Journal of Petroleum Science and Engineering 170 (2018) 218–230

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Journal of Petroleum Science and Engineering

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Effects of magnesium oxide on carbonic acid resistance of oil well cement T

∗
Aman Srivastava, Ramadan Ahmed , Subhash Shah
University of Oklahoma, 100E. Boyd St., Norman, OK, 73019, USA

A R T I C LE I N FO A B S T R A C T

Keywords: This paper presents the results of an experimental study on the effects of magnesium oxide additive on the
Oil well cement performance of oil well cement under a high-pressure high-temperature (HPHT) carbonic acid environment.
Magnesium oxide Magnesium oxide (MgO) is a well-known expanding agent that improves sealing performance of cement.
Carbonation However, the performance of MgO-based cement has not been tested in a carbonic acid environment. Therefore,
Degradation
to investigate the impact of MgO on carbonic acid resistance of cement, two cement slurry formulations: Class H
Expansion
Porosity
cement with 35% silica (baseline or HS) and baseline cement with MgO (HSMG) were compared after exposure
to an acidic environment. To evaluate their performance, cylindrical cores and shear bond strengths (SBS)
samples were prepared and aged in HPHT autoclave containing brine (2% sodium chloride solution) saturated
with mixed gas containing CH4 and CO2. Six aging tests were conducted varying CO2 concentration, tempera-
ture, and pressure. After aging for 14 days at constant pressure and temperature, the samples were recovered,
and their physical (bond and compressive strength, porosity and permeability) and mineralogical composition
were measured and compared with those of unaged samples. The results suggest that addition of 5% MgO
reduces the carbonation of cement and could potentially prolong the operational life of cement by protecting its
binding components (calcium hydroxide and calcium silicate hydrate).

1. Introduction
Cement is extensively utilized in various industrial applications. In
the petroleum industry, it is applied in well construction applications.
Cement is mainly required to support steel casings and seal the annular
space between the casings and wellbore. As a result, it isolates different
formations from one another and the surface. Cement also protects the
casing from corrosion. Zonal isolation is maintained by preserving the
original sealing performance of cement. Porosity, permeability, and SBS
are properties that have a major impact on its sealing performance.
Cement degradation can be caused by mechanical or chemical process
or both. Mechanical degradation happens due to excessive loads re-
sulting from casing ballooning, thermal expansion and volume change
during hydration. In addition to mechanical deterioration (reduction of
compressive strength and SBS), cement is prone to chemical attack.
Cement exposed to acidic fluids undergoes a combination of physico-
chemical reactions. Depending on the composition of the surrounding
fluid, various level of cement degradation can occur. The degradation
often substantially changes the sealing and structural performance of
cement.
Currently, oil and gas production from resources containing a sig-
nificant amount of CO2 is expanding. A considerable amount of the
world's remaining gas reserves contain more than 2% acidic gases such
as CO2 (Lecolier et al., 2008). In gas injection wells, the concentrations
of acidic gases can be substantial (Fakhreldin et al., 2010). Further-
more, several projects have been embarked upon on carbon capture and
storage (CCS) in various parts of the world. Successful storage of carbon
dioxide in geological formations requires cement formulations that can
keep the injected CO2 within the formation for long periods of time.
Appropriate cement formulations require careful selection of additive
materials that prevent acid attack.
Oilfield cement is vulnerable to acid attack and harsh downhole
environments. Different physicochemical mechanisms are involved in
the deterioration of cement properties. Very limited studies have been
conducted to develop acid resistant cement that can be applied in the
development of CO2 containing gas resources. Published data on de-
gradation mechanisms of cement-based materials exposed to a CO2
environment are very scarce (Fakhreldin et al., 2010). More studies are
needed to better understand the impact of additives such as MgO on the
degradation of oil field cement and ensure long-term well integrity.
2. Literature review
2.1. Cement degradation
In the presence of water and CO2, cement is exposed to carbonic

∗
Corresponding author.
E-mail address: r.ahmed@ou.edu (R. Ahmed).

