Cementing Solutions for Corrosive Well
Environments
A. Brandl, J. Cutler, A. Seholm, M. Sansil, and G. Braun, Baker Hughes Incorporated
Summary
Main factors that are responsible for the corrosion of the cement
sheath in wells are determined on the basis of laboratory tests and
field analyses from a literature survey. A description of the chem-
istry, mineralogy, and physical properties of American Petroleum
Institute (API) well cements and their mechanisms of corrosion
in the presence of aggressive formation and injection fluids [such
as magnesium- or sulfate-containing brines and carbon dioxide
(CO2)] is given. API cement hydration mainly produces calcium-
silicate-hydrate (C-S-H) phases (xCaO·ySiO2·zH2O), which are
responsible for the strength, and portlandite [Ca(OH)2], which
is basically a weak point within the cement matrix. Increasing
the permeability and the portlandite content reduces strength and
chemical resistance of set cement toward corrosive media. The
addition of pozzolanic materials eliminates portlandite and allows
lowering the water content in the cement system. Both effects can
reduce the permeability and improve the mechanical properties
of set cement. Cement specimens were prepared and exposed to
CO2-loaded water at 300°F and 3,000 psi for 6 months. Mechani-
cal-properties tests, microscopy, and quantitative CaCO3 analyses
revealed significantly less corrosion and fewer negative impacts for
a pozzolan/API cement blend compared with a conventional API
cement design at the same density. These findings were related to
the effect of the used pozzolans on the formed C-S-H. Practical
concepts for improvements of the cement sheath with respect to
cement-slurry design, cementing process, and the impact of factors
such as temperature or cement admixtures are presented to mitigate
cement corrosion.
Introduction
Well cementing is a fundamental and essential part of the process
of drilling a well. The primary goals of the annular cement sheath
in wells are zonal isolation, supporting the casings, and protecting
the casings from corrosion. The cement sheath must not only with-
stand downhole stresses induced by pressure and temperature fluc-
tuations, but also corrosive attacks from aggressive formation and
injection fluids (such as in CO2 flooding for enhanced oil recovery
or in CO2 capture and storage). Cement-sheath failures leading to
loss of zonal isolation are the biggest concerns because they affect
the wellbore integrity and so the life of the well, with economic
consequences: decline in production rates; loss of production time
for remedial cementing; and in the worse case, even complete well
failure/collapse, so that well abandonment necessary.
These problems create an imperative to design cement systems
that counteract all negative impacts on the sheath integrity during
the life of a well to ensure maximum durability. Synthetic and
epoxy-resin-based binders provide high chemical resistance and
good mechanical properties in the well (Cole 1979). Nevertheless,
their high costs limit their use to special applications. Calcium
aluminate- or phosphate-based cements also proved to be more
highly corrosion resistant than Portland cements (Sugama 2006).
But these cements are sensitive to contamination with Portland
cements and so must be handled separately, requiring advanced
Copyright © 2011 Society of Petroleum Engineers
This paper (SPE 132228) was accepted for presentation at the International Oil and Gas
Conference and Exhibition in China, Beijing China, 8–10 June 2010, and revised for
publication. Original manuscript received for review 23 March 2010. Revised manuscript
received for review 8 October 2010. Paper peer approved 13 October 2010.
208
planning and expensive logistics. Portland-cement-based systems
are still preferred because of their economical and practical advan-
tages as well as their ready availability. The objective of this study
was to find cementing solutions for corrosive well environments
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using Portland cement-based systems. The following steps were
executed to approach this goal:
1. Understand the mineralogy, chemistry, and physical proper-
ties of set API cements.
2. Study the mechanisms of different corrosion types for API
cements and potential solutions based on a literature survey.
3. Test and evaluate a designed pozzolan API cement system
in comparison with a conventional system for a corrosive well
scenario (CO2, bottomhole static temperature of 300°F, 3,000-psi
pressure) with occurring mechanical downhole stresses.
4. Compose cementing guidelines for best practices in corrosive
well environments.
Mineralogy and Properties of Set API Cements
The API well cements (A–H) are Portland cements manufactured
according to API Specification 10A. Today, the universal cements
API Class G or H are normally used for well cementing. Dur-
ing cement hydration, essentially C-S-H phases and portlandite
are formed (Eqs. 1a and 1b) because 3CaO·SiO2 and 2CaO·SiO2
make together approximately 85 wt% in API Class G/H clinker.
