Journal of Petroleum Science and Engineering 201 (2021) 108408

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Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

Class C fly ash-based alkali activated cement as a potential alternative

cement for CO2 storage applications
Priyesh Jani a, b, Abdulmohsin Imqam b, *
a
Schlumberger Oilfield Services, USA
b
Missouri University of Science and Technology, USA

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

Keywords: Long-term storage of carbon dioxide (CO2) inside depleted reservoirs can help reduce the impact of greenhouse
Fly ash geopolymer cement gas emissions. Portland cement has been shown to degrade significantly during long-term contact with CO2. This
CO2 research aims to provide a new environmentally friendly, Class C fly ash-based cement as a potential alternative
Portland cement
to Portland cement for CO2 storage wells. This was achieved by comparing the mechanical degradation of
Portland cement and Class C fly ash-based alkali-activated cement in a CO2 environment. A specially designed
setup was constructed to create an in situ high pressure and high-temperature CO2 environment. Seventy-two
cores of Portland cement and Class C fly ash-based cement were prepared for this study. The results show
that CO2 reacted with the water in the vessel and formed carbonic acid, which reduced the water pH to 6.8.
Millimeter-sized crystals of calcium carbonate (CaCO3) were observed on the surface of the Portland cement
cores after the CO2 exposure. The surface of the fly ash-based alkali-activated cement cores was not substantively
changed after the exposure. No significant change in density was observed for both types of cement during the 14
days of CO2 exposure. Portland cement showed a significant reduction in compressive strength, and this
reduction developed as the exposure time increased. Interestingly, Class C fly ash-based cement showed no
reduction in compressive strength, and only a small amount of reduction was observed after 14 days of exposure.
This research compared the mechanical degradation of Portland cement and Class C fly ash-based alkali-acti­
vated cement in a high-pressure and high-temperature CO2 environment.

1. Introduction silica, which leads to the formation of microcracks, a reduction in

strength, and ultimately, loss of zonal isolation. This effect can be
Long-term underground storage of CO2 is an effective solution to reduced by decreasing the surface area of the cement that can be con­
provide safe and low-cost CO2 sequestration (Gielen, 2003; Sarmiento tacted by the CO2 using a proper primary cementing job, thereby
and Gruber, 2002). Three main types of storage media are available to reducing the materials inside the cement matrix that can chemically
store CO2: (1) depleted oil and gas reservoirs, (2) deep saline aquifers, react with CO2.
and (3) unmineable coal beds. These reservoirs need to be at depths Many researchers have added pozzolanic materials, such as fly ash or
greater than 800 m to store CO2 in a supercritical state as this allows silica flour, to Portland cement to make it more CO2-resistant. Santra
storage within a relatively small volume. Also, a leakage rate less than et al. (2009) conducted an experiment with five cement mixes con­
0.1%/year is all that is needed to make the sequestration processes taining 16.7%, 28.6%, 37.5%, 44.4%, and 50% fly ash combined with
successful. The leakage path can be natural, through faults or open Portland cement. The results showed that the depth of the carbonation
fractures, or it can be artificially created through cap rock or wells was directly proportional to the amount of the pozzolanic supplement.
drilled in that formation (Bachu and Bennion 2009). Portland cement is Kutchko et al. (2009) experimented with cement mix containing fly ash
used to cast wells to provide integrity and to mitigate leakage from the and found out that after total carbonation, this chemical alteration did
production zones. Thus, primary cementing is key to providing not reflect in the mechanical alteration as was found with Class H
long-term zonal isolation and preventing gas leakage. However, CO2 can cement. Santra et al. (2009) showed that an addition of pozzolan (i.e.,
chemically react with Portland cement to form CaCO3 and amorphous Class F fly ash) into Portland cement reduced the amount of portlandite

* Corresponding author.
E-mail address: [email protected] (A. Imqam).

https://doi.org/10.1016/j.petrol.2021.108408
Received 10 September 2020; Received in revised form 11 January 2021; Accepted 12 January 2021
Available online 22 January 2021
0920-4105/© 2021 Elsevier B.V. All rights reserved.
P. Jani and A. Imqam Journal of Petroleum Science and Engineering 201 (2021) 108408

