ray beams,
which can be used to obtain the chemical bond information. XRD has
also been used to obtain the structural footprint of the unknown (Car­
tledge et al., 1989). Alterations in the wellbore cement fracture surface
caused by fluid exposure will be characterized by comparing the XRD
diffractograms (Le Saout et al., 2006).
Measurements were performed for exposed cement specimen sur­
faces using the Rigaku Smartlab system that used CuKα radiation with a
I. Anwar et al.
wavelength of ʎ = 0.154 nm to record the diffraction measurements. The
system was coupled with a computer program to automate the specimen
alignment. The operation of this system functioned under the open
attenuator of 40 kV and 40 mA with optimization for scattering angles,
ϕ, of 5⁰< ϕ < 140⁰. The XRD spectra were acquired in about 16 min with
a rate of 8⁰/m. The information obtained from the EDS was re-sorted
using the Joint Committee of Powder Diffraction (JCPDS) pattern
numbers, to identify the materials of different compositions. One spec­
imen was used of each of the three specimen categories (A3, B3 and C3)
for the comparative study.
3. Results and discussion
The nanoindentation measurements of the hardened cement speci­
mens presented in this section reveal the alteration in micro-mechanical
properties of cement after being exposed to advective fluid flow.
Comparative studies from the additional analytical measurements are
presented to better understand the alteration in chemical, physical and
mechanical characteristics of the exposed cement specimens.
3.1. Nanoindentation measurements
Nanoindentation tests were conducted on the hydrated composites of
exposed and unexposed wellbore cement specimens. As mentioned
before, any indentation on the unhydrated composites or unpolished
cement surface was not used in this study. Fig. 3 presents the median
load vs. indentation curves obtained from the nanoindentation test for
the Blank as well as the specimens exposed to three different fluids.
Observing the median plot of the nanoindentation measurements, it is
reasonable to infer that the response of the cement specimens (peak load
and indentation depth) are different and exposed specimen surfaces are
softer than the Blank. The dispersion in shapes and slopes of the load-
indentation curves was observed, which suggests an alteration in the
surface (Schuh, 2006). The median plot of load vs. indentation curves in
Fig. 3 shows the parameters obtained for the calculations described in
section 2.3.
As described earlier, the load - indentation depth curve shows three
segments – the elastic-plastic loading, hold period to diminish time
dependent plastic effects followed by the elastic unloading zone. The
curves also showed the local perturbation caused by energy-absorbing/
releasing phenomenon of elastic-plastic material.
Numerous nanoindentation measurements were made on cement
specimens, a heterogeneous material that mainly includes different
hydrated composites. The frequency distribution of the results is also
Fig. 3. Median load vs. indentation curves obtained from the nanoindentation
tests for the Blank and specimens A1, B1 and C1, exposed to three different
fluids - nitrogen gas, silicone oil and crude oil.
5
Journal of Petroleum Science and Engineering 205 (2021) 108935
graphically displayed in by means of histograms for further under­
standing of the alteration in the type and stiffness of the calcium-silicate-
hydrate (C–S–H) gels, major hydration product of hardened cement
paste (Larbi, 1993; Jennings and Tennis, 1994).
Fig. 4 and Fig. 5 show the histogram of elastic modulus and nano-
hardness extracted from all of the nanoindentation test results ob­
tained for the experimental investigation on the hydrated composites of
the blank and specimens exposed to three different fluids – nitrogen gas,
silicone oil and crude oil. All nanoindentation test data distributions
exhibit two normal distribution curves combined, showing two peaks.
Such distributions indicate the presence of two different material types
in the test specimens. Hence, the bi-modal structure frequency distri­
bution can be attributed to two different types of C–S–H known as low
density (LD) and high-density (HD) C–S–H reported by others (Con­
stantinides and Ulm, 2004; Tennis and Jennings, 2000; Jennings, 2000).
The elastic modulus extracted from nano-indentation of blank speci­
mens was found to be 22.5 ± 1.6 GPa (for LD-C-S-H) and 29.6 ± 1.5 GPa
(for HD-C-S-H), which agrees well with the reported values of E found to
be 18–21 GPa (for LD-C-S-H) and 28–31 GPa (for HD-C-S-H) for type G
cement presented by Griffin et al. (2014).
The histogram showed in Figs. 4 and 5 can be represented by two
Gaussian curves and the values of E and H within the area can be
associated with the volume fraction of two types of hydrated compos­
ites. The volume-fraction ratio of the two types of C–S–H for the Blank is
roughly 70:30, which resembles the volume fraction provided for
cementitious material (for water to cement ratio of 0.5) available in the
literature (Tennis and Jennings, 2000; Jennings, 2000). The similarity in
the ratios of (LD-C-S-H and HD-C-S-H) on Blank and all other cements
exposed to Nitrogen, silicone oil and crude oil suggests that no major
chemical alteration took place and that the chemical or/and physical
alterations do not affect the volume fraction of the gel structured hy­
drated composites. Nevertheless, an obvious reduction in the mean
value of both E and H can be observed for cement surfaces exposed to
silicone oil and crude oils when compared with blank cement. Inde­
pendent sample t-tests were undertaken to check if the differences in
obtained values of E and H are reliable. Using student t-statistics, it was
observed that the obtained values of P were less than 0.05 for all spec­
imen group comparisons. The obtained values of P were substantially
low (<0.02) for the specimen group B and C in comparison to Blank as
well as specimen group A. These results suggest that at 0.05 level of
significance, the values of each group are different and lower than the
Blank. These statistical analyses also suggest that there is enough evi­
dence that the mean values of E and H (LD-C-S-H and HD-C-S-H of
wellbore cement) to be significantly lower for specimens exposed to
crude oil compared with Blank and cement specimens exposed to ni­
trogen or silicone oil.
Fig. 6 contains a summary of the micro-mechanical test data from the
depth-sensing nanoindentation experiments. Any inadvertent indenta­
tion on porous material or pure un-hydrated clinker grain was not
incorporated in the results.
Fig. 6 also shows that the reported values (both LD and HD hydrated
composites) of E for the specimen group A (A1, A2 and A3) are less than
Blank/control specimen. Under pressure, nitrogen gas may have caused
the drying of water from the embedded capillary pores in between the
C–S–H gel sheets. This physical phenomenon is known as D-drying
(Taylor, 1997). Thus, the reduction in stiffness may be attributed to the
loss of interlayer water of the C–S–H structure due to Nitrogen exposure.
A further reduction of the cement stiffness value, obtained from the
specimens A, was observed in specimen groups B and C, due to liquid
(silicone and crude oil) exposure and is presented in Fig. 6. The modulus
of elasticity decreased due to silicone oil exposure. This may result from
the physical displacement of interlayer/capillary water molecules by
silicone oil, which can cause a reduction in cement stiffness (Taylor,
1997).
Further reduction in E was also observed for the cement specimens C
that are exposed to the crude oil, a chemically active fluid as shown in
I. Anwar et al. Journal of Petroleum Science and Engineering 205 (2021) 108935

