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A Diffusion Controlled Model for Prediction of Long-Term Cement Sheath

Carbonation

Conference Paper · June 2015

DOI: 10.2118/174328-MS

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SPE-174328-MS

A Diffusion Controlled Model for Prediction of Long-Term Cement Sheath

Carbonation
Cristina Aiex, and Gilson Campos, Petrobras;
Abhinandan Chiney, Abhimanyu Deshpande, Rahul Patil, Maria Paiva, and Kris Ravi, Halliburton

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the EUROPEC 2015 held in Madrid, Spain, 1– 4 June 2015.

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
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
The recent increase in production from reservoirs containing in-situ CO2 and H2S; and injection of
produced CO2 for geological carbon dioxide storage and enhanced oil recovery (EOR) has prompted strict
risk assessment, well construction best practices, and long-term monitoring. Isolation materials used in
these wells, particularly casing and cementing slurries, are to be resistant to CO2 attack. A long-term
experimental approach might be too slow to meet industry needs; therefore, model-based simulation is
essential to guide a design that helps ensure zonal isolation for the life of the well.
This work presents a diffusion-controlled model for simulating the conversion of cement hydration
products to calcium carbonate and subsequently to water-soluble calcium bicarbonate, predicting the
depth of penetration of the two reaction fronts. Temperature, total pressure, and partial pressure of CO2
are considered, corresponding to downhole conditions. After calibration with short-term experiments, the
model is able to extrapolate the degradation to long term.
A simulation tool based on this model was developed and validated using available literature results
and experiments performed with this purpose. Simulation results show that progress of the carbonation
reaction front is faster than the subsequent conversion to calcium bicarbonate. The extent of degradation
is quantified by depth of penetration of the two reactions. Strong dependency on temperature, pressure,
and partial pressure of CO2 was observed. The formation permeability also plays an important role, acting
as an additional mass transfer resistance.
The results demonstrate that the need for long-term experiments can be reduced or eliminated using this
model-based simulation tool. The tool does not only evaluate and compare current slurry formulations, but
also guides the design of new CO2 resistant materials. The extent of cement degradation attributed to CO2
injection can be predicted in downhole conditions, providing one of the most important parameters for
assessing the risk of CO2 leakage in the long term, for long-term safety of wells.

Introduction
When CO2 in formations/wellbores comes in contact with water or brine, it dissolves in the liquid, as
given by Eq. 1. Some of the dissolved CO2 reacts with water to form carbonic acid (Eq. 2).
2 SPE-174328-MS

(1)

(2)

The amount of CO2 that dissolves in water is thermodynamically governed by Henry’s Law (Eq. 3),
which states that at a given temperature the concentration of CO2 in water is directly proportional to the
partial pressure of CO2 in the gaseous phase, which is in equilibrium with the liquid. Not all of the
dissolved CO2 reacts with water to form carbonic acid (H2CO3). Only a small fraction of the gas takes part
in the reaction given by Eq. 2. That fraction is computed mathematically from Eq. 4.
(3)

(4)

The formed H2CO3 dissociates in water to form bicarbonate and hydrogen ions. The respective
concentration of the different species is given by the dissociation constant of carbonic acid in water.
Decomposition of cement occurs in two distinct steps, as visually observed in experiments conducted by
Duguid and Scherer (2010) and Brandl et al (2010). These two steps are (1) carbonation and (2) calcium
carbonate dissolution, which are explained in the following.