(Ca(OH)2) present in the neat cement. Lesti et al. (2013) showed that • Carbonic acid will react with calcium hydroxide Ca(OH)2(s) (Equa­
slag cement blended with fly ash provided good results to mitigate tion (2)) to form calcium carbonate CaCO3(s). As the molar volume of
CaCO3 precipitation and crystallization. Zhang and Talman (2014) CaCO3(s) is higher than that of Ca(OH)2(s), this will lead to volume
conducted an experiment using lightweight and normal weight cement. expansion and a decrease in porosity/permeability. However, this
Lightweight cement was prepared by adding 1% sodium metasilicate to reaction can also lead to the formation of microcracks as the volume
the fly ash, while normal weight cement was prepared by adding 2% expansion can cause higher stress inside the cement matrix.
bentonite to the fly ash. The results showed that normal-weight cement
Ca(OH)2(s) + H2CO3 → CaCO3(s) + 2H2O (l) (2)
experienced no reduction in durability or permeability. Thus, the ma­ (aq)

jority of these studies found that the cement mix containing fly ash
performed better in the CO2 environment. studies showed that geo­ • Longer exposure to carbonic acid leads to the further dissolution of
polymer mixtures have better potential to replace Portland cement and calcium carbonate to form calcium bicarbonate, which can easily
this cement can be produced with very less environmental impact. Based leach out of the cement matrix (Equation (3)). Next, the carbonic
on Salehi et al., (2016) the authors’ knowledge, no one has tried to use a acid will dissolve the C–S–H gel to form an amorphous silica, which
100% fly ash-based geopolymer cement to test in the CO2 environment; lacks structure and is highly porous. This reaction will lead to an
instead, only Class F fly ash had been used as an additive in the previ­ increase in the porosity/permeability and a decrease in strength
ously mentioned studies. (Equation (4)).
Nasvi et al. (2012), Neetu et al. (2013), and Sugumaran (2015)
performed experiments with Class F fly ash-based geopolymer cement CaCO3(s)+H2CO3 (aq) → Ca(HCO3)2 (3)
(0% Portland cement) and found that this cement had a higher
C–S–H and/or crystalline phases + H2CO3 → SiO2 (gel) + CaCO3(s) +
compressive and shear strength, better durability in an acidic environ­
(aq)
H2O (l) (4)
ment, and a lower chemical shrinkage than Portland cement. In our
recent studies (Ahdaya and Imqam 2019a, b), we had successfully Carbonation of cement paste ultimately leads to an increase in the
formulated a Class C fly ash-based geopolymer and tested it against density as CaCO3 is deposited, and a decrease in strength, along with an
drilling fluid contaminations. We found drilling fluids enhanced the increase in the porosity/permeability. This can pose a risk of gas
geopolymer rheological behavior. Xiangyu et al. (2019) also show migration from the cement matrix. Cement can be made CO2-resistant
alkali-activated fly ash provides improved compatibility with oil-based either by (1) reducing the amount of portlandite (Ca(OH)2) and
and synthetic-based drilling mud. Khalifeh et al. (2014) found in the changing the structure of C–S–H, or (2) reducing the water: cement ratio
studies that Class C fly ash-based alkali-activated geopolymer cement to reduce the porosity/permeability of the cement. Pozzolans are
has the potential to be utilized as an alternative material to cement in generally introduced to reduce the amount of portlandite. Pozzolans
P&A operations. Class C fly ash differs from Class F in chemical mainly react with Ca(OH)2 to form secondary C–S–H, thus reducing the
composition, where Class F has a lower calcium content than Class C. portlandite content. Fly ash is one of the most common types of poz­
Class C fly ash provides early strength, which can be beneficial in the zolans that can be used to achieve this purpose. Fly ash is a by-product of
CO2 environment. Our results found the geopolymer cement to with­ the coal combustion process and is basically a waste material. Fly ash is
stand drilling fluid contamination, with better rheological and me­ mainly composed of alumina and silica, which, when combined with an
chanical properties than Portland cement. alkaline solution, undergoes a geopolymerization process. These con­
The current study is an extension of our most recent work where verts fly ash into a binder, mainly an aluminosilicate gel, which, when
Class C fly ash-based cement performance was tested in a CO2 envi­ mixed with water, behaves as a cement. Additionally, fly ash-based
ronment, and its results were compared to Portland cement. The dura­ cement is environmentally friendly and cost-effective.
bility of a Class C fly ash-based cement in CO2 environments was
measured by performing a carbonation experiment on this cement. 2. Experimental description and mixing procedure
Carbonation of both types of cement was indirectly measured by visual
degradation as well as changes in the density and the compressive 2.1. Materials
strength. Carbonation experiments were carried out under static con­
ditions as this was a realistic representation of downhole carbonation. Portland Cement. Class H Portland cement, obtained from Halli­
burton Company, was used in this study. Table 1 shows the elemental
composition of Class H Portland cement measured using X-ray fluores­
1.1. Reasons that a fly ash-based cement could be a good choice to use in
cence (XRF).
CO2 storage reservoirs
Fly Ash. Fly ash (Class C) was used in this study, obtained from Rolla
Ready Mix LLC. Table 2 shows the composition of fly ash that was ob­
Class H Portland cement mainly consists of 30% dicalcium silicate
tained by XRF. In general, there are two types of fly ash: Class C and
(C2S), 50% tricalcium silicate (C3S), 5% tricalcium aluminate (C3A), and
Class F. According to the American Society for Testing and Materials
12% tetra calcium aluminoferrite (C4AF) (Kutchko et al., 2008; Nelson
(ASTM C 618), Class C fly ash has a lime content greater than 20%, while
1999). Upon hydration, the main product form is 70% C–S–H gel and
Class F has a lime content lower than 20%. Therefore, fly ash (Class C) is
15–20% Ca(OH)2 (Kutchko et al., 2008). The main binding material in
also known as high-calcium fly ash, whereas fly ash (Class F) is known as
the hydrated cement is C–S–H. Chemical reactions involved in Portland
cement carbonation are discussed in many studies extensively and can
Table 1
be summarized as follows:
Elemental compositions of Class H cement.

