SPE-193059-MS

Nanoclay Content Influence on Cement Strength for Oil Wells Subjected to

Cyclic Steam Injection and High-Temperature Conditions

Ahmed Abdulhamid Mahmoud, Salaheldin Elkatatny, Abdulmalek Ahmed S., and Mohamed Mahmoud, King Fahd
University of Petroleum & Minerals

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference held in Abu Dhabi, UAE, 12-15 November 2018.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
The hydrated products of Portland cement drastically change after exposure to high-temperatures,
compromising the cement physical properties, especially, its compressive and tensile strengths, this
phenomenon is known as strength retrogression.
Previous studies showed that the use of silica flour (SF) enhances Class G oil wells cement (OWC)
resistance to the strength retrogression due to the formation of long silica chains. In this work, the influence
of adding modified montmorillonite nanoclay (NC) particles, which are nanoparticles of layered mineral
silicates, on Class G cement strength retrogression resistance under the high-temperature condition of 300°C
was evaluated.
Six cement slurries were considered in this study, the base sample which has no silica or nanoclay
particles, one sample contains 35% BWOC of SF particles only, and 4 samples incorporating 1.0, 2.0, 3.0,
and 4.0% BWOC of NC and 35% BWOC of SF were prepared and tested under conditions of low (38°C)
and high (300°C) temperature after 7 days of curing. The 300°C was selected to represent one thermal
cycle condition when steam is injected into the oil well to increase the oil production for the purpose of
enhanced oil recovery (EOR). After preparation, the samples were poured into different molds with specific
dimensions based on the targeted test, then cured at the low-temperature condition of 38°C using a water
bath, the samples were cured for 7 days. Some of the samples cured at the low temperature for the whole
period while others removed in the last three days and cured at a high temperature of 300°C to mimic one
steam injection cycle condition.
In order to evaluate the effect of the NC particles on mitigating the cement strength loss at high-
temperature, the unconfined compressive strength (UCS) and tensile strength tests were performed. The
change in the permeability of the samples as a function of NC content and temperature were evaluated.
The percentage loss in the water absorbed by NC particles after exposing the cement samples to the high-
temperature condition (300°C) was measured.
The results revealed that the use of NC (up to 3.0% BWOC) can prevent the cement deterioration under
extremely high-temperature conditions of 300°C. This is attributed to two facts, first of all, the NC particles
reduced the initial permeability of the samples by filling the nanoscale porous these expected to dominate
2 SPE-193059-MS

the control samples (i.e. sample with 0% nanoclay), secondly acceleration of the hydration reaction which
results in formation of more stable forms of calcium silicate hydrates (CSH) which leads to enhancement
in the cement matrix resistance to the expected forces. At high-temperature environment, the original
permeability of the NC-based cement matrix increased mainly due to evaporation of the water absorbed by
NC particles when their concentration is maintained below 3.0% BWOC, the use of NC content beyond
that concentration (i.e. >3.0%) severely damaged the cement matric microstructure due to agglomeration
of nanoparticles.

Introduction
The main functions of the oil wells primary cementing are to provide the desired mechanical stability,
prevent any communication between the drilled formations by preventing the cement/formation annulus to
present, protect the casing to be contacted by formation corrosive fluids, and prevent the formation fluids to
flow up toward the surface. In this kind of operations, the wellbore/casing annular space is filled by one or
more cement slurries which must form hard enough and durable cement matrix to meet the needed isolation
efficiency throughout the well life. To achieve these goals, the cementing project must be well evaluated,
discussed, planned and executed (Rabia, 2001).
One of the most essential parameters to be considered during the cement slurry design is the operating
of the well. The effect of the temperature on both the liquid phase when the slurry is pumped through the
casing/wellbore annular space, and on the solid phase (hydrate cement) when the cement matrix is required
to meet the physical and chemical properties considered when the cement program is designed was early
addressed by different studies like Luke (2004), Vu et al. (2012), Shahab et al. (2015), Costa et al. (2017),
and Wang (2017).
Alteration of the mechanical properties of the hydrated Portland cement is expected at high-temperature
conditions since the elevated temperature adversely effects on the cement hydrated products (Costa et al.,
2017). The conditions of elevated temperature are expected in deep wells and in wells subjected to steam
injection for enhanced oil recovery (EOR). Currently, thermal oil recovery is a widely used technique around
the world to produce the heavy oil in many projects, examples are: a) Kern Field in California, USA, b)
the Athabasca Oil Sands in Alberta, Canada, c) Mene Grande in Venezuela, d) Northeast Region in Brazil,
and e) the Surplacul de Barcau Field in Romania, (Curtis et al., 2002; Panait-Patricia et al., 2006; Ichim
and Teodoriu, 2017).
The Portland cement experience major chemical and microstructural transformations under high-
temperature conditions (when the temperature exceeds 110°C), such a phenomenon is known as strength
retrogression which intensifies as long as the temperature increases beyond 110°C (Taylor, 1990; Luke,
2004; Nelson and Guillot, 2006). During such a phenomena calcium-rich products are formed in the cement
matrix which will result in an increase of the matrix permeability and a deterioration of its mechanical
properties.
Several early studies confirmed that when the temperature exceeds 110°C and based on the temperature
value, the addition of specific concentration of the silica (SiO2) particles (usually greater than 30% BWOC)
into the cement could considerably enhance the cement resistance to the strength retrogression. Interaction
of the SiO2 particles with portlandite phase (Ca(OH)2 or CH) which is one of the main products of the cement
hydration process usually lead to formation of another stable phases of calcium silicate hydrated (CSH)
species like tobermorite, trucostite, and xonotlite which are able to enhance the cement matrix mechanical
properties (Eilers and Root, 1976; Taylor, 1990; Nelson and Guillot, 2006; Richardson, 2008; Iverson et
al., 2010). Anti-retrogression agents are materials rich in silica such as silica sand and silica flour which
mostly added to the oil well cement.
Table 1 summarizes the reaction velocities of the silicate (pozzolan) cement hydration and the reaction
of CH with the pozzolan.
SPE-193059-MS 3