Carbonation Step
In this step, the bicarbonate ions formed by dissociation of carbonic acid migrate into the cement matrix
and, as they do, they react with portlandite (Eq. 5) and C-S-H phases (Eq. 6) of cement to form hard
precipitates of calcite. Calcite deposits have two positive effects on the cement—(1) because calcite is a
harder material compared to the basic ingredients of hydrated cement, the deposition of calcite increases
the hardness of the cement and (2) porosity and permeability decreases.
Eq. 5 is thermodynamically favored compared to Eq. 6, as discussed by Santra et al. (2009). This means
that the portlandite, Ca(OH)2, is more prone to react with CO2 than is the C-S-H phase. Hence, it helps
decrease the amount of portlandite in the cement sheath to help reduce the reaction with CO2.
As the reaction proceeds, it has been observed experimentally that the outer layer of the cement
gradually becomes converted to calcite and the size of the unreacted core decreases progressively.
Visually, this process can be imagined as a shrinking core model, as shown in Fig. 1. In this step, it has
been assumed that the key external reactant is bicarbonate ion.
SPE-174328-MS 3

Figure 1—Schematic view of the shrinking core representation of the carbonation step.

(5)

(6)

Calcium Carbonate Dissolution Step

This step is responsible for the loss of integrity of the cement sheath that occurs after the first carbonate
layer is formed. Here, the principal external reacting agent is hydrogen ion. Hydrogen ion reacts with the
formed calcite in the cement matrix to form soluble calcium bicarbonate. The bicarbonate leaches out with
water present in the system, resulting in a loss of calcium ions, and hence loss of structural integrity of
the cement. The chemical reaction proceeds as given by Eq. 7. From a modeling perspective, this
fundamental step can also be viewed as a shrinking core model, as in the case depicted in Fig. 1.
(7)

To develop a simple, yet scientifically accurate, model, some of the observations and assumptions that
could prove useful during the development of the model are enumerated next.
1. The process of reaction consists of two primary distinct steps— diffusion of reactants into the
unreacted core and the chemical reaction itself. These two processes can be imagined in series.
Because reactions occurring are much faster than the process of diffusion, the entire process can
be said to be diffusion controlled, and the reaction kinetics can be ignored in the model. This is
evidenced by the sharp boundaries of the reaction fronts in the photographs of reacted samples.
a. Because the reaction is instantaneous compared to the time-scale of the whole process, it is
evident as a result that the reactants are instantaneously consumed at the reaction front (i.e., the
concentration of the reactants at the reaction front [reaction zone in Fig. 1] is 0.
4 SPE-174328-MS

b. As a direct outcome of 1(a), there will be no unreacted portlandite left in the carbonated zone.
c. As a result of the foregoing assumptions, step profiles for diffusivity of the reactants in
different cement zones are expected.
2. As reaction of portlandite with carbonic acid is favored thermodynamically compared to the
reaction of carbonic acid with C-S-H, only the portlandite reaction is modeled.
3. The rate of movement of the reaction front is negligible compared to the time scale of the entire
process. Duguid and Scherer (2010) studied explicitly the rate of movements of the individual
reaction zones in a similar experiment. They reported that the rate of movement was in the order
of 20 to 400 microns per day over an experimental period of 31 days. Hence, a pseudosteady state
can be assumed.
4. Duguid and Scherer (2010) reported that the rate reaction for the bicarbonation reaction is slower
than that of the carbonation because of the following reason. It is hypothesized that the rate of
diffusion of hydrogen ions through the cement matrix is reduced considerably by the counter
diffusion of bulkier calcium and bicarbonate ions (products in Step 2). This assumption has also
been observed in the preliminary results of the experiments conducted in this study.
5. Because most formations have low permeability, the amount of CO2 that actually forms carbonic
acid and reaches the cement sheath is significantly less than that experienced in the laboratory. The
model is designed to also address that consideration.

Model Development
The model/tool is based on the shrinking core model described in the foregoing sections. The model
derives its characterizing parameters from the results of the static CO2 corrosion experiments described
later.
The parameters of the model were determined from data reported in this area of study by other
independent researchers. The development of the model for carbonation required data of higher resolution
during the carbonation phase. Suitable experiments were performed to provide better fitting results for
diffusivity.
This model is based on pure diffusion and the assumptions listed in the previous sections. There are
two kinds of diffusion data available in literature—(1) pure radial diffusion and (2) pure axial diffusion.
To validate the concept for both cases, two separate models have been developed with the same
underlying features and were then tested against the data available.