• In the case of carbon dioxide storage, injected carbon dioxide dis­ Element Concentration (%)
solves in water to form carbonic acid (Equation (1)), and it decreases SiO2 20.36
the pH of the Portland cement (which normally has a pH above 12.5); Al2O3 3.17
thus, this in equilibrium will lead to diffusion of the carbonic acid Fe2O3 6.19
CaO 65.72
inside the cement matrix. MgO 1.32
SO3 2.26
CO2 (g) + H2O (l) → H2CO3 (aq) (1) K2O 0.43
Other components 0.55

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P. Jani and A. Imqam Journal of Petroleum Science and Engineering 201 (2021) 108408

Table 2 curing period can resemble the cement already containing CO2 that is
Elemental compositions of Class C fly ash. used in wells drilled in reservoirs (Garnier et al., 2010).
Element Concentration (%) Table 4 shows the summary of the experimental test conditions for
both class C fly ash-based alkali-activated cement and class H Portland
SiO2 28.93
Al2O3 14.82 cement.
Fe2O3 6.40
CaO 39.80 3. Description of the experimental setup and tests
MgO 4.86
Na2O 1.10
K2O 0.56
A specially designed setup (Fig. 2) was used to create an in situ CO2
Other components 2.63 environment. Two accumulators, a water bath, a CO2 cylinder, and a
syringe pump were used in the experimental setup. The syringe pump
was used to increase the CO2 pressure to the desired value. Pressure
low-calcium fly ash. gauges were installed to monitor pressure changes. One pressure relief
Sodium Hydroxide (NaOH). The purity of sodium hydroxide is valve was installed to bleed CO2 pressure at the end of the experiment.
96%. It was mixed with distilled water and hand stirred until it was Twelve experiments were conducted, in which six experiments were
completely dissolved. For each 1 molarity concentration, 40 gm of so­ conducted at 500 psi pressure, while the others were conducted at 1500
dium hydroxide powder was added to 1 L of distilled water. The molarity psi CO2 pressure, all at 110 ◦ F, for 3,7, and 14 days. The procedure
is defined as the number of moles divided by the volume (i.e., the con­ followed for each experiment is described below:
centration of a solution).
Sodium Silicate (Na2SiO3). Sodium silicate is an essential material a) A total of six samples were prepared for each run. Out of these six,
in providing another source of silicate (other than fly ash) to the three samples were fully immersed in water inside Accumulator 2 for
mixture. The materials were obtained from PQ Corporation. The NaOH the CO2 exposure. Water was used rather than saline (1% NaCl) to
solution was mixed with Na2SiO3 to allow an alkaline activator for the provide more extreme conditions, as CO2 is more soluble in water
fly ash-based slurry preparation. (Spycher and Pruess 2005).
Carbon Dioxide (CO2). A CO2 cylinder with a pressure of 1000 psi b) Accumulator 2 was kept inside the water bath to keep the tempera­
was used as a source of gas CO2. ture stable. The temperature was kept constant at 110 ◦ F for all the
experiments. As CO2 gas was continuously getting dissolved inside
2.2. Portland Cement preparation procedure the water, it was very hard to get a stable liquid to gas volume ratio.
This reflects field condition as in the field injected CO2 will be getting
Portland cement was mixed according to American Petroleum dissolved in the water so one stable ratio is not possible under this
Institute recommendations (API specification 10A, 2010). All Portland condition.
cement slurries were mixed at ambient temperature and atmospheric c) CO2 was first injected inside Accumulator 1 from the CO2 cylinder.