Hydration of 3CaO·Al2O3 and 2CaO·(Al2O3,Fe2O3), in the presence
of a setting control agent (e.g., gypsum CaSO4·2H2O), results in
[Ca4Al2(OH)12](SO4)·6H2O monosulfate or [Ca4(Al,Fe)2(OH)12]
(SO4)·6H2O monosulfo-aluminate (-ferrite), respectively (Eqs. 1c
and 1d).
3CaO·SiO2 + xH2O → yCaO·SiO2·[y–(3–x)]H2O
(= C-S-H) + (3–y) Ca(OH)2 (= portlandite), . . . . . . . . (1a)
2CaO·SiO2 + xH2O → yCaO·SiO2·[y–(2–x)]H2O
(= C-S-H) + (2-y) Ca(OH)2 (= portlandite), . . . . . . . . (1b)
3CaO·Al2O3 + CaSO4·2H2O + 10H2O
→ [Ca4Al2(OH)12](SO4)·6H2O, . . . . . . . . . . . . . . . . . . (1c)
3[2CaO·(Al2O3,Fe2O3)] + 2CaSO4·2H2O + 23H2O
→ 2([Ca4(Al,Fe)2(OH)12](SO4)·6H2O) + 2(Al,Fe)(OH)3.
. . . . . . . . . . . . . . . . . . . . . . . (1d)
C-S-H phases occur in fine needles—during cement hydration
they grow in length and grab onto each other like a zipper, resulting
in high strength. Portlandite, on the other hand, consists of large
hexagonal crystals between the C-S-H phases. The amount of
formed portlandite in a set, pure Portland cement depends on the
degree of hydration, temperature, exact clinker-phase composition,
water-to-cement ratio, and composition of formed C-S-H phases,
and it can be up to 35 wt% (Milestone et al. 1986). Portlandite
does not contribute to the strength and so is a weak point in the
cement matrix. On a microscopic level, even a set Portland cement
is still a porous, water-filled system, into which corrosive fluids can
penetrate and cause deterioration. Increasing the amount of mix
water increases the percentage of capillary pores in the hardened
cement. Capillary pores are mainly responsible for the perme-
ability. Increasing permeability reduces a cement’s strength and
resistance to corrosive media.
June 2011 SPE Drilling & Completion
Effect of Pozzolanic Materials. An efficient way to reduce the
amount of portlandite, strengthen the matrix, and decrease the perme-
ability of set cement is to add fine pozzolanic materials (e.g., diato-
maceous earth, volcanic ash, silica fume, metakaolin, calcined clay,
and/or fly ash) to the cement. The SiO2 (and Al2O3) constituents of the
pozzolanic additions react with portlandite and convert it to further
C-S-H phases (or C-A-S-H phases: xCaO·wAl2O3·ySiO2·zH2O,
with A standing for Al) according to the pozzolanic reaction:
xCa(OH)2 + ySiO2 (and wAl2O3) → xCaO·ySiO2·zH2O
(and xCaO·wAl2O3·ySiO2·zH2O). . . . . . . . . . . . . . . . . . (2)
Pozzolanic materials have typically been added to API cements as
extenders to design filler slurries. Pozzolanic materials generally
have a lower specific gravity (s.g. of 2.0–3.0 g/cm3) than cement
(s.g. of 3.2 g/cm3). Consequently, at a constant water/solid ratio, the
pozzolanic additions will reduce the density of the cement slurry,
or, at a constant slurry density, the pozzolan additions will reduce
the water/solid ratio in the cement slurry. This will decrease the
permeability of the set cement significantly (Nelson and Guillout
2007). Finally, the partial substitution for cement by relatively
chemically inert pozzolanic materials essentially contributes to
further improvement of corrosion resistance.
Cement Corrosion Because of High
Temperatures
At elevated temperatures, a number of thermodynamically stable
C-S-H phases occur, depending on the formal molar ratio of CaO
to SiO2 in the Portland cement (Taylor 1964). The formal molar
CaO/SiO2 ratio for a neat cement is approximately three, resulting
in the formation of conventional C-S-H phases. Above a tempera-
ture of 230°F, these C-S-H phases will transform into a thermo-
dynamically more stable ␣-Ca2[SiO3(OH)](OH) (␣-C2SH) phase
with higher crystalline density, reducing compressive strength
and increasing permeability of set cement (strength retrogression).