Fig. 4. Histogram of elastic nanoindentation results of the hydrated composites of wellbore cement (a) Blank with no fluid exposure, exposed to (b) nitrogen, (c)
silicone oil and (d) crude oil for about eight weeks.

Fig. 5. Histogram of nano-hardness measurements of the hydrated composites of wellbore cement (a) with no fluid exposure, exposed to (b) nitrogen, (c) silicone oil
and (d) crude oil for about eight weeks.

Fig. 6. This can also be attributed to the additional physical and chem­
ical alteration of the major hydrated products - the C–S–H gel and
crystalline compounds. If the hardened cement paste structure agrees
with the Feldman-Sereda model (Ramachandran and Feldman, 1996),
such alterations may change the physical properties of cement. This
hypothesis can be further examined using physical and chemical testing
of cement specimens exposed to crude oil as discussed below.
The nano-hardness (H) for all measurements are summarized in
Fig. 6. The maximum H was obtained for the specimens exposed to ni­
trogen gas. The hardness decreased due to the exposure to silicone oil
and crude oil. The minimum H was obtained for the specimens that
experienced the crude oil flow test. The nano-hardness of the Blank was
found to be 0.86 ± 0.18 GPa (for LD-C-S-H) and 0.94 ± 0.20 GPa (for
HD-C-S-H), which agrees with the reported values of 0.80 ± 0.20 GPa
(for LD-C-S-H) and 0.90 ± 0.30 GPa (for HD-C-S-H) for cement (Con­
stantinides et al., 2003).
From Fig. 6, it is evident that the values of H obtained from speci­
mens A, exposed to Nitrogen, are a little less than the H observed for
Blank. This might be attributed to the effect of the nitrogen pore pres­
sure on the cement leading to D-drying, resulting in the slight reduction

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I. Anwar et al. Journal of Petroleum Science and Engineering 205 (2021) 108935

chemical alteration taking place in cement during the exposure to crude

oil. The results of additional analytical measurements are presented in
the next sections to understand the alterations.