https://doi.org/10.1016/j.petrol.2018.06.059
Received 1 March 2018; Received in revised form 18 June 2018; Accepted 20 June 2018
Available online 21 June 2018
0920-4105/ © 2018 Elsevier B.V. All rights reserved.
A. Srivastava et al.
acid resulting in deterioration of its properties (Santra and Sweatman,
2011; Benge, 2009; Gerard et al., 2002; Nakarai et al., 2006; Kutchko
et al., 2007; Duguid, 2009; Duguid et al., 2005; Moroni et al., 2009;
Gasda and Celia, 2005). During the acid attack, the binding components
of cement, calcium hydroxide (CH) and calcium silicate hydrate (CSH)
dissolve and react with carbonic acid to form CaCO3 crystals in the
pores. The degradation process of hydrated cement is represented by
the following chemical reactions:
CO2 + H2O → H2CO3 (1)
H2CO3 + Ca(OH)2 → CaCO3 + 2H2O (2)
CSH + H2CO3 → CaCO3 + amorphous silica + H2O (3)
CaCO3 + H2CO3 → Ca(HCO3)2 (4)
The degradation process involves: i) the dissolution of CO2 in water
and the formation of carbonic acid (Eq. (1)); ii) carbonation of CH and
CSH (Eqs. (2) and (3)); and iii) bi-carbonation of CaCO3 (Eq. (4)). Once
formed, the crystals of CaCO3 deposit in the pore space and throat,
reducing the Porosity and Permeability (PP) of cement. In the presence
of excess carbonic acid, CaCO3 converts to soluble Ca(HCO3)2, which
can be readily leached out from cement. The leaching increases porosity
and permeability and exacerbates the penetration of CO2 into the ce-
ment matrix by improving ionic diffusion (Santra and Sweatman, 2011;
Benge, 2009; Kutchko et al., 2007; Duguid, 2009; Moroni et al., 2009).
The process results in the development of a progressive degradation
front, which moves toward the center of cement matrix.
Another mechanism of cement degradation is direct leaching of CH
and CSH by the surrounding fluid (Nakarai et al., 2006). The leaching is
caused by the dissolution of CH and CSH into the surrounding fluid. The
dissolution process is mainly affected by the solubility of CH and CSH,
which is a function of brine and carbonic acid concentrations, and
temperature. The solubility of CH decreases with temperature. Al-
though the leaching is directly related to dissolution, its rate can be
controlled by the diffusion of ions in the pores, which is affected by
porosity and permeability of the matrix. Thus, carbonation, leaching,
and diffusion processes are strongly coupled, and significantly affect the
degradation of cement.
Cement degradation in the annulus can lead to micro-channeling
and loss of zonal isolation, resulting in an undesirable flow of formation
fluid among various zones and corrosion of the casing. Gasda and Celia
(2005) presented possible scenarios of oil well zonal isolation failure.
The scenarios include micro-channeling between casing and cement,
high permeability leaky cement, micro-cracked cement, and corroded
and cracked casing. The degradation of cement leads to an unexpected
leakage in the wellbore and causes different well integrity issues. It is
necessary to understand the mechanism of degradation of cement and
simultaneously device methods to minimize it.
2.2. Cement expansion
One way of limiting cement degradation is reducing the initial
matrix porosity and permeability. The reduction restricts acid pene-
tration and lessens carbonation and subsequent leaching of CH and
CSH. Initial porosity and permeability of cement could be reduced by
the addition of additives that induce expansion. The additives should be
chosen such that they promote matrix expansion and pore shrinkage
during cement hydration and hardening. The expansion could help to
reduce the pore space in the matrix, diminishing the porosity and
permeability (Ghofrani and Plack, 1993). Gypsum and gypsum-con-
taining substances with high alumina binder or high alumina slag or
anhydrous calcium sulfo-aluminate results in quickly solidifying cement
which can expand. These additives are used in the construction industry
and are best suitable for a temperature range of 20–80 °C. Chromate
and aluminate additives are also used as expanding additives; however,
their swelling tendency reduces in the presence of brine (Agzamov
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Journal of Petroleum Science and Engineering 170 (2018) 218–230
et al., 2013). As reported by Rubiandini et al. (2005), Danjusevsky
(1983) proposed calcium oxide and magnesium oxide as expanding
cement additives. However, the expanding tendency of CaO diminishes
at higher pressures (Ghofrani and Plack, 1993; Rubiandini et al., 2005).
Hence, the current research is focused on studying the behavior of
magnesium oxide as a cement additive in a high-pressure acidic en-
vironment.
Magnesium oxide is known for its expanding tendency during ce-
ment hydration. A number of studies (Ghofrani and Plack, 1993; Ali and
Mullick, 1998; Cheung, 1999; Buntoro et al., 2000; Rubiandini et al.,
2005; Zhang et al., 2011, 2012; Nokken, 2010; Agzamov et al., 2013)
investigated the expansive property of MgO in cement. Expansion of
cement due to MgO was first reported in 1884 when some bridges in
France failed two years after their construction (Mehta and Monteiro,
2006). Around the same time, the town hall of Kassel (Germany) had to
be rebuilt due to expansion and cracking of cement. The cement during
that time contained 16–30% MgO. As a result, the maximum permis-
sible MgO has been restricted to 6% in Portland cement.
Industrially, magnesium oxide is produced by calcining magnesium
carbonate (MgCO3) or dolomite (CaMg(CO3)2). The calcination tem-
perature, its concentration in cement and curing temperature determine
its reactivity. The hydration process of MgO essentially involves the
formation of voluminous Mg(OH)2 crystals in pore space which results
in porosity reduction and swelling of the cement matrix (Rubiandini
et al., 2005). To reduce porosity and permeability, swelling must occur