This conversion reaction can be prevented by adding 35–40% by
weight of cement (BWOC) of SiO2 to the cement (silica-stabilized
cement). This reduces the formal molar CaO/SiO2 ratio to approxi-
mately unity, and the more-stable tobermorite phase is formed
at temperatures of approximately 230°F, preserving high com-
pressive strength and low permeability in the set cement. Above
302°F, tobermorite converts into xonotlite and/or gyrolite. Both of
these higher-temperature phases result in improved well-cementing
qualities (low permeability and high compressive strength).
Cement Corrosion Caused by Poor Cement Quality or Incom-
patible Additions. Insufficient conversion of CaO or MgO during
the cement-manufacturing process results in high free-lime (CaO)
or periclase (free-MgO) content of the clinker. Hydration of free
lime or periclase after cement setting can cause destructive expan-
sion within the set cement (Odler 1998):
CaO, MgO + H2O → Ca(OH)2, Mg(OH)2 => expansive
. . . . . . . . . . . . . . . . . . . . . . . (2)
Therefore, the free-lime and periclase contents must be limited to
2 wt% or 6 wt%, respectively, to mitigate expansion issues.
Increasing the alkali content increases the hydroxide concentration
in the pores of set cement. The combination of reactive (amor-
phous) silica aggregates (such as chert, quartzite, opal, strained
quartz crystals, and glass) and high concentrations of hydroxides
results in a gel (alkali-silica reaction), increasing in volume by
taking up water and so exerting an expansive pressure:
NaOH, KOH + SiO2 (amorphous) + water
→ alkali-silica-gel => expansive. . . . . . . . . . . . . . . . . . (4)
The results are cracks throughout the cement matrix. Therefore,
the total alkali content must be limited to 0.75 wt% of Na2O
equivalents, as required for API cements. Another way to reduce
June 2011 SPE Drilling & Completion
the likelihood of alkali-silica reaction is to decrease water content
or use pozzolans as a partial cement replacement in the system;
the latter also reduces the alkalinity of the pore fluid.
Cement Corrosion Caused by Expansive Attack. Generally,
there are two categories of cement corrosion induced by chemical
attacks: that by expansive attack and that by dissolving attack.
During the expansive (or expanding) attack, the corrosive fluid
penetrates the cement pores and forms voluminous water-insoluble
products. As their crystal size increases, these products create high
pressure inside the set cement, resulting in cracks, fractures, and
fragments. The most well-known expansive attack is the sulfate
attack. Sulfate-containing formation fluids penetrate into the pores
of the cement sheath and react with the 3CaO·Al2O3 phase of the
cement and its hydration products to form secondary or delayed
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ettringite crystals, which fill the cement pores (Morales at al.
2003):
3CaO·Al2O3 + 3(CaSO4·2H2O) + 26H2O
→ [Ca6Al2(OH)12](SO4)3·26H2O ettringite, . . . . . . . . . . (5)
3CaO·Al2O3·6H2O + 3(CaSO4·2H2O) + 20H2O
→ [Ca6Al2(OH)12](SO4)3·26H2O ettringite, . . . . . . . . . . (6)
3CaO·Al2O3·CaSO4·12H2O + 2(CaSO4·2H2O) + 16H2O
→ [Ca6Al2(OH)12](SO4)3·26H2O ettringite. . . . . . . . . . . (7)
These formed ettringite crystals can reach sizes up to 50 µm, caus-
ing high internal pressures in the cement pores until fractures of
the cement sheath occur. Besides ettringite, sulfate can also react
with portlandite of the set cement to form secondary (or delayed)
gypsum crystals:
Ca(OH)2 + Na2SO4 + 2H2O
→ CaSO4·2H2O secondary gypsum + 2NaOH. . . . . . . (8)
Bellmann and Stark (2006) found that cement deterioration caused
by the formation of secondary ettringite and gypsum at ambient
conditions occurs only above a sulfate concentration of 1500 mg/L
or 3000 mg/L, respectively. Because the water solubility of sodium
and magnesium sulfates is low at temperatures above 140°F, sul-
fate attack is not a big issue at this temperature or higher (Suman
and Ellis 1977). For temperatures below 140°F, it is essential to
use high sulfate-resistance cements (3CaO·Al2O3 phase content
below 3 wt% for API cements) and to eliminate portlandite in the
set cement. Morales et al. (2003) discovered that decreasing the
permeability is an even more efficient way to avoid sulfate attack.