3.1.2. Phase transformation

The load-indentation depth curves (Fig. 7) obtained from the nano­
indentation tests show local perturbations or changes in volume of the
material beneath the indenter during the unloading stage. This may be
attributed to a material phase transformation that results in a volume
increase (Schuh, 2006). Such transformations are normally caused by
the large stresses beneath the indenter.
A similar phenomenon has been observed by other researchers. For
diamond-cubic semiconductors, Si and Ge, the mean contact pressure of
hardness indentation is quite close to the critical pressure to trigger
phase transformation (Gerk and Tabor, 1978; Clarke et al., 1988). Such
transformation is often called the pop-out phenomenon and commonly
observed during the unloading stage to the transformation of
high-pressure β-Sn phase to metastable body-centered cubic phase
(Domnich et al., 2000; Suprijadi et al., 2002). This transformation
causes a volume increase to work against the indenter tip, resulting in
the pop-out effect.
In our current investigation, phase transformation has been observed
in all of the specimens tested and found to be more obvious for the
specimens exposed to crude oil. As observed by Tachi et al. (Suprijadi
et al., 2002), such transformation is due to the involvement of plastic
deformation or flow under the indenter tip, which can affect the meta­
stable phase. This suggests that the specimen exposed to crude oil
exhibited relatively more plastic deformation than the other three types
of specimens, beneath the indenter. A sample SEM image of the spec­
imen C3 is presented in Fig. 8 for locations with one nanoindentation.
From the image, it can be observed that the material underneath the
indenter tip has been physically or chemically transformed.

3.2. Energy dispersive spectroscopy

A total of 120 EDS spectrum analyses were undertaken for each

specimen. A summary of all the EDS results for the wellbore cement
specimens - A1, B1, and C1, exposed to different fluids for eight weeks, is
given in Fig. 9. As shown in Fig. 9, the spectra for the specimen exposed
Fig. 6. The mean elastic moduli (E) and nano-hardness (H) and of (a) LD-C-S-H
to nitrogen gas (A1) shows that the wellbore cement contains Ca, O, Si,
(b) HD-C-S-H unexposed specimen (Blank) and exposed specimens to three
different fluids. Values reported at a 95% confidence interval (indicated as solid
line segments).

of hardness. Fig. 6 displays a further reduction in the nano-hardness of

the cement specimens exposed to liquid oils. The values of H decreased
due to the exposure of silicone oil, a chemically inert fluid. This may also
result from the replacement of interlayer water molecules by silicone oil,
which can cause a reduction in the hardness of the hydrated composite.
A further decrement in H was encountered for the specimen group C.
This can also be attributed to the additional physical and chemical
alteration of the major cement microstructural components as described
in the literatures (Taylor, 1997; Ramachandran and Feldman, 1996).

3.1.1. Effect of the exposure time period

Fig. 6 also shows the variation of modulus of elasticity and hardness
values with specimen exposure time. As shown in Fig. 6, the modulus of
elasticity is nearly constant for the specimen groups A and B, but the
value decreases with exposure time for specimen group C. The crude oil
consists of a variety of chemicals which may degrade the cement and
increase the plasticity of the material through some chemical process.
Similarly, the nano hardness is almost constant for the specimen groups
A and B, but the value decreases with increase in exposure time for Fig. 7. Two sample load-indentation depth curves, illustrating the phase
specimen group C. The variation in modulus of elasticity and hardness transformations for individual locations on the cement specimen after
with exposure time can be attributed to the continuous physical and fluid exposure.