pressure. Dry cement was added to the water and mixed at low speed for The CO2 pressure was increased to the desired level (i.e., 500 and
15 s, followed by another 35 s at high speed. 1500 psi) using the syringe pump.
d) Pressurized CO2 was injected inside Accumulator 2 to create a CO2
environment for the cement cores. After the exposure time, the
2.3. Fly ash-based alkali activated cement preparation procedure
pressure was reduced slowly to avoid breaking the cement due to a
sudden pressure drop.
The mix design for fly ash cement was well explained in our previous
e) Samples were taken out of Accumulator 2 and dried gently before
work (Ahdaya and Imqam 2019b). The optimum mix design (Table 3)
conducting further tests.
was obtained for Class C fly ash-based cement. An alkaline activator was
prepared by mixing 10 Molarity of NaOH and Na2SiO3.
Test Observations. Two types of exposure conditions were used in
In our previous work (Ahdaya and Imqam 2019b), the pumping
this research to mimic the effect of increasing the CO2 partial pressures
performance of different formulations of Class C fly ash-based alka­
and CO2 physical state on both types of cement. At 500 psi and 110 ◦ F,
li-activated cement slurries were tested. An elimination process was
CO2 will behave like a gas, while at 1500 psi and 110 ◦ F, CO2 will be in a
followed to determine the most optimal slurry (Table 3) at the testing
supercritical state. In both exposure conditions, CO2 will dissolve in
condition. The criteria followed for each test was as follows: i) cement
water and reduce the pressure. Thus, the pressure was regularly
slurry density should be in the range of normal cement, which is 14–17
increased to the desired value. The following is a brief description of the
lb/gal, ii) acceptable pumping performance, fly ash formulation that
tests conducted to determine the CO2 interaction with the Portland
shows similar rheological behavior to the Portland cement is selected,
cement and fly ash cement cores.
and iii) lower fluid loss.
After mixing, all the cement slurries were poured into a 2 x 2-inch
1) The pH of Water. The pH of the water was measured by a pH meter
cylindrical mold (Fig. 1) and placed inside a water bath at atmo­
before the injection of CO2 into the accumulator. The pH of the water
spheric pressure and a temperature of 110 ◦ F. The cement paste was
was again measured after the CO2 injection to see if there was any
allowed to set for 3 d before each experiment to gain 40% of its full
change.
strength (Neville 2012). The cement cores were strong enough to avoid
2) Visual Degradation. The exposed cores were compared with unex­
breaking during demolding but were also weak enough to allow quick
posed cores in terms of color and texture changes.
chemical reactions due to CO2 attack (Qingyun et al., 2015). This shorter
3) Density. A change in the bulk density of the cores was measured
before and after the exposure. A high resolution (0.001 g) weight-
Table 3
balance with a hook option (Fig. 3) was used to take the weight
Optimum mix design of Class C fly ash-based cement (Ahdaya and Imqam
measurements of the cement core sample. A bulk density equation
2019b).
was used to calculate the density of every segment.
Total AA/ Fly Na2SiO3/ NaOH Na2SiO3 Water 4) Compressive Strength. Compressive strength is a key factor to
Water FA Ash NaOH Solution Solution
investigate the strength of the fly ash-based alkali activated cement
33% 0.4 600 1 120 gm 120 gm 193.2 and Portland cement under a CO2 environment. A hydraulic press
gm gm