Using pore-blocking additives (such as latex, sodium silicate, or
microsilica) or a lower water/cement ratio will improve the sulfate
resistance of an API Class A cement.
Magnesium attack is another example of expansive attack.
Magnesium-containing formation fluids precipitate under high pH
conditions in the pores of set cement or react with the portlandite
to form brucite [Mg(OH)2] by ion base exchange:
Ca(OH)2 + Mg2+ → Ca2+ + Mg(OH)2 => expansive.
. . . . . . . . . . . . . . . . . . . . . . . . (9)
The formation of expansive Mg(OH)2 induces mechanical stresses
in the set cement, resulting in destruction. In addition, calcium ions
in the C-S-H phase lattice are exchanged with magnesium ions,
resulting in strength retrogression and ultimately complete deterio-
ration, as reported by Steinmann (1972). Wollherr (1999) tested the
chemical resistance of a conventional API Class G cement com-
pared to a blast-furnace-slag/pozzolan/Portland-cement system
(high-magnesium-resistance cement) in a high-MgCl2 (200-g/L)
brine at 257°F. Only the high-magnesium-resistance cement still
possessed integrity after 6 months; the conventional API Class G
cement system showed severe expansive deterioration and loss of
integrity.
209
Cement Corrosion Caused by Dissolving Attack. When cement
exposure to corrosive fluids creates water-soluble products, the
set cement is leached from the surface (dissolving attack). During
reservoir stimulation, the cement sheath (in particular around the
perforation zone) may be exposed to strong acids [hydrochloric
acid (HCl) and hydrofluoric acid (HF)]. Lécolier et al. (2010)
estimated that 40% of all gas reservoirs contain at least 100 ppm
of sour gas (H2S), a relatively weak acid. Conventional set API
cements do not withstand acidic conditions and will dissolve over
time with decreasing pH. The portlandite becomes unstable at a pH
below 12.6 (Grabau 1994) and so will leach out first:
2H+ + Ca(OH)2 → Ca2+ + 2H2O. . . . . . . . . . . . . . . . . . . . (10)
Below a pH of 8, the strength-giving C-S-H phases (e.g.,
3CaO·2SiO2·3H2O) are also destabilized, followed by leaching of
Ca2+ and formation of amorphous silica (SiO2):
6H+ + 3CaO·2SiO2·3H2O → 3Ca2+ + 2SiO2 + 6H2O.
. . . . . . . . . . . . . . . . . . . . . . . (11)
The remaining amorphous silica forms a protective coating that
slows the acid reaction rate. The rate of deterioration is accelerated
if the amorphous silica is washed away (e.g., dynamic conditions).
As reported by Brady et al. (1989), conventional Class G cement
showed a significant weight loss (96%) within a short time when
exposed to 12–3% HF/HCl (HCl-/HF-containing mud) at 190°F
under dynamic conditions. Mud-acid systems are typically used to
stimulate sandstone reservoirs. According to Blount et al. (1991),
the resistance of Portland cement toward acid attacks can be
improved by 700% when substituting for the cement with greater
amounts of American Society of Testing Materials (ASTM) Class
F fly ash in conjunction with the use of liquid-latex dispersion. The
fly ash eliminates acid-susceptible portlandite, reduces the perme-
ability of the set cement, and partly replaces Portland cement with
relatively chemically inert siliceous materials. Adding latex will
form an artificial barrier between the cementitious phases and the
attacking fluid. Adding ASTM Class F fly ash or the liquid latex
alone was found to improve the mud-acid resistance by 48% or
>85%, respectively.
Al-Taq et al. (2009) recently explained that pretreating a neat
cement with a mixture of 10% acetic acid + 1.5% HF leads to a
protective layer of CaF2, which significantly improves resistance
to mud-acid attack. The weight loss for pretreated neat cement in
mud acid at 150°F after 2 hours was only 2 wt% compared to 32
wt% for untreated cement. Therefore, it was recommended to start
stimulation of sandstone reservoirs with a preflush of 10% acetic
acid + 1.5% HF. This is a simple and cost-effective procedure to
protect conventional cement between the casing and the formation
from severe acid corrosion.