Radial Diffusion
In this case, it was assumed that diffusion occurs only in the radial direction, as shown in Fig. 2.
SPE-174328-MS 5

Figure 2—Pure radial diffusion in a cylinder.

There are two reactions that place in the system simultaneously—the carbonation reaction, where the
major reactant is bicarbonate ion, and the mechanical degradation reaction, where the primary reactant is
the hydrogen ion.
The corresponding final equations for each of the two processes are shown in Eqs. 8 and 9.
(8)

(9)

In the above equation, b is a generalized coeffient which represents the stoichiometric coefficient of the
calcium based reactant and ␳ is the density of the material in cement. The boundary conditions for Eqs.
8 and 9 indicate the initial conditions of the system. At the start of the observation time (t⫽0), both
reactions have fronts at the edge of the cylinder (r⫽R). As time progresses, the reaction front for both the
reactions moves inward, as explained in the shrinking core model previously.
The left-hand side derivative of Eqs. 8 and 9 indicates the rate of progress of the reaction front. The
negative sign indicates that, because the movement of the reaction front is inward, the absolute value of
“r” decreases with increased time (t). The fitting parameter for the discussed models is the diffusivity of
the cement matrix for the given reactant.

Axial Diffusion
In this case, it has been assumed that the diffusion of reactants take place only in the axial direction, as
shown in Fig. 3. The corresponding final equations for this case are given by Eqs. 10 and 11.
6 SPE-174328-MS

Figure 3—Pure axial diffusion in a cylinder.

(10)

(11)

In Eqs. 10 and 11, the differential on the left-hand side does not bear a negative sign because the
dependent variable of the differential (z) is set up in a manner in which, as the reaction proceeds with
increasing time, the value of the z (position of the reaction front) moves axially downward, resulting in
an increase in the value of z.
Calculation of Henry’s Constant
As explained previously, the concentration of the gas dissolved in liquid water is calculated by Henry’s
law. The constant of proportionality of Eq. 3 is known as Henry’s constant, which is characteristic of the
liquid and gases involved. Henry’s constant is also a strong function of temperature. The equations, which
assess the dependence on temperature of Henry’s constant, are of the forms of Van’t Hoff equations. Eq.
12 shows this dependence.
(12)

where C is a constant dependent only on the gas, T is the temperature at which the dissolution is
examined, and T* is the reference temperature.
Short-Term Experiments
The model developed has been calibrated against short-term experimental data. To gather these data
points, short-term corrosion experiments have been performed. Fifteen cured cement cylinders were
exposed to aqueous carbon dioxide environments for 30 days, as shown in Fig. 4, under necessary
SPE-174328-MS 7

conditions of temperature and pressure in a corrosion-resistant hastelloy high-pressure chamber of

1200-mL capacity. These tests were performed at 160°F and 1, 200 psi pressure. Sets of three cylinders
were withdrawn from the test setup at intervals of five days to study the progress of the reactions. It is
to be noted that the model predicts progress of the individual reaction by tracking its reaction front.
Therefore, in the given test, the cylinders that are withdrawn from the autoclave were cut axially and
phenolphthalein was applied on the cut faces. The indicator, which is pink in alkaline environments, such
as cement, creates a colorless band on the cement, as shown in Fig. 5. The colorless band appears because
of the neutralization reaction that occurs between carbonic acid and portlandite. This clearly demarcates
the extent of progression of the first reaction, which ends with formation of calcium carbonate. Visual
study under microscope of the degraded zone on the outer edge of the cement cylinder was performed to
track the second reaction, which involves leaching out of calcium ions.

Figure 4 —Schematic of the set of experiments for short-term tests.

Figure 5—Cement sheath after phenolphthalein test (a) noncarbonated (b) after partial carbonation.