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P. Jani and A. Imqam Journal of Petroleum Science and Engineering 201 (2021) 108408

Fig. 1. Fly ash-based alkali activated cement core sample preparation.

before and after CO2 was injected at 500 psi and 1500 psi for both types
Table 4
of cement cores. The reduction in the pH was observed for both types of
Test matrix for the conducted experiments.
cement cores. In both cases, the pH was reduced to around 7. As Portland
Test conditions Class C fly ash-based alkali- Class H Portland Cement cement has a pH above 12.5 (Rendell et al., 2002; Neville 2012), this
activated cement
caused an equilibrium in the pH solution during 14 days of exposure.
Number of cores 6 6
prepared for
each run 4.2. Visual degradation
Initial curing Curing time - 3 days Curing time - 3 days
Curing temp - 110◦ F Curing temp - 110◦ F
Portland Cement. Millimeter-sized precipitates of calcium carbon­
After Initial Curing ate (CaCO3) were observed on the surface of the cores. Fig. 7 shows the
With CO2 Without With CO2 Without
Exposure CO2 Exposure CO2
comparison between the surfaces of the Portland cement cores after
Exposure Exposure exposure to CO2 partial pressures of 500 psi and 1500 psi. The amount
the precipitates increased with an increase in the CO2 exposure pressure,
Number of Cores 3 3 3 3
CO2 Pressure, psi 500 1500 N/A 500 1500 N/A as was also observed by Rimmelé et al. (2008).
Temperature, 0F 110 110 110 110 110 110 Fly ash-based Alkali Activated Cement. Almost no change in the
Duration of Test, 3 3 3 3 3 3
days 7 7 7 7 7 7
14 14 14 14 14 14

unit (Fig. 4 was used to determine the compressive strength of

exposed and unexposed cores.

4. Results and analysis

Cement cores were exposed to CO2 at two CO2 partial pressures (i.e.,
500 and 1500 psi) at 100 ◦ F in a static condition. The results from each
test are discussed and a comparison is provided between Portland and
fly ash-based alkali activated types of cement.

4.1. The pH of water

As CO2 was injected into the accumulator, the CO2 dissolved in the
water and formed carbonic acid, as stated in Equation (1). As a result,
Fig. 3. Mass measurement setup.
the pH of the water decreased. Figs. 5 and 6 show the pH of the water

Fig. 2. Experimental setup to test cement resistance to CO2 exposure.

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P. Jani and A. Imqam Journal of Petroleum Science and Engineering 201 (2021) 108408

4.3. Density of cement

Due to the pH being in equilibrium between the cement pore water

(pH ~ 13) and the aqueous solution (pH = 6), carbonic acid (H2CO3)
diffused inside the cement matrix and dissolved the portlandite (Ca
(OH)2) to form calcium carbonate (CaCO3). Shen and Pye (1989)
showed that the formation of CaCO3 leads to volume expansion, as the
molar volume of CaCO3 is higher than that of Ca(OH)2. This will increase
the density of the material, as the available pore space inside the cement
matrix is filled by CaCO3.
Fig. 9 shows the difference in the density observed in Portland and
fly ash-based alkali-activated cement cores after CO2 exposure at 500
and 1500 psi CO2 exposure. The results showed no significant increases
in density during the 14 days of CO2 exposure for both Portland and fly
ash-based alkali-activated types of cement. Zhang and Talman (2014)
observed the same behavior for the Class G neat Portland cement, as the
density remained unchanged. However, Barlet-Gouedard et al. (2006)
Fig. 4. Hydraulic press unit.
observed that the density increased from 16 to 18 ppg after the first
week of exposure in CO2-saturated water, which could be due to the
higher temperature (90 ◦ C) and higher pressure (4061 psi) conditions
used in their experiments.