in parallel with cement hydration. Early expansion during the slurry
phase has little impact on the properties of set cement and its ultimate
characteristics. Expansion happening after the complete cement hard-
ening is undesirable because it causes the cement to crack. Hence, ex-
pansion needs to occur during the gelling or curing phase of cement so
that its porous space is effectively reduced (Ghofrani and Plack, 1993).
The level of expansion increases with the amount of MgO in cement
(Zhang et al., 2012). Also, fine MgO leads to a higher early expansion of
cement while MgO with coarse particles results in a significant expan-
sion in late-stage (Zhang et al., 2011). This means that the hydration
rate of MgO increases with decreasing particle size. This phenomenon is
more pronounced in high-temperature calcined MgO.
Despite a number of studies (Ghofrani and Plack, 1993; Rubiandini
et al., 2005) on magnesium oxide, the full extent of its benefit is not
well realized. This is because the hydration rates of cement and mag-
nesium oxide are highly dependent on the number of factors including
cement composition, concentration, and fineness of MgO, curing tem-
perature, pressure, composition, and properties of surrounding fluid. In
addition, a calcination temperature of MgO affects its hydration rate. A
calcination temperature of greater than 900 °C reduces the reactivity of
MgO and makes it to hydrate gradually. MgO calcined less than 900 °C
hydrates quickly, resulting in early stage expansion of cement (Ivan,
2000).
Nokken (2010) presents several case studies showing how the ef-
fectiveness of MgO as an expanding agent is evaluated. Different ex-
pansion measuring methods were discussed. Although the article dis-
cusses the applicability of the methods under various conditions, all the
measurement techniques show some level of expansion after hydration
of MgO cement. The results indicate that matrix expansion can be
achieved by the addition of MgO. The hydration rate of MgO is directly
related to the level of cement expansion. Measurements (Nokken, 2010;
Pang et al., 2013) presented in Fig. 1 show cement hydration and vo-
lume expansion due to MgO addition can occur simultaneously if sui-
table curing condition and appropriate cement composition are selected
to synchronize cement hydration and MgO volume expansion. Other-
wise, expansion occurring after cement hardening cracks cement or
MgO becomes ineffective if most of the volume expansion occurs before
the cement begins solidifying.
The expansion of cement due to MgO improves the bonding strength
between cement sheath and casing and compressive strength
(Rubiandini et al., 2005). Experimental results (Ghofrani and Plack,
A. Srivastava et al.
Fig. 1. Measurements of: a) Volume expansion of Portland cement (data from Nokken, 2010); and b) Hydration of API Class H cement (data from Pang et al., 2013).
Fig. 2. The effects of MgO on compressive strength and SBS of Class G cement at different temperatures and wall conditions (Ghofrani and Plack, 1993).
Fig. 3. Micro-cracked 10% MgO cement core.
1993; Buntoro et al., 2000) suggested that 3–5% of MgO by weight of
cement (BWOC) is sufficient to create cement with high compressive
and shear bond strength. Although Mg(OH)2 undergoes carbonation to
form MgCO3, these crystals are insoluble in water. Hence, they do not
easily leach out like calcium bicarbonate (Cheremisinoff, 1995). These
properties made MgO a suitable cement additive for HPHT applications.
Ghofrani and Plack (1993) studied the effects of MgO on compressive
strength and SBS of Class G cement at different temperatures (Fig. 2).
The compressive strength of MgO containing cement (GMG) was sig-
nificantly higher than the baseline when curing was performed at
150 °C (Fig. 2a). The baseline was neat Class G cement and GMG con-
tained 20% MgO as an additive. The impact of MgO addition was more
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Journal of Petroleum Science and Engineering 170 (2018) 218–230
pronounced on SBS of the cement. Regardless of the curing tempera-
ture, MgO containing cements (GMG and GMGC) exhibited sub-
stantially higher SBS as compared to the baseline, particularly when the
bonding walls were covered with clay suspensions (i.e. in the case of GC
and GMGC). As expected, clay contamination reduced the SBS of the
cements.
3. Experimental study
3.1. Slurry composition and properties
Cheung (1999) recommended a wide range of MgO concentration
(0.1–20% BWOC) to obtain good sealing between casing and cement.
The addition of MgO reduced porosity and permeability of cement. In
this study, MgO with calcination temperature of approximately 1250 °C
was used. As reported by previous studies (Rubiandini et al., 2005;
Buntoro et al., 2000; Cheung, 1999), this calcination temperature is
useful in producing MgO that can cause a reduction in porosity and
permeability of the set cement. However, the amount of MgO needs to
be optimized to avoid an extreme expansion that can cause cracks in
cement and increase the penetration of carbonic acid. To determine the
optimum amount of MgO, two concentrations (5% and 10%) of MgO
containing cement formulations were initially considered in this study.
However, because of microcracking (Fig. 3), the permeability of base-
line cement significantly increased after the addition of 10% MgO.
Hence, only 5% MgO cement was investigated. The compositions and
properties of baseline (HS) and 5% MgO (HSMG) cement slurries are
presented in Tables 1 and 2. The slurry properties (density, viscosity,
filter loss and thickening time) of HS and HSMG were maintained
comparable.
3.2. Aging conditions
Six different batches of cement slurries were prepared and exposed
A. Srivastava et al. Journal of Petroleum Science and Engineering 170 (2018) 218–230