Regression Analysis
The models were fitted to the experimental data of Duguid and Scherer (2010) and Hyvert et al. (2010)
to obtain the values for diffusivity using regression. The fit of the model to the experimental data is shown
in Figs. 6 and 7. The dependence of the calculated diffusivity on the temperature and partial pressure of
CO2 is shown in Figs. 8 and 9. It was observed that the diffusivity increased with increased temperature,
which is intuitive. This is attributed to the fact that reaction kinetics and diffusion dynamics of the
reactants are temperature dependent. An increase to temperature therefore causes an increase to the rate
of reaction and rate of diffusion of the reactants.
8 SPE-174328-MS

Figure 6 —Fitting of the model to the experimental data reported by Duguid and Scherer (2010) for pure radial diffusion as a function
of temperature.

Figure 7—Fitting of the model to experimental data reported by Hyvert et al. (2010) for pure axial diffusion. patm is partial pressure of
CO2 in number of atmospheres as unit; pCO2 signifies the atmospheric CO2 concentration.
SPE-174328-MS 9

Figure 8 —Dependence of diffusivity (normalized with the maximum value of diffusivity) on partial pressure of CO2.

Figure 9 —Regression fit of model to short term experimental tests.

It was also observed that the diffusivity decreased with increased partial pressure of CO2.This can be
attributed to the increased amount of bicarbonate ions in the system compared to lower partial pressure
of CO2. Because the rate of reaction is always dependent on the amount of bicarbonate that reaches the
10 SPE-174328-MS

calcium hydroxide (CO2 is the limiting reactant in the system) and C-S-H in cement, an increased amount
of bicarbonate should increase the amount of reactant available to the system. This results in a higher
amount of calcium carbonate being formed in the cement cylinder by virtue of higher depth of penetration,
thus reducing permeability of the cement. This creates higher resistance for the remaining reactant from
reaching the cement core, which now is comparably smaller than for the lower pressure situations,
effectively reducing the effective diffusivity of the cement cylinder. This is reflected in the depth of
penetration of the reactions, as shown in the experimental results.
Short-term experiments were performed to validate the model for high-pressure/high-temperature
(HP/HT) conditions. As explained, phenolphthalein was used to track the progress of the carbonation
reaction in the cement. The model was fitted to these data, as shown in Fig. 9. The cement used in this
exercise is the same cement recommended by the authors in Aiex et al. (2015).
The value of diffusivities obtained was then reinserted in the model and solved to predict long-term
performance of the cement under similar conditions of temperature and pressure, as shown in Fig. 10.

Figure 10 —Prediction of long-term cement corrosion from short-term experiments.

A simple flow chart is shown in Fig. 11 to help understand how the model uses short-term corrosion
testing to extend the results to better understand long-term behavior of the cement under similar
conditions.

Figure 11—Flow chart to show usage of model to better understand long-term behavior of cement from short-term testing.
SPE-174328-MS 11

Understanding the cement behavior can aid cement design and help design better cement jobs.
Traditionally, to understand long-term behavior of cement, tests are performed for prolonged durations.
Although these tests provide great understanding of the system, they are extremely time-consuming and
separate long-term testing should be performed for every expected wellbore condition. The developed
model and the proposed workflow not only help understand the system, but also provide the operator an
opportunity to predict long-term behavior of the cement by performing a few simple short term
experiments.
This simple model developed can also be used to better understand the behavior of cement under
downhole conditions. Testing performed in laboratories is highly accelerated because the cement blocks
are exposed to pure carbonic acid directly without any interference of the surrounding. In reality, the
carbon dioxide present in the atmosphere experiences an additional resistance in the form of the formation
permeability. Because most formations have low permeability, the amount of CO2 that actually forms
carbonic acid and reaches the cement sheath is significantly less than that experienced in the laboratory.
The model described in the previous sections can be combined with a calculation (Eq. 13) to determine
the effect of formation permeability on corrosion of cement where Q is the mass flux of CO2 coming in
from the formation. Eq. 13 solves a steady state Fick’s Law, assuming the resistance is dependent solely
on the permeability of the formation. This model also assumes continuity of flux across the interfaces of
the formation and cement. This implies there will be no material accumulated at the interface of the two
materials—whatever comes in from the formation will be instantly be taken by the cement sheath for
reaction.