7
I. Anwar et al.
Fig. 8. BSE Scanning electron microscope image of a cement specimen exposed
to crude oil with the nanoindentation footprint (Left). A zoomed-in view of the
material beneath the indenter displaying the local perturbation (Right).
Fig. 9. Summary of SEM-EDS analysis for specimens – A1 (nitrogen exposed),
B1 (silicone oil exposed), and C1 (crude oil exposed). Values reported at a 95%
confidence interval (indicated as solid line segments).
Al, C as dominant elements. The results are in agreement with the
characteristic features found by Hughes et al. (1995). The nanocoating
(required for better SEM imaging) of the cement specimens has caused
the existence of carbon in specimen groups A and B. The cement spec­
imen exposed to hydrocarbon displayed a substantially higher concen­
tration of elements containing carbon than the other two specimens
exposed to nitrogen gas and silicone oil, respectively.
From the EDS observations, the dissimilarity in elemental composi­
tion among the three types of specimens is observed. It is evident that
the weight percentage of the dominant elements of wellbore cement
specimens have been altered due to liquid exposure. The EDS spectra of
the specimens is presented in Fig. 10. The increasing concentration of
chemical elements with silicone may have caused the physical replace­
ment of molecular water from the capillary pores. A decrease in the CaO
to SiO2 ratio (Figs. 9 and 10) is encountered in the specimen B1, which
can affect the strength and stiffness of hydrated wellbore cement.
Similarly, for the specimen, C1, a substantial decrease in weight per­
centage of Ca is observed, which results in a significant decrease of CaO
to SiO2 ratio (Figs. 9 and 10). The results also confirm a substantial
decrease in unreacted C3A and C4AF in the specimen exposed to crude
oil.
The increasing concentration of chemical elements with carbon
identified in the spectrum may have been caused by the physical
replacement of the cement molecular water from both interlayer and
adsorbed off the hydrated composite gel structures. Furthermore, a
8
Journal of Petroleum Science and Engineering 205 (2021) 108935
Fig. 10. A sample energy dispersive spectrum, indicating the elemental
composition for specimens - A1 (nitrogen exposed), B1 (silicone oil exposed),
and C1 (crude oil exposed).
substantial increment in Carbon concentration also suggests that the
relatively small carbonate molecules (amorphous material) replaced the
relatively bigger molecular volume after a complex chemical reaction
and caused a further reduction in E and H of the specimen.
3.3. Fourier transform infrared (FT- IR) spectroscopy
The spectra of exposed cement specimens for eight weeks - A1, B1,
and C1 are presented in Fig. 11. Dashed line in the figure represents the
demarcation between functional group and fingerprint regions.
3.3.1. Functional group region
Within the functional group region, the obtained IR spectra was
compared with the IR spectrum for API Class G cement reported by
Hughes et al. (1995). A peak at approximately 3450 cm− 1 is an indica­
tion of symmetric and antisymmetric stretching vibrations of adsorbed
water molecules while the same band for free water molecules in the
vapor phase appears at about 3700 cm− 1 (Hughes et al., 1995; Farmer,
1974). However, none of the spectra clearly showed such a response
which can be attributed to physical drying of capillary pores (D-drying)
and/or molecular water of hydrated C–S–H gel.
Furthermore, for all three specimens the band for the O–H bond
shifted to a lower energy level and different frequency peaks were
observed at different wave numbers. The displacement covalent O–H
bonds from the hydrated composites can cause such a response. The shift
can be attributed to the alteration in O–H bond which can affect the
portlandite: Ca(OH)2, ettringite and other hydrated products contrib­
uting to the strength of wellbore cement.
Multiple peaks have been observed at about 2360 cm− 1 for A1, which
indicates the presence of N–N bond stretching vibrations (Verdes et al.,
I. Anwar et al. Journal of Petroleum Science and Engineering 205 (2021) 108935

3.4. X-ray diffraction

The phase identification for specimens - A3, B3, and C3 respectively,

at ambient temperature (23 ± 0.5 ◦ C) and atmospheric pressure, using
XRD are presented in Fig. 12. The results obtained from XRD analysis
were compared with a previous study (Le Saout et al., 2006) undertaken
on wellbore cement not exposed to any advective fluid flow. The dif­
fractogram obtained by Le Saout et al. (Le Saout et al., 2006) is used to
compare the variation in wellbore cement minerology due to the
exposure of fluids.
The specimen exposed to nitrogen gas (A3) shows that the wellbore
cement (API class G) contains un-hydrated phases – alite C3S (Hatrurite),
belite C2S, ferrite phase C4AF (Brownmillerite), and usual hydrated
phases such as portlandite and ettringite. Based on the peak intensity,
width and position, as observed on the diffractogram presented in
Fig. 12, no substantial change or alteration of the un-hydrated clinker
phases such as C3S, C2S, C4AF, etc. was observed due to the exposure of
nitrogen and silicone exposure. Minor changes in the peak intensities of
the un-hydrated clinker phases indicates alteration in the crystal lattice
due to the exposure of crude oil.
The diffuse peak in the diffractogram at 0.27–0.31 nm (2θ = 29.8⁰ –
30⁰) is attributable to hydrated phases – exposed C–S–H. The change in
the peak position and intensity is observed for the specimens exposed to
silicone and crude oil, which indicates the repositioning of atoms as well
as change in microstructures of the hydrated cement product. An
increased amount of calcite is encountered in specimen C3. Further­
more, the peak at 0.71–0.81 nm (2θ = 11⁰ – 12.5⁰) of the diffractogram
in Fig. 13, displays the presence of amorphous materials (mainly gypsum
and lizardite) for the specimen C3. An elevated amount of calcite or
CaCO3 (2θ = 23⁰) has also been observed, which may result from com­
plex chemical alterations of Ca(OH)2 and C–S–H with crude oil. Similar
to the findings from FT-IR measurements, alteration of the O–H bond
can affect the hydrated product of the cement. Again, this process of
replacing larger hydroxide molecules with relatively small carbonate
molecules decreases the strength by reducing the relative volume. The
alteration, as mentioned above, may contribute to the significant
Fig. 11. ATR FT-IR spectrum of wellbore cement exposed for about eight weeks
reduction in E and H of the specimen exposed to crude oil.
- A1 (nitrogen exposed), B1 (silicone oil exposed), and C1 (crude oil exposed).