Table 1 injection and heating processes were discontinued when the desired cell
Slurry compositions. pressure and temperature were established. Then, the autoclave is fully
Component Base Slurry Cement (HS) MgO Cement (HSMG) closed and left for two weeks. Autoclave pressure and temperature were
monitored and maintained at the desired level. In some experiments,
Cement Class H 100% 100% slight variation in pressure ( ± 0.6 MPa) and temperature ( ± 2.5 °C)
Silica flour 35% BWOC 35% BWOC
were observed during the test due to surrounding temperature change
HEC 0.1% of water for silica 0.1% of water for silica
flour flour
and minor gas leak from the aging cell. After completion of aging, the
Anti-Foaming Agent 0.378 L/sack of cement 0.378 L/sack of cement autoclave was depressurized slowly to prevent excessive gas expansion
Water for Class H 38% BWOC 38% BWOC in specimens. Then, the cores were recovered, and degradation as-
Water for silica flour 38.5% of silica flour 38.5% of silica flour sessment tests were performed.
Magnesium oxide – 5% BWOC

3.4. Sample preparation and testing protocol

Table 2
Slurry properties. Fig. 5 is a block diagram of the experimental program that shows all
phases of the test protocol. Baseline and HSMG cement slurries were
Slurry Density Power-Law Rheology API Filter Thickening Time
prepared according to the API procedure (RP 10B) and poured into
[kg/m3] Parameters Loss (mL) (Min.)
rubber molds and carbon steel pipes (length of 4.45 cm and inner dia-
n k (Pa.sn) meter of 1.88 cm). One end of the pipes was plug to prevent fluid loss.
The molds and steel pipe with cement slurries (SBS samples) were
HS 1941.2 0.438 6.90 100 170
immersed in 2% NaCl brine and placed in an oven to cure. The tem-
HSMG 1953.2 0.516 3.83 112 160
perature of the oven was maintained at 93 °C. After five days, the cured
and hardened cement and SBS samples were taken out of the oven, and
Table 3 cylindrical cores (3.81 cm long × 2.54 cm diameter) were cut from the
Aging conditions for the experiments. hardened cement while SBS samples were spray painted to prevent
corrosion of the pipe in the autoclave. After curing and painting, most
Exp. 1 Exp. 2 Exp. 3 Exp. 4 Exp. 5 Exp. 6
of the cores and samples were placed in the aging cell. Some cores and
T (°C) 38 107 107 107 107 177 SBS samples (unaged samples) were kept in 2% NaCl brine under am-
P (MPa) 41 41 41 62 62 62 bient condition while aging other samples.
CH4 (%) 0 0 60 60 0 60 The composition of unaged HS cement after five days of curing is
CO2 (%) 100 100 40 40 100 40
presented in Fig. 6 to show the level of hydration. After aging, all aged
cores and SBS samples were recovered and placed in vials for temporary
to different aging conditions as described in Table 3. The gas percentage preservation. Then, compressive and bonding strength of the samples
in the table refers to the partial pressure ratio (i.e. partial pressure/total were tested. Cores used for porosity and permeability test were dried in
pressure). It was observed during preliminary testing of baseline ce- an oven at 44 °C to remove any moisture in pore space. The drying was
ment that the effect of methane on degradation is minimal. Therefore, continued until the sample mass change with respect to time became
any change occurring in cement is considered to be because of dissolved negligible. For each type of cement, four tests were conducted using
CO2. two cores for each cement type. Average values of four porosity and
permeability measurements are reported. Dried cores used to measure
porosity and permeability were transversely cut. As illustrated in Fig. 7,
3.3. Experimental setup three different (inner, middle and outer) zones were selected to take
samples for FTIR analysis. Then, a mineralogical analysis was per-
Fig. 4 presents schematic of the experimental setup used for aging formed on the samples using a standard FTIR instrument (Thermo –
cores. The main components of the setup includes: i) HPHT jacketed Scientific Nicolet 6700).
aging cell (autoclave) with volume capacity of 3.4 L; ii) CO2 and CH4 Before beginning the experimental program, a test protocol was
supply gas cylinders; iii) gas injection system to boost supply gas developed to minimize experimental artifacts. The testing protocol of
pressure and maintain the desired gas composition in the aging cell; iv) baseline (HS) and additive containing (HSMG) were maintained iden-
heating system; and v) instrumentation and data acquisition (DAQ) tical. During slurry preparation, slurry volume and mixing time and
system. The injection system has a cylinder with a floating piston that procedures were maintained the same for both types of cements. The
separates the cylinder into two parts. The lower part is used to measure slurries were prepared as per the API procedure (RP 10B). A fully au-
and inject the gases needed for the experiment. The upper part is tomated API recommended blender was used. The blender runs at 4000
connected to an oil pump which is powered by compressed air. By RPM initially (for 15 s), during which all the components are added to
pressurizing the upper portion of the cylinder, the pump forces the the blender, and then at 12000 RPM for 35 s. The sequences of addition
piston to move downward to inject the gas phase into the autoclave. of components were identical except for MgO addition. Sample curing,
The hydraulic oil returns to the oil reservoir when the lower part of the coring, aging and drying were conducted using the same equipment at
cylinder is replenished with supply gas. The position of the piston is the same time. All unaged samples were preserved under identical
determined by measuring oil-level in the tank. In the autoclave, the conditions. SBS, CS and PP tests were performed using the same test
specimens were arranged on a perforated cylindrical shelf. The cell was equipment and running the tests consecutively in alternating order.
partially (80%) filled with brine, and the specimens were fully im-
mersed in it. The ratio of the volume of acidic fluid to cement samples 3.5. Degradation assessment techniques
was approximately 3:1. To perform the test, autoclave cover was as-
sembled, and gas injection tube was connected. The cell temperature After aging, porosity, permeability, compressive strength (CS), and
was raised slowly (approximately 20 °C per hour) by circulating heated shear bond strength (SBS) of cement samples were measured to eval-
oil through autoclave jacket. To keep the CO2 in the gaseous form, gas uate the level of degradation.
injection was started when the autoclave temperature reached the cri- Porosity – Permeability (PP) Measurement: Initial porosity and
tical temperature of CO2 (30.5 °C). Then, CO2 and CH4 were injected permeability reductions is an indication of MgO hydration during ce-
into the autoclave consecutively using the injection cylinder. The ment hardening. Reductions in porosity and permeability occurring