Table 1—Cement hydration and pozzolan reaction description (Bezerra et al., 2011).

Costa et al. (2017) examined the use of silica particles to enhance the oil wells cement resistance to the
high-temperature conditions. As a result, they reported that the optimum concentration of silica particles
that could considerably enhance the cement resistance to the high-temperature conditions of 300°C is 35%
BWOC.
The NC particles are currently used in cement industry to enhance the strength of the cement matrix
because of their ability to fill microporous of the matrix due to their considerably small size, the property
which will increase the density of the solidified cement. Wang (2017) studied the effect of replacing the
ordinary Portland cement (OPC) with 0.1 to 0.5% of the NC particles on the concrete strength at a variable
temperature from 25 to 1000°C. As a result, the author reported that, the NC particles are able to enhance
the concrete compressive strength with the increase of the temperature up to 300°C, a significant decrease
in the concrete compressive strength was noticed when the temperature is between 440 to 580°C, and the
compressive strength of the concrete reduced to about 10% of the original strength when the temperature
reached 1000°C.
The goal of this study is to evaluate the applicability of using different percentages of NC and 35% BWOC
of SF particles to enhance the compressive strength of Class G OWC under high-temperature conditions
encountered in geothermal environments and in wells experience steam injection.

Methodology
Materials
The slurries considered in this work were formulated using class G cement, silica flour, silica flour, friction
reducer additive, different concentrations of the NC particles, and deionized water the cement slurries
compositions are summarized in Table 2.

Table 2—Cement slurries compositions.

4 SPE-193059-MS

Samples Preparation
The cement slurries were prepared and tested following the American Petroleum Institute procedure (API,
2013). Six slurries with the composition in Table 2 were prepared. The first slurry (S0NC0) has no SF and no
NC particles in its formulation which is considered as the base case. In the second formulation (S35NC0),
35% BWOC of SF was added, since the 35% is considered as the optimum silica content for applications
of 300°C temperature (Costa et al., 2017). S35NC1, S35NC2, S35NC 3 and S35NC4 in Table 2 denote the
cement slurries incorporating 1.0, 2.0, 3.0, and 4.0% BWOC of the NC, respectively.
After preparation, some of the slurries was poured into 50.8 mm edge metallic cubical molds for
compressive strength testing and the remaining poured into cylindrical molds of 38.1ϕ × 76.2 mm for
permeability measurements and tensile strength testing, the molds were then submerged into a water bath at
38°C for a specific time. All the formulations in Table 2 were evaluated in two different scenarios. The low
temperature of 38°C (first scenario) which is used as a reference, and the high temperature of 300°C (second
scenario) which is used to represent the average temperature for wells undergoes cyclic steam injection for
EOR.
In the case of the first scenario, the samples were submerged into the water bath for 7 days before tested
for the UCS, tensile strength, and permeability. On the other hand, other samples were kept into the water
bath at the low temperature of 38°C for 4 days and then subjected to the high temperature of 300°C and 3000
psi for more three days (total 7 days) to represent one cycle of steam injection condition (second scenario),
after that these samples were tested for the same properties evaluated in the case of the low-temperature
scenario.