3.4.1. Comparative study on the analytical measurements

1999). Several peaks were also observed at about 2830 cm − 1 for B1, due
Alteration in the chemical composition of wellbore cement due to
to multiple functional groups of silicon. Peaks in vibrational frequency
fluid exposure was observed in the elemental compositional analysis
were observed at around 2956 cm − 1 for C1, which can be assigned to
from EDS. The ratio of the dominant elements of cement specimens have
the asymmetrical and symmetrical stretching vibrations of methyl and
been changed due to the exposure to advective flow of fluids. Based on
methylene groups of alkyl chains. Similar response was reported for the
IR spectrum of asphaltene, a major component of crude oil (Buenros­
tro-Gonzalez et al., 2002).

3.3.2. Fingerprint regions

The frequencies within the fingerprint region describes the charac­
teristics of the molecule as a whole. However, the functional groups in
the molecule can affect the vibrations as well, making the section of the
IR spectrum less reliable for identification. The fingerprint regions of the
IR spectra contain many peaks that account for a large variety of single
bonds in cement. No significant variation in the spectra were observed
for the specimens A1 and B1, which suggests that no significant physi­
ochemical alteration occurred at the molecular level. However, the re­
gion 1100 to 500 cm− 1, which typically includes most of the vibrational
frequencies from the clinker minerals, is increasingly distorted for
specimens C1. The comparison of peaks with the frequencies of speci­
mens A1 and B1, suggests the material alteration at the molecular level
occurred due to crude oil exposure. The peaks of the obtained IR spectra
(functional group and fingerprint region) of Specimen group C is
different from other IR Spectra, which suggests that the crude oil
exposure chemically altered the hydrated composites of cement.
Fig. 12. X-ray diffractograms (CuKα Radiation) of wellbore cement for speci­
mens – A3 (nitrogen exposed), B3 (silicone oil exposed), and C3 (crude
oil exposed).