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A. Srivastava et al. Journal of Petroleum Science and Engineering 170 (2018) 218–230

Fig. 4. Schematic of the experimental setup (Omosebi et al., 2015).

Fig. 5. Block diagram of the experimental program.

after cement hardening in carbonic acid environment shows carbona-
tion. To assess the effect of MgO on carbonation of cement, the porosity
and permeability of cores were determined using an automatic
Permeameter–Porosimeter (Coretest Systems AP-608) maintaining
3.45 MPa confining pressure and 1.38 MPa differential pressure.
Helium gas was used as a test fluid.
Confined Compressive Strength: The Compressive Strength (CS) of
cement varies with its formulation and level of hydration and de-
gradation. The CS of cement cores was determined using experimental
setup developed during the investigation. The confining pressure of

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A. Srivastava et al.
Fig. 6. Composition of unaged Class H cement after 5 days of curing at 93 °C (Omosebi et al., 2015).
Fig. 7. Carbonated cement core.
6.9 MPa was maintained in all experiments. The tests were performed
according to the ASTM standard (ASTM-C39/C39M-12). Five tests were
conducted for each type of cement, using five cores. Average values of
the measurements are reported. Fig. 8 presents the schematic of test
setup used to determine the compressive strength of the cores (Ahmed
et al., 2015; Omosebi et al., 2016).
The experimental setup consists of: i) confining cell (maximum
pressure 2500 psi) with a Hassler rubber sleeve to isolate the core from
the confining fluid, ii) air driven pump to pressurize the cell with water;
iii) double acting hydraulic cylinder with displacement sensor to locate
the position of the piston, iv) syringe pump which is connected to data
acquisition computer to allow accurate load rate control. During the
experiment, the test sample (core) was placed in a Hassler rubber sleeve
and mounted in the confining cell. The cell was sealed by placing its lid
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Journal of Petroleum Science and Engineering 170 (2018) 218–230
and pressurized to 6.9 MPa using an air-operated water pump. Then,
the syringe pump was operated to increase the pressure in the hydraulic
cylinder at the desired rate which maintained the standard stress
loading rate of approximately 0.24 MPa/s. The application of the load
resulted in a vertical movement of the piston and stress load on the core
placed in the Hassler sleeve. Syringe pump speed was precisely con-
trolled using a computer. As the load increased, the position of the
piston, and confining and hydraulic cylinder pressures (P1 and P2) were
measured. The experiment was ended when the cylinder pressure
abruptly dropped to a near-zero value indicating core failure. The
maximum stress load (compressive strength) was recorded when the
experiment was completed. To account for a reduced diameter ratio
(i.e. L/D ≈ 1.5), the recorded compressive strength were corrected
according to ASTM C39/C39M procedure.
Fourier Transform Infrared Spectroscopy (FTIR): The FTIR ana-
lysis is a reliable and established method to detect the change in mi-
neralogical compositions of cement and rocks. The FTIR of aged and
unaged cement cores was determined to perform mineralogical analysis
by comparing peak strength at a particular wavelength that corresponds
to specific mineral present in the sample.
Shear Bond Strength: The shear bond strength of cement shows wall
shear stress needed to break down the bond between casing/borehole
and cement. An apparatus shown in Fig. 9a was used to measure the
shear bond strength of samples. The device consists of a pipe holder,
plunger (Fig. 9b) connected to a hydraulic power cylinder, and an oil
pump. To measure shear bond strength, an SBS specimen is placed in
the pipe holder. Testing begins by slowly pumping hydraulic oil into the
cylinder and pushing the plunger to apply force on a cement surface. As
pumping continues, the plunger moves and the cylinder pressure gra-
dually increases until the bond between pipe and cement breaks. During
the test, cylinder pressure and plunger displacement are measured as a
function of time (Fig. 9c). The experiment ends when a sudden reduc-
tion in pressure is observed. The maximum pressure (Pmax) measured
during the experiment is applied to compute SBS as:
Pmax Dc2
SBS =
4LDp (5)
where L is the contact length. Dp is the inner diameter of steel pipe and
Dc is the diameter of the hydraulic cylinder. Five tests were conducted
using five samples for each type of cement. Average values of the
measurements are reported.
A. Srivastava et al.
Fig. 8. Schematic of compressive strength testing apparatus.
4. Results and discussion
4.1. Porosity and permeability
Several past studies (Condor and Asghari, 2009; Kutchko et al.,
2007; Barlet-Gouédard et al., 2007, 2009) observed a decline in por-
osity and permeability in the early stage of cement carbonation.
Nevertheless, long-term carbonation studies (Barlet-Gouédard et al.,
2007, 2009) demonstrated a significant reduction in the strength of
cement. Porosity data is shown in Fig. 10. As expected, the addition of
MgO slightly reduced (in average about 1%) the initial porosity of the
HSMG samples. Even though the porosity reduction is limited, its im-