The corrosive H2S attack on Portland cement under well
conditions was studied by Lécolier et al. (2010). A low-perme-
ability Portland cement containing silica fume was exposed to
H2S-saturated fluid (pH = 4) at 248°F and 2,176 psi for 21 days.
Within a corrosion depth of 11 mm, all portlandite was completely
removed and calcium from the C-S-H phases was partly leached
out. It was concluded that alternative cements must be used to
guarantee long-term integrity for H2S-affected injection wells.
Noïk and Rivereau (1999) designed a “reactive powder cement”
composed of API Class G cement with sand and silica fume. The
system mixed at 15.8 lbm/gal (ppg) and had a low water/cement
ratio of 0.27, resulting in low water permeability of less than 10–6
md after curing at 356°F for 3 months. Reactive-powder-cement
samples were exposed to seawater in the presence of 10% H2S gas
at 248°F. After 1 year of aging, the compressive strength actually
increased by 30%, which proved durability of the system in H2S
under the given conditions.
Cement Corrosion in the Presence of CO2. Lécolier et al. (2010)
also reported that 40% of the world’s remaining gas reserves naturally
contain more than 2 vol% of CO2. Some gas reserves contain more
than 50 vol% of CO2. Moderate concentrations of CO2 (5–30 vol%)
210
are most common in gas wells. Furthermore, supercritical CO2 is
used for enhanced oil recovery during CO2 flooding. In recent years,
CO2-sequestration/-injector wells have come to have great impor-
tance in reducing CO2 emissions and so the effect of greenhouse
gas. Onan (1984) was the first to test CO2 attack (under well condi-
tions at elevated temperatures and pressure) and concluded that the
presence of CO2 in wells could be a serious problem.
As part of the present study, CO2 attack was simulated by
exposing a 2-in.-long, 1-in.-diameter cylinder of set cement (Class
G + 40% BWOC silica flour mixed at 15.8 ppg) to CO2-loaded
water at 250°F and 650-psi CO2 pressure for 30 days. A thin sec-
tion was prepared from a cylinder half and was analyzed under the
optical microscope (Fig. 1). Evaluation of the photomicrograph
confirms the findings published earlier by Barlet-Gouédard et al.
(2006) and Kutchko et al. (2007, 2008).
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Cement corrosion in the presence of CO2 is a special case of
dissolving attack because it consists of three sequential steps: First,
(Step 1 in Fig. 1c) is the formation of carbonic acid in the presence
of moisture (Eq. 12). The solubility of CO2 gas in water is (with
1.45 g/L under ambient conditions) relatively low, and only 0.2%
of the dissolved CO2 reacts with water to form carbonic acid and its
dissociated form. This explains that CO2 or carbonic acid, respec-
tively, is a very weak acid compared to HCl or mud acid. Even at
high partial pressure, the pH value will not drop below 3.5.
The second step (Step 2 in Fig. 1c) is the carbonation of the
cement components: The carbonic acid penetrates the cement
matrix and preferentially reacts with the portlandite, converting
it into calcium carbonate and water (Eq. 13). The conversion of
portlandite to calcium carbonate reduces the pH from 13 to less
than 10. Carbonic acid also reacts with the C-S-H phases to form
CaCO3 and amorphous (porous) silica (Eq. 14). Carbonation of
portlandite is believed to be faster than that for the C-S-H phases
(Santra et al. 2009). Because calcium carbonate has a higher molar
volume than portlandite (+11%) (Stark and Wicht 2001), the total
pore volume is reduced and so the permeability of the cement
matrix is initially decreased by carbonation. Carbonation of the
cement also increases its mass and its compressive and tensile
strength. However, the amorphous silica gel does not contribute
to strength like the CaCO3 (calcite).
The final step (Step 3 in Fig. 1c) is the leaching (Eq. 15) and
deposition process (Eq. 16), which is actually the detrimental reac-
tion: Further carbonic acid reacts with the formed calcium carbon-
ate and converts it into calcium bicarbonate, which is highly water
soluble and can be leached out of the cement matrix easily. All
reactions are thermodynamically driven, but their kinetics depend
on the given conditions (e.g., temperature, pressure, concentrations
of educts and products within the reaction equilibria).