Figure 12—Depth of penetration of the carbonation reaction as predicted by the model after exposure to CO2 for 30 years after
incorporating formation permeability of 200 md (model calibrated for same cement as discussed).

(13)

Carey et al. (2007) reported field data for cement in a well where CO2 was injected for EOR for 30
years after 25 years of regular production. The investigators found carbonation depth of approximately 2
12 SPE-174328-MS

mm. The model when simulated for the same scenario with the cement for which it was previously
calibrated, exhibited a depth of penetration of approximately 1.1 mm. The depth of penetration predicted
by the model, although of the same order of magnitude as that reported in literature, is different
quantitatively. This is attributed to the different kinds of cement slurry that have been used in each of the
cases. Also, formation permeability used is a general value and might not represent that of the true well
data. This exercise validates the model subject to availability of data.

Conclusions
A simple diffusion based model has been developed in the present work aimed to provide a short-term
testing method to better understand the behavior of cement under long-term corrosion attack in any
condition. A workflow using the model has been proposed to extend the short-term test results to long
term corrosion effects on the cement. The model is capable of handling any condition of temperature and
pressure as long as thermodynamic properties to calculate kinetic constants are available. Formation
permeability is also accounted for by incorporating an additional layer of resistance.
This work enables remedial work to help improve cement jobs, even before cement is pumped into the
well, and thus potentially extend the life of the well.

Symbols
Symbol Meaning
px Partial pressure of component “x” in the gaseous phase in equilibrium with the liquid
kH Henry’s constant
Cx Concentration of component “x” in the liquid phase
rd Radial position of bicarbonation reaction front
rc Radial position of carbonation reaction front
t Time of exposure
D Diffusivity
K2 Equilibrium constant for Eq. 2
s Solid phase
aq Aqueous phase

References
Aiex, C., Campos, G., Chiney, A. et alet al. 2015. An Experimental Study on Effects of Static CO2
on Cement under High-Pressure/High-Temperature Conditions. Presented at the Offshore Tech-
nology Conference, Houston, Texas, 4 –7 May.
Brandl, A., Cutler, J., Seholm, M.S. et alet al. 2010. Cementing Solutions for Corrosive Well
Environments. Presented at the International Oil and Gas Conference and Exhibition, Beijing,
China, 8 –10 June. SPE-132228-MS. http://dx.doi.org/10.2118/132228-MS.
Carey, J.W., Wigand, M., Chipera, S.J. et alet al. 2010. Analysis and Performance of Oil Well Cement
with 30 Years of CO2 Exposure from SACROC Unit, West Texas, USA. International Journal of
Greenhouse Gas Control 1(1):75–85. http://dx.doi.org/10.1016/S1750-5836(06)00004-1.
Duguid, A. and Scherer, G.W. 2010. Degradation of Oilwell Cement due to Exposure to Carbonated
Brine. International Journal of Greenhouse Gas Control 4(3):546 –560.
Hyvert N., Sellier, A., Duprat, F. et alet al. 2010. Dependency of C-S-H carbonation rate on CO2
pressure to explain transition from accelerated tests to natural carbonation. Cement and Concrete
Research 40: 1582–1589. http://dx.doi.org/:10.1016/j.cemconres.2010.06.010.
 SPE-174328-MS 13

Santra, A.K., Reddy, B.R., Liang, F. et alet al. 2009. Reaction of CO2 with Portland Cement at
Downhole Conditions and the Role of Pozzolanic Supplements. Presented at the SPE International
Symposium in Oilfield Chemistry, The Woodlands, Texas, 20 –22. SPE-121103-MS. http://
dx.doi.org/10.2118/121103-MS.

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