pact on ionic diffusion can be substantial as hydrated MgO particles
(Mg(OH)2 crystals block the pore throat and obstruct fluid movement.
Aged HS and HSMG samples consistently displayed a reduction in
porosity after exposure to the carbonic acid environment. The reduction
is attributed to the carbonation of CH and CSH, and the formation of
calcium carbonate crystals in pores. HS cores predominantly exhibited
more reduction in porosity than HSMG cores indicating potentially
greater carbonation in HS than HSMG cores. When tests were con-
ducted mostly at a low CO2 concentration (Exp. 3, 4 and 6), HSMG
Fig. 9. Shear bond measuring apparatus: a) oil pump; b) pipe holder and specimen; and c) hydraulic pressure versus strain.
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Journal of Petroleum Science and Engineering 170 (2018) 218–230
cores didn't experience a significant reduction in porosity due to ex-
posure to the acidic environment. The degradation process of HSMG
cement is significantly different from that of the baseline. The de-
gradation of HSMG cement not only involves carbonation of CH and
CSH and subsequent bi-carbonation but also the carbonation of Mg
(OH)2. As a result, the leaching and carbonation processes of HSMG
cement are not only influenced by aging condition parameters (tem-
perature, pressure and CO2 concentration) but also affected by the
presence of MgO and its hydration and carbonation products such as
magnesium hydroxide, magnesium carbonate, and magnesium bi-
carbonate. The presence of these chemicals in crystal and/or ionized
forms strongly affects ionic diffusion occurring in cement pores and the
process of carbonation and leaching of CH and CSH. Environmental
conditions and the exposure time are very critical in determining de-
terioration of cement property. Even though carbonation which occurs
in the first phase of acid attack reduces porosity, in the presence of
excess acid, cement porosity eventually can increase after prolonged
exposure.
Fig. 11 presents the permeability of aged and unaged cores of HS
and HSMG cement. Even though unaged HS and HSMG cores demon-
strated approximately the same average porosity (∅HSMG = 29.1% and
A. Srivastava et al.
Fig. 10. Porosity of aged and unaged samples: a) HS; and b) HSMG.
∅HS = 29.3%), unaged HSMG showed considerably higher average
permeability (kHSMG = 0.088 mD ) than the baseline cement
(kHS = 0.054 mD ). The increase in permeability could be due to the
formation of microcracks as magnesium oxide crystals grow in pore
space excessively. A recent study (Sugama et al., 2011) reported the
development of visually noticeable cracks in cement cores when MgO
content is greater than 2%. Visual examination of the cross-section of
cores (Fig. 12) indicates the depth of degradation front and level of acid
attack. All HSMG cores displayed a greater depth of degradation than
HS cores presumably due to micro-cracking. MgO addition can be
beneficial if micro-cracking is prevented by optimizing cement for-
mulation and curing conditions. Cores aged at low temperature (Exp.
1), didn't display visually visible degradation front (Fig. 12a). However,
reduction in porosity and permeability of the cores indicates the oc-
currence of some level of carbonation. Consistent with the porosity
measurements, HS samples predominately demonstrated more reduc-
tion in permeability than HSMG samples, which indicates a higher level
of carbonation of HS samples as compared to HSMG cores.
4.2. Confined Compressive Strength
Confined compressive strengths of the aged and unaged cores are
displayed in Fig. 13. Data from low-temperature experiment (Exp. 1)
shows a minor difference between the compressive strength of aged and
unaged cores of HS and HSMG cement. The absence of compressive
strength variation after exposure to carbonic acid demonstrates the
absence of a major carbonation. This observation is in agreement with
the visual inspection of degradation depth (Fig. 12a). Nevertheless,
reductions in porosity and permeability shown in Figs. 10 and 11 in-
dicate noticeable carbonation of CH and CSH. Temperature is a major
factor that affects the degree of carbonation and its kinetics. It also
influences the solubility of reactants and products of carbonation re-
action. Moreover, the temperature has a substantial impact on ionic
diffusion, the solubility of CO2 and carbonic acid dissociation.
Fig. 11. Permeability of aged and unaged samples: a) HS; and b) HSMG.
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Journal of Petroleum Science and Engineering 170 (2018) 218–230
Therefore, it is difficult to provide a precise explanation for this ob-
servation. HS and HSMG cores tested in other experimental conditions
(Exp. 2 to 6), experienced a significant increase in compressive strength
due to carbonation. Although carbonation seems to increase the com-
pressive strength, it is detrimental to cement because calcium carbonate
can react with remaining acid to form highly soluble calcium bicarbo-
nate that can be leached out due to ionic diffusion. The overall de-
gradation process is controlled by temperature, pH, acid concentration,
ionic concentrations, and pressure. The addition of MgO in the cement
slightly reduced (approximately 8%) initial compressive strength of
cement. The reduction could be due to the binding behavior of Mg