In summary, then, cement corrosion caused by CO2 attack can
be described with the following chemical equations.
Formation of carbonic acid:
CO2 + H2O ⇌ H2CO3 ⇌ H+ + HCO3–. . . . . . . . . . . . . . . . (12)
Carbonation of the cementitious phases:
Ca(OH)2 + H+ + HCO3– ⇌ CaCO3 + 2H2O, . . . . . . . . . . . (13)
xCaO·ySiO2·zH2O (= C-S-H ) + x H+ + x HCO3–
⇌ xCaCO3 + y SiO2 (amorphous and porous silica)
+ (z+x) H2O. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (14)
Leaching out and deposition, respectively, of calcium
carbonates:
CO2 + H2O + CaCO3 ⇌ Ca(HCO3)2, . . . . . . . . . . . . . . . . (15)
Ca(HCO3)2 + Ca(OH)2 ⇌ CaCO3 + H2O. . . . . . . . . . . . . (16)
In the Scurry Area Canyon Reef Operators Committee field
study by Carey et al. (2007), a cement section with casing and
June 2011 SPE Drilling & Completion
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Fig. 1—(a) Set-cement cylinder (Class G+40% BWOC silica flour mixed at 15.8 ppg) after 30-day exposure to CO2-loaded
water at 250°F/650-psi CO2 pressure. (b) Cylinder was cut in half, and a thin section was prepared. (c) Thin-section petrography:
Unaltered set cement (I ) still exists having C-S-H phases and portlandite. On the far right side is the corrosive fluid (V ) with the
CO2 that has reacted with water to form carbonic acid (Step 1). The carbonated cement and its propagation front (Step 2) can
be clearly seen in the middle part (III ). The leaching of the carbonated cement with further attack of carbonic acid (Step 3) has
already taken place, resulting in a soft and porous rim (IV) dark black zone at the rim because of stronger penetration of the
blue dye is indicating higher porosity).

formation right above the perforation zone from a 55-year-old well
was cored and analyzed. The original pumped system was a neat
Portland cement with a density of approximately 15.5 ppg. After
25 years of production, CO2 was injected for enhanced oil recovery
for 30 years. The recovered cement samples showed a corrosion
depth of 2 to 10 mm. This suggests that cement corrosion in the
presence of CO2 is a very slow process. It was concluded that
“the cement retained its capacity to prevent significant transport
of fluid through the cement matrix.” Recovered field samples from
this well indicated that degradation occurs mainly along existing
or induced migration pathways. Consequently, the cement’s abil-
ity to resist CO2 attack seems to be secondary: More important
is the ability to obtain a good initial bond with the casing and
formation.
Crow et al. (2009) published a similar detailed field study
(CCP—CO2 Capture Project Phase 2) concerning a 30-year-old
well from a natural-CO2-production reservoir (96% CO2). Infor-
mation about cement and casing samples recovered from different
side walls and reservoir-fluid and -pressure measurements were
collected and analyzed. The well was cemented 30 years ago with a
system of 50:50 fly ash/API Class H cement including 3% benton-
ite mixed at 14.2 ppg (extended pozzolan API cement system). The
temperature was up to 140°F, and the pressure was approximately
1,500 psi. Mineralogy of the cement cores revealed maximum
CaCO3 content near the CO2 reservoir and original cement phases
more abundant further from the reservoir. This pozzolan extended
API cement system inhibited CO2 migration, although carbonation
occurred and permeability and porosity increased. No casing
pressure was observed during the life of the well, confirming no
leakage. Furthermore, evaluation-log information was presented
in detail, indicating generally good cement-bond quality. Con-
sequently, Portland-cement-based systems can be used in a CO2
environment if good cementing practices are employed.
Milestone et al. (1986) investigated the effect of silica addi-
tions to Portland-cement systems after 14 days of exposure to
CO2 at 302°F. They found that increasing additions of silica will
reduce the portlandite content and increase the carbonation depth
in the set cement system. Any portlandite present will react with
CO2 to form a protective layer of calcite, which decreases perme-
ability and inhibits further attack. Therefore, the authors suggested
that the amount of added silica be reduced from 35–40% to 15%
BWOC to retain a certain amount of portlandite in the set cement
to improve CO2 resistance. The evaluation of the recommended
design regarding water permeability and long-term integrity was
not presented. Consequently, it was not proved that the reduced
silica content is sufficient to prevent strength retrogression or that
the actual detrimental leaching step caused by further CO2 attack
was mitigated.