4.4. Compressive strength of cement

Cement strength measurement is considered an indirect method of

ensuring well integrity. Longer exposure of cement to a CO2 environ­
ment leads to the dissolution of the main cement binding phases (Ca
(OH)2 and C–S–H), and the dissolution of the carbonation product
CaCO3 (shown earlier in the chemical reactions). This will decrease the
compressive strength of the cementitious material and can jeopardize
the effectiveness of well plugging. CaCO3 has a higher molar volume
than Ca(OH)2; thus, the formation of CaCO3 will cause volume expan­
sion. Since there is less available space, it will produce higher stress,
which could result in microcracks inside the cement matrix and ulti­
mately lead to a reduction in strength. Table 5 shows the compressive
strength of Portland and fly ash-based alkali-activated cement at a
temperature of 110 ◦ F and without any CO2 exposure at different du­
Fig. 5. The pH of the water before and after CO2 injection into Portland
cement cores.
rations. Class C fly ash-based cement has a low compressive strength
compared to Class H neat Portland cement, so these results do not
contradict our previous results (Ahdaya and Imqam 2019b). This change
in trend occurred because the fly ash-based alkali-activated cement mix
design from our previous work was performed at room temperature. In
the current work, the experiment was performed at a high temperature
(110 ◦ F), where an increase in the curing temperature led to a decrease
in the strength of the Class C fly ash-based cement. However, it was still
above the acceptable API range of 500 psi for well-plugging purposes. In
our future work, we need to synthesize new fly ash-based alka­
li-activated cement formulations for high-temperature environments.
Compressive strength measurement comparisons were made be­
tween the cement strength of the exposed and unexposed cores. Unex­
posed cores were kept in the water bath at all times, whereas exposed
cores were kept inside the water bath for the first three days and then
kept inside the accumulator for CO2 exposure. The strength results of the
cement cores after exposure to 500 and 1500 psi CO2 pressure for 3, 7,
and 14 days were plotted in graphs with the strength results of the
cement cores without exposure (Figs. 10 and 11). The Portland cement
strength decreased after exposure to a CO2 environment, and it
decreased substantially as the CO2 pressure and exposure time
Fig. 6. The pH of the water before and after CO2 injection into Class C fly ash-
increased. However, the fly ash-based alkali-activated cement showed a
based activated cement cores.
negligible strength reduction. This result implies that the fly ash-based
alkali-activated cement cores did not react intensively with the CO2 as
surfaces of the cement cores was observed before and after exposure to
compared to the Portland cement cores.
both pressures (Fig. 8). At 1500 psi, only a small amount of the pre­
The strength reduction percentages were calculated from Figs. 10
cipitates was observed. This suggests that the fly ash-based alkali-acti­
and 11 and plotted to further analyze the effects of the increased CO2
vated cement did not react intensively with CO2 or carbonic acid.
partial pressure, exposure time, and physical state of CO2 on both types
of cement. Fig. 12 shows that increased CO2 partial pressure raised the

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P. Jani and A. Imqam Journal of Petroleum Science and Engineering 201 (2021) 108408

Fig. 7. Images of the surface of Portland cement before and after 14 days of CO2 exposure: (a) unexposed cores, (b) after 500 psi exposure, and (c) after 1500
psi exposure.

Fig. 8. Images of the surface of alkali activated based cement before and after 14 days of CO2 exposure: (a) unexposed cores, (b) after 500 psi exposure, and (c) after
1500 psi exposure.

strength reduction percentage in both kinds of cement as the increased cement decreased by approximately 12.06% in strength after 14 days of
pressure changed the physical state of the CO2 and also changed its exposure compared to 41.54% for Portland cement. This shows that CO2
solubility in water. In the case of the Portland cement, a 41.54% did not significantly affect the strength of the fly ash-based alkali-acti­
reduction in strength was observed at a CO2 partial pressure of 1500 psi, vated cement.
whereas only a 27.77% reduction was observed at a CO2 partial pressure The effect of exposure time on the compressive strength of both types
of 500 psi after 14 days of exposure. These results imply that an increase of cement is shown in Fig. 13. The fly ash-based alkali-activated cement
in the CO2 injection pressure inside the geological reservoir will showed a very low reduction in strength. However, the long duration of
adversely affect the cement’s integrity. CO2 exposure significantly affected the integrity of the Portland cement
In the case of fly ash cement, no reduction was observed in the fly ash when it was exposed for 14 days. For the Portland cement, a possible
cement strength at 500 psi pressure after 3, 7, and 14 days of exposure explanation is that after long-term exposure, precipitated CaCO3 started
and at 1500 psi pressure after 3 days of exposure. However, after 7 and dissolving along with the main binding phase C–S–H, leaving amor­
14 days of 1500 psi CO2 exposure, fly ash-based alkali-activated cement phous silica in the structure (as explained in Equations (3) and (4)).
showed a small reduction in strength, but it was still less than the Amorphous silica is highly porous and lacks structure, which can cause a
decrease found in Portland cement. The fly ash-based alkali-activated reduction in strength.