The UCS Testing

The compressive strength of the samples was evaluated based on the API procedure (API, 2013). For each
temperature condition, and for all compositions under study (Table 2) three cubical samples with 50.8 mm
edge were used to evaluate the cement matrix average compressive strength.

Permeability Measurements
The permeability of the different cement matrix compositions was measured on cylindrical samples of 38.1φ
× 76.2 mm through the application of Darcy’s law using the nitrogen as the measuring fluid.

Tensile Strength Measurement

Cylindrical samples of 38.1φ × 22.9 mm were prepared for the purpose of tensile strength testing. The
indirect tensile strength testing method (Brazilian test) was used to measure the maximum load that the
sample could resist before falling under tension. Then Eq. 1 was used to calculate the tensile strength of
the sample.

Eq. 1

Where σt denotes the Brazilian tensile strength in (MPa), P is the failure load in (N), d and l are the cement
sample diameter and length, respectively, both are in (mm).

Non-Evaporable Water Content

The samples mass loss due to exposing the samples to a high temperature was investigated which could be
then related to permeability enhancement at high-temperature conditions, cylindrical samples of 38.1φ ×
22.9 mm were aged for 4 days at 38°C then they were firstly oven dried at 105°C for 2 hours, the samples
were then weighted before and after being subjected to the high temperature of 300°C for 3 days. The loss
in the weight after exposing the samples to (300°C) of is related to the loss in the amount of the water
absorbed by NC particles.
SPE-193059-MS 5

Results and Discussion

UCS Results
Figure 1 compares the change in the strength for all the cement formulations under study with and without
subjection to 300°C. After the 7 days of curing, the base sample (S0NC0) which has zero SF and NC
content, lost 81.05% of its original strength when exposed to high temperature of 300°C as expected since
this temperature is highly more than 110°C as explained by Taylor (1990), Luke (2004), and Nelson and
Guillot (2006). The strength of the S0NC0 after 7 days decreased from 6451.0 psi to 1222.5 psi and when
undergoes a condition similar to one cycle of steam injection.

Figure 1—The UCS of the samples cured at 38°C and 300°C for 7 days.

When 35% BWOC of the SF only is added to the cement slurry (sample S35NC0), a considerable increase
in the samples resistance to the strength retrogression at a temperatures of 300°C was observed as shown in
Figure 1, which shows that the strength of the sample S35NC0 exposed to 300°C after 7 days is 6028.0 psi
compared to 1222.5 psi for the base sample (S0NC0), this is attributed to the fact that during the pozzolanic
reaction, interaction of silica particles with the CH leads to the formation of more stable CSH products
during the hydration process (Bezerra et al., 2011).
Addition of nanoclay particles up to 3.0% BWOC to the slurry of 35% SF enhanced the cement strength
no matter the temperature used. At low temperature (38°C), 3.0% of the nanoclays were able to increase the
strength of the cement by 1639.8 psi over that obtained by using 35% of SF only (S35NC0), this could be
explained as a result of the quick reaction of the NC particles which are characterized by the extremely large
surface area and its amorphous state (small particle size) with the free lime during the hydration process,
and hence, more secondary CSH gel will be produced which will effectively fill the cement matrix capillary
pores (Stefanidou and Papayianni, 2012; Hakamy et al., 2015), and thus, densifying the microstructure of
the matrix.
At high temperature (300°C), including 1.0, 2.0, or 3.0% BWOC of the NC particles to the slurry with
35%BWOC of SF was able to enhance the strength retrogression resistance compared to the sample S35NC0
which has only SF particles (Figure 1). The strength increased to 7687.9 psi when 3.0% NC is included
compared to 6028.0 psi for sample S35NC0.
6 SPE-193059-MS

In both cases of low and high temperatures, addition of 4% BWOC of NC (sample S35NC4) lead to
deterioration of the strength which after 7 days in the case of high temperature scenario becomes 4186.3 psi
which is less than that of the sample with zero nanoclay (6028.0 psi), a result which is attributed to the fact
that the use of high concentration of nanoparticles will lead to nanoparticles agglomeration in the mixes
(Shebl et al., 2009; Hakamy et al., 2014). Formation of weak zones will form due to these aggregations which
in turn prevents homogenous hydrate formations to form, and the cement strength retrogression resistance
will drastically decrease at high temperature.

Tensile Strength Results

The tensile strength results of the cement samples are presented in Figure 2, sample S0NC0 loss 66.3% of
its tensile strength after 7 when subjected to the high-temperature scenario. Including 35% of SF particles
(sample S35NC0) considerably enhanced the cement resistance to failure under tensile force and high-
temperature conditions, due to the formation of stable forms of CSH during the pozzolanic reaction between
SiO2 and CH. Incorporating NC (up to 3.0% BWOC) into the cement formulation improved its tensile
strength under high temperature, which is a result of the accelerated hydration process, before the cement
resistance to tension declined when 4.0% of NC is added, since the system overloaded with the nanoparticle,
and hence, irregular microstructure is expected to be developed.