(OH)2 and its impact on the structure development process of CH and
CSH.
4.3. Shear bond strength
The shear bond strength of cement is another important parameter
which determines the integrity of a well. Low shear bond strength can
cause failure at the interface of cement and casing resulting in micro-
channeling. The conversion of CSH and CH to CaCO3 during the car-
bonation process results in cement expansion (Ceukelaire and Van
Nieuwenburg, 1993). The expansion has a positive impact on shear
bond strength (SBS) and sealing performance. Nevertheless, the car-
bonation product (CaCO3) can react with acid gradually to form a so-
luble product (Ca(HCO3)2) that can be leached out from cement matrix.
Fig. 14 shows shear bond strength (SBS) of aged and unaged specimens
of HS and HSMG. Unaged HSMG specimens exhibited slightly higher
(8.11%) average SBS than HS cores. All tested specimens displayed an
increase in SBS due to carbonation. In Experiment 1, the increase in SBS
was limited (HSMG = 44.6% and HS = 24.7%) due to low temperature.
The increase in SBS is consistent with permeability and porosity mea-
surements. Visual examination of cement samples recovered from SBS
specimens indicated the absence of acidic fluid penetration at the in-
terface between cement and pipe.
A. Srivastava et al.
Fig. 12. Cross sections of aged cores.
4.4. FTIR
To assess the impact of MgO on carbonic acid resistance of cement,
FTIR analysis was performed by taking samples from three different
regions (inner, middle and outer zones) of cores as discussed in Section
3.5. FTIR results were able to indicate the presence of various minerals
in zones of interest. The mineralogical analysis is focused on carbona-
tion reaction related components Ca(OH)2, CSH, CaCO3, MgO, Mg
(OH)2 and MgCO3. The CaCO3 and MgCO3 are the carbonated compo-
nents of CH/CSH and MgO/Mg(OH)2, respectively. As discussed earlier,
in the presence of carbonic acid, CaCO3 further reacts with acid to form
Ca(HCO3)2. On the other hand, the reaction mechanism of MgCO3 is
different (Smithson and Bakhshi, 1973). MgO reacts with brine satu-
rated with carbon dioxide to form aqueous Mg(HCO3)2 which decom-
poses and precipitates into two forms of hydrated magnesium carbo-
nates (MgCO3·5H2O and MgCO3·5H2O). Once formed, magnesium
carbonate is stable, and it does not transform into soluble compounds in
the temperature range of 25–200 °C (Cheremisinoff, 1995). Hence, the
presence of MgCO3 indicates carbonation, which causes reductions in
porosity and permeability, and increases in compressive strength and
SBS. The FTIR spectrum wavelength peaks for the components of ce-
ment and carbonation products are presented in Table 4.
4.4.1. Outer Zone
Samples taken from outer most zones represent the most degraded
part of cores. FTIR charts of samples collected from the outer zone of
cores tested in the second experiment are shown in Fig. 15. Various
peaks are marked in the chart indicating the peak spectrums of various
minerals. The unaged samples demonstrated the least carbonation
while HS (baseline) cores exhibited the highest carbonation.
Fig. 13. Compressive strengths of aged and unaged samples: a) HS; and b) HSMG.
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Journal of Petroleum Science and Engineering 170 (2018) 218–230
The FTIR spectrums of the outer zones are summarized and pre-
sented as bar charts in Fig. 16 considering only the peaks of interest. It
should be noted that the bar chart strengths are only comparative for a
single mineral. Between the two samples (HS and HSMG), the highest
peak for any mineral is taken as 100 and the lower peaks are converted
to a proportionate value of peak strength. Two different minerals
should not be compared with respect to the peak obtained. The amount
of CaCO3 and MgCO3 are found to be the highest in this zone. It should
be noted that the spectrum peaks of MgCO3 are available at 880 cm−1
and around 1480 cm−1. Hence, the peak at 1480 cm−1 does indicate
not only the amount of CaCO3 but also MgCO3. Examining the charts for
all experiments, it can be seen that Ca(OH)2, Mg(OH)2 and CSH were
entirely consumed in both types of cement (HS and HSMG). The con-
sumption of these components demonstrates the occurrence of severe
carbonation on the outer rims of cores even though visual examination
and compressive strength measurements didn't indicate strong carbo-
nation or degradation. Nevertheless, MgO was preserved in cores aged
at low-temperature (38 °C), which shows the carbonation in Experiment
1 was not as severe as in other experiments. Visual examination of the
cross-section of cores indicates a very thin degraded outer zone.
4.4.2. Middle zone
The middle zone of cores indicates predominantly severe matrix
carbonation. All cores accept the ones aged at low-temperature (38 °C)
showed complete carbonation of CH and CSH in their middle zones
(Fig. 17). The HS and HSMG cores exposed to the acidic environment at
low-temperature displayed strong peaks for Ca(OH)2 and MgO which
indicates limited carbonation. This observation is consistent with visual
examination and compressive strength measurements that indicate
minor carbonation. CSH was entirely consumed in both types of
A. Srivastava et al. Journal of Petroleum Science and Engineering 170 (2018) 218–230