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P. Jani and A. Imqam Journal of Petroleum Science and Engineering 201 (2021) 108408

Fig. 9. Changes in the density of Portland and fly ash-based alkali-activated cement before and after CO2 exposure.

5. Conclusions
Table 5
Compressive strengths of both types of cement without CO2 exposure cured at
A new cement, Class C fly ash-based alkali activated cement, was
110 ◦ F and atmospheric pressure for different durations.
proposed for use in carbon capture and storage wells for the purpose of
Total Curing Time (Days) 6 10 17
reducing the leakage of carbon dioxide into the atmosphere. Negligible
Compressive Strength Strength (psi) Strength (psi) Strength (psi) visual degradation and minimal reduction in the strength of the fly ash
Portland Cement 5111 5850 6773 cement compared to Class H Portland cement suggest that this new
Fly ash Cement 1464 1628 1733
cement mixture can be a possible alternative to Portland cement for
carbon dioxide storage operations. However, there is still much more
Fig. 14 shows the effect of the physical state of CO2 on the cement’s work to do in this area; for example, we observed that the compressive
integrity. Gaseous CO2 had less of an effect on the strength than did strength of the fly ash-based alkali-activated cement was very low
supercritical CO2. In a geological reservoir, CO2 will be in a supercritical compared to Class H Portland cement due to the higher curing tem­
state, and thus, strength reduction will be greater. perature of the fly ash cement. Although it was above the acceptable API
range, it is necessary to determine a new formulation of Class C fly ash-
based cement that would meet higher temperature applications. The
following conclusions were drawn from this work:

Fig. 10. Compressive strength of Portland and fly ash cements before and after 500 psi CO2 exposure.

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P. Jani and A. Imqam Journal of Petroleum Science and Engineering 201 (2021) 108408

Fig. 11. Compressive strength of Portland and fly ash cements before and after 1500 psi CO2 exposure.

Fig. 12. Effect of increased CO2 partial pressure on the strength of Portland and fly ash cement.

Fig. 13. Effect of increased exposure time on the strength of Portland and fly ash cement.

• No significant change in the density was observed in either type of cement. This suggests that the fly ash cement did not react inten­
cement, as was also observed by Zhang and Talman (2014). How­ sively with CO2 or carbonic acid.
ever, Barlet-Gouedard et al. (2006) observed density changes after • The fly ash cement’s compressive strength decreased slightly after
the first week of exposure that were probably due to the higher CO2 exposure. However, Portland cement’s strength was reduced
temperature (90 ◦ C) and higher pressure (4061 psi) used in their significantly. Each cement’s compressive strength decreased as the
experiments. CO2 partial pressure increased and with longer CO2 exposure.
• An almost negligible change in the surface of the fly ash cement cores
was observed after CO2 exposure when compared to Class H Portland

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P. Jani and A. Imqam Journal of Petroleum Science and Engineering 201 (2021) 108408

Fig. 14. Effect of the CO2 physical state on the strength of Portland and fly ash-based alkali activated cement.

Declaration of competing interest Khalifeh, M., Saasen, A., Vralstad, T., Hodne, H., 2014. Potential Utilization of
Geopolymers in Plug and Abandonment Operations. April 2. Society of Petroleum
Engineers. https://doi.org/10.2118/169231-MS.
The authors declare that they have no known competing financial Kutchko, B., Brian, R. Strazisar, Gregory, V. Lowry, Dzombak, David A., Thaulow, Niels,
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