Figure 2—the tensile strength of the samples cured at 38°C and 300°C for 7 days.

Permeability Measurement Results

Figure 3 illustrates that when the cement matrix has no SF or NC (S0NC0) its permeability increased by
71.88% from 0.0032 md to 0.0055 md when exposed to one cycle of steam injection. When 35% BWOC
of SF is added (sample S35NC0), the samples permeability under high temperature scenario decreased by
23.68%, which could be attributed to voids filling up due to matrix expansion as the temperature increases
as noticed for concrete mortars saturated with silica fume particles by Frazadnia et al. (2013).
SPE-193059-MS 7

Figure 3—The permeability of the samples cured at 38°C and 300°C for 7 days.

Incorporating the nanoclays (< 3.0%) into Class G cement decreased its original permeability
considerably which is a direct result of the high rate of hydration and the denser microstructure of the cement
matrix. For the high-temperature scenario, the permeability increased for all NC based cement samples as a
direct effect of the induced microcracks shrinkage due to loss of bound water and absorbed water from the
cement matrix and NC particles, respectively. However, the permeabilities of the NC-based samples (with
NC of less than 3.0%) are still less than that of the base samples S0NC0 and S35NC0.
Increasing the NC concentration beyond 3.0% (i.e. 4.0% of nanoclay) as in case of sample S35NC4
leads to a huge increase in the permeability under low temperature condition by 108% compared to sample
S35NC3, which is caused by the agglomeration of the nanoparticles mentioned earlier which results in
irregular microstructure, and hence, high permeability. Under high temperature scenario, the permeability
of the sample was drastically increased from 0.0027 md to 0.0052 md, which could be related to the induced
microcracks caused by the high concentration of nanoparticles (i.e. more than 3.0%) and to the evaporated
water from the cement matrix and the loss of the water absorbed by nanoclays at high temperature.

Non-Evaporable Water Content

Figure 4 summarizes the mass loss of the samples exposed to 300°C for 3 days after being dried for 2 hours
at 105°C. These samples exposed to the high-temperature condition after being aged for 4 days at low-
temperature conditions of 38°C, so the total aging time is 7 days. The results in Figure 4 show that the
sample with no SF or NC particles loss minor non-evaporable water of 1.21%, this result confirms that the
huge enhancement in the permeability of sample S0NC0 (Figure 3) when exposed to a high-temperature
condition is related to the matrix damage and not water evaporation. Adding SF particles increased the non-
evaporable water content to 3.55% after 7 days.
8 SPE-193059-MS

Figure 4—The mass loss after exposing the dried samples to 300°C for 72 hours.

Incorporating the NC into the cement matrix increased the concentration of the non-evaporable water,
which confirms that the increase in the samples S35NC1, S35NC2, and S35NC3 permeabilities are related
mainly to the evaporation of the water absorbed by the NC particles. Although sample S35NC4 non-
evaporable water content is the highest, this does not confirm that the enhancement in the permeability of
this sample is mainly related to the non-evaporable water when compared with the non-evaporable water
content and permeability enhancement for sample S35NC3, since both samples have high non-evaporable
water concentration but the permeability enhancement for the sample S35NC4 is very high compared to
sample S35NC3 (Figure 3).

Conclusions
In this study, the effect of incorporating nanoclay particles into the cement formulation contains Class
G oil well cement and 35%BWOC silica flour on the cement matrix unconfined compressive strength,
tensile strength, permeability, and non-evaporable water content at low (38°C) and high (300°C) temperature
conditions was evaluated.
Adding nanoclay particles with concentrations not more than 3.0% BWOC improved the cement
resistance to failure under compression and tension at low and high temperature situations as a result of
accelerating the cement hydration reaction, it also showed an reduction in the permeabilities at both low
and high temperatures by 62.5% and 54.5, respectively, compared to the cement samples with no silica
and nanoclay as well as with the samples contains silica only, the permeability of the nanoclay samples
increased at high temperature conditions (300°C) mainly because of the loss of the non-evaporable water
from the nanoclays interlayers.
When the nanoclays are added with concentration greater than 3.0% BWOC, agglomeration of the
nanoparticles adversely effects on the compressive and tensile strengths at 38°C and 300°C, the permeability
of the samples was also increased considerably at low temperature due to the microstructure irregularity
caused by nanoparticles agglomeration and at high temperature due to samples damage and loss of non-
evaporable water.
SPE-193059-MS 9

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