Fig. 14. SBS of aged and unaged cores: a) HS; and b) HSMG.

Table 4 Even though the preserved amount of Ca(OH)2 was higher in HS than
FTIR Spectrum wavelength peaks for various minerals. HSMG cores, the level of preserved Mg(OH)2 was maximum in HSMG
Mineral Wavelength (cm−1)
cores indicating that the pore volumes were occupied by magnesium
hydroxide crystals. CSH was also partially preserved in both cement
Ca(OH)2 3645 (Nasrazadani and Eureste, 2008) types when temperature and pressure were maintained at 107 °C and
CSH 950 (Berzina-Cimdina and Borodajenko, 2012) 41 MPa. However, when the pressure is increased at constant tem-
CaCO3 ∼1460 (Baciu and Simizis, 2007)
MgO 500 (Sadtler, 1982)
perature (107 °C and 61 MPa), CSH was preserved only in HSMG cores
Mg(OH)2 3700 (Hlaing, 2007) aging was conducted at a low CO2 concentration (40%). This is ex-
MgCO3 ∼1480 and 880 (Sadtler, 1982) pected because as the pressure increases more gas dissolves in liquid
increasing the concentration of carbonic acid and acid attack.

cement, even though HSMG cores displayed a lower amount of CaCO3
as compared to HS cores in the majority of cases (Exp. 2 to 5). When the
aging was conducted at high-temperature (177 °C), the trend was re-
versed, and HSMG cores showed more carbonation than HS cores. This
could be due to the development of micro-cracks from the expansion of
Mg(OH)2 in HSGM cores. The high temperature is expected to facilitate
the expansion of magnesium hydroxide (Cheung, 1999) and induce
micro-cracks, which results in severe carbonation of cement.
5. Conclusions
Class H cements with and without magnesium oxide additive were
prepared and exposed to brine saturated with mixed gas containing
carbon dioxide and methane at HPHT condition. After the exposure,
cement specimens were tested to determine their physical and miner-
alogical characteristics. The following conclusions can be drawn from
the results:

4.4.3. Inner zone

• Adding magnesium oxide has the potential to improve the carbonic
acid resistance of cement; however, it requires meticulous slurry
The inner zone is expected to be the least degraded as it is not di- design and suitable curing conditions to synchronize hydration ki-
rectly exposed to the aging environment. Magnesium hydroxide was netics of cement and MgO to prevent micro-cracking that results in
preserved in most of the experimental conditions (Fig. 18). Baseline increased permeability.
cores exhibited largely higher carbonation than HSMG cores. Calcium
hydroxide, magnesium hydroxide, and magnesium oxide were partially
• Temperature, pressure and CO2 concentration have major influences
on carbonation behavior of cement. Low-temperature limits
preserved in both types of cores when aged at low-temperature (38 °C).

Fig. 15. FTIR spectrum for Outer Zone of samples aged at 107 °C, 41.4 MPa (100% CO2), 2% Brine for 14 days.

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A. Srivastava et al. Journal of Petroleum Science and Engineering 170 (2018) 218–230

Fig. 16. FTIR spectrum charts of the outer zones of HSMG and HS cores at different aging conditions.

carbonation and degradation of cement. High pressure increases formation of crystals in pores and matrix expansion.
CO2 solubility, and as a result, promotes more acid attack and de- • Cement degradation due to carbonation is uniform around the
terioration of cement. specimen. A concentrated acid attack on a particular location on the
• Adding MgO improves the shear bond strength of cement due to the specimen was not observed.

Fig. 17. FTIR spectrum charts of the middle zones of HSMG and HS cores at different aging conditions.

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A. Srivastava et al. Journal of Petroleum Science and Engineering 170 (2018) 218–230

Fig. 18. FTIR spectrum charts of the outer zones of HSMG and HS cores at different aging conditions.

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