9
I. Anwar et al. Journal of Petroleum Science and Engineering 205 (2021) 108935

may translate into a constant leakage rate) will not be appropriate

without considering both the exposure time period and the type of fluids
in the fracture.
Phase transformation is observed for all the specimens, with more
obvious plastic deformation in specimens exposed to crude oil. The re­
sults suggest that cement fracture surfaces exposed to crude oil will
become increasingly compressible and more sensitive to confining stress
and pore pressure the longer the exposure lasts.
The outcomes of the additional analytical measurements (EDS, FT-
IR, and XRD) demonstrate the physical and chemical alteration of
wellbore cement that may result in the reduction in stiffness and nano-
hardness of the cement. Alteration in the chemical composition of the
cement due to fluid exposure was observed. Physiochemical change of
the cement was observed for all three specimens exposed to fluids, and
the modification was significant and up to the molecular level in spec­
imens exposed to crude oil. No significant chemical change of the un-
Fig. 13. A zoomed in view of the X-ray diffractogram (2θ = 11⁰ – 12.5⁰) -well
hydrated clinker grains was spotted due to the nitrogen and silicone
cement for specimens – A1 (nitrogen exposed), B1 (silicone oil exposed), and C1
(crude oil exposed).
oil exposure. An increased amount of calcite deposition and minor
alteration in the lattice arrangement were observed due to crude oil
exposure. Changes in the microstructures of the hydrated substance
the spectra of the bond vibrational frequencies, physiochemical alter­
were observed due to silicon and crude oil exposures.
ation is observed for all three cement specimens exposed to fluids, and
At present, the assessments of wellbore leakage repair techniques do
the change was significant in specimens exposed to crude oil. Similar to
not factor in the alteration in micro-mechanical characteristics of
the findings from the elemental compositional analyses using EDS, the
cement due to fluid exposure, mainly liquid hydrocarbons, which may
FTIR spectrum displays the drying (for nitrogen gas exposure) or the
significantly impact the success of common remediation efforts. A
replacement of capillary pore/molecular water (for silicone and crude
significantly high injection pressure may open up the fracture, flatten
oil exposure). A reduction in OH bond and the formation of new bonds
the fracture asperities or create additional cracks due to the reduced
were observed in the functional group region. The comparison of the IR
stiffness, can make the remediation infeasible by triggering unknown
spectra obtained from ATR-FTIR, especially in the fingerprint region,
consequences. Innovative techniques to repair leaky wellbores using
suggests an alteration of the cement at the molecular level.
materials similar to the cavern fluids with no injection pressure, such as
Together with the findings from the EDS investigation, the dif­
asphaltene based sealant transported utilizing electric potential differ­
fractogram from XRD analyses allows us to investigate the crystalline
ence (Anwar et al., 2019b) are recommended.
phases in hardened wellbore cement. No significant change in the
Further study is recommended using different/multiple fluids (e.g.,
chemistry of the clinker grains (un-hydrated) was detected due to the
mineralized water) from different sources together with additional
nitrogen and silicone oil exposure. However, similar to the FTIR ana­
analytical measurements in order to comprehend if a systematic rela­
lyses, a minor alteration in the lattice arrangement was observed in the
tionship exists between the cement (hydrated composites) stiffness and
XRD diffractograms of specimens with crude oil exposure. A decrease in
duration of fluid exposure. The analytical measurements in this study
the unreacted C3A and C4AF in the cement specimen C suggests a
(SEM, EDS, FT-IR, and XRD) were undertaken without any confining
chemical interaction in between wellbore cement and active compo­
stress. Future investigations should include analytical measurements
nents of the crude oil, under pressure. Changes in the microstructures of
under confining stress that may reveal different physical and chemical
the crystalline hydrated substances were observed due to liquid (silicone
alteration of wellbore cement due to fluid exposure. The effects of fluid
and crude oil) exposure. Furthermore, an increased amount of calcite
exposure on the other components other than the hydrated compositions
was encountered in the specimen exposed to crude oil.
have not been investigated in this paper but can also be pursued in a
future study.
4. Conclusion
Declaration of competing interest
The micro-mechanical characterizations of wellbore cement speci­
mens were evaluated in this study to determine the effect of liquid
The authors declare that they have no known competing financial
exposure on cement stiffness. The experimentally obtained values of E
interests or personal relationships that could have appeared to influence
and H for the hydrated composites of the specimen group C are found to
the work reported in this paper.
be the minimum. Whereas the values of E and H for the specimen group
B are greater than specimen group C but smaller than the specimen
Acknowledgments
group A and Blank (without any fluid exposure). Based on the study, the
reduction in wellbore cement stiffness adjacent to the fracture is not
This work was completed as a part of the Strategic Petroleum Reserve
always constant and depends on the type of fluid the cement is exposed
(SPR) wellbore flow project and was funded by Sandia National Labo­
to. The present study also reveals that the movement of crude oil
ratories. Sandia National Laboratories is a multi-mission laboratory
through a cement fracture of a leaky wellbore can substantially decrease
managed and operated by National Technology & Engineering Solutions
the cement stiffness in the areas adjacent to the flow. Such a reduction
of Sandia, LLC, a wholly owned subsidiary of Honeywell International
can dramatically alter the fracture asperities and, thus, how the fracture
Inc., for the U.S. Department of Energy’s National Nuclear Security
responds to stress, crack propagation and, eventually, the leakage rate.
Administration under contract DE-NA0003525. This paper describes
The elastic modulus and nano-hardness decrease with the period of
objective technical results and analysis. Any subjective views or opin­
exposure for all of the specimens exposed to nitrogen and silicone oil,
ions that might be expressed in the paper do not necessarily represent
but the values significantly decrease with increased exposure time for
the views of the U.S. Department of Energy or the United States Gov­
the specimens exposed to crude oil. Thus, the stiffness of the asperities,
ernment. SAND2021- 5728J.
that hold the fracture geometry, is also dependent on the exposure time
period. Hence, the assumption of constant hydraulic aperture (which

10
I. Anwar et al. Journal of Petroleum Science and Engineering 205 (2021) 108935

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