For the current study, a pozzolan-containing API cement sys-
tem, with sufficient silica additions to prevent strength retrogres-
sion, was designed at a density of 15.0 ppg without bentonite but
with reduced water content. The goal of the study was to evaluate
the effect of CO2 on the integrity of the pozzolan cement system
at 300°F and 3,000 psi over a period of 6 months.
Testing and Evaluation
Cement Designs and Chemical Analyses. For the CO2 tests a
pozzolan/API-Class-G/silica-flour system mixed with seawater
at a density of 15.0 ppg was used (pozzolan) (Table 1). This
system was compared directly to a “conventional” cement system
(API Class G with 35% BWOC silica flour) at the same density.
Less mixing water was required for the pozzolan system. The
same chemical admixture package was added to both systems to
stabilize the slurry (no free water, no channeling, no settling) and
to achieve static API fluid-loss control below 100 cm3/30 min at
300°F and thickening times of 7 hours at bottomhole circulating
temperature of 260°F and 3,000 psi. Slurries were mixed accord-
ing to API RP 10B procedures, and cement specimens [2-in.-long,
1-in.-diameter cylinders and briquettes (“dog bones”) according
to ASTM-307] were cured at 3,000 psi and 300°F for 96 hours.
After recovering from the curing chamber, all grease was properly
removed from the specimens by intensive washing with water and
soap. Specimens showing cracks or irregularities on their surfaces
were discarded. Analyses of both cured systems revealed almost
identical composition (Table 1). For both systems, the formal CaO
content was 47 wt% (±1). Sufficient silica was present in both
cement systems to reduce the formal molar CaO/SiO2 ratio to
approximately 1.1 to prevent strength retrogression. According to
X-ray powder diffraction analyses, practically no portlandite was
found in either system.

June 2011 SPE Drilling & Completion 211

 TABLE 1—CEMENT-SYSTEM DESIGN, PROPERTIES, AND OXIDIC
COMPOSITION

Cement System Pozzolan Conventional

Base blend Pozzolan + API Class G API Class G + 35% BWOC

+ silica flour of silica flour

Slurry density 15.0 15.0

(lbm/gal)
Water: solid (wt/wt) 0.55 0.72
Portlandite (wt%) Not detected Not detected

Oxidic Composition of Set Sement Systems (Calculated From EDS Analyses)

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CaO (wt%) 46.6 47.5
SiO2 (wt%) 40.8 39.8
C (wt%) 2.4 2.3
Na2O (wt%) 0.6 0.6
M g O (w t % ) 0 .4 0.4
Al2O3 (wt%) 2.4 2.2
SO3 (wt%) 3.1 2.8
Cl (wt%) 0.7 0.6
K2 O (wt%) 0.1 0.2
Fe2O3 (wt%) 2.9 3.4
Total (wt%) 100.0 100.0

CO2 Tests. To simulate the CO2 or carbonic acid attack within
the cement specimens under static conditions, a modified high-
temperature/high-pressure (HT/HP) curing chamber (Model 4000,
Nordman Instrument Incorporated, Houston, Texas) was used and
was attached to a CO2 bottle (Fig. 2a). The rack with the cement
specimens (Fig. 2c) was released into the 5.1-L interior of the curing
chamber (Fig. 2b). The chamber was then completely filled with tap
water, and CO2 gas was injected constantly from the bottom of the
chamber with the help of a high-pressure booster for 5 minutes to
generate CO2-loaded water (measured pH = 5). The curing chamber
was pressurized with CO2 gas to 3,000 psi and heated to 300°F
within 4 hours. Any pressure reduction was automatically compen-
sated with further CO2 injection through pump cycles, guaranteeing
a continuous supply of CO2.. After 1, 3, and 6 months of exposure,
the pressure and temperature in the HT/HP curing chamber were
gradually decreased over 12 hours and a set of cement specimens
was recovered for mechanical and mineralogical analyses. Because
of the increase of the pH to 6, the CO2-loaded water was refreshed
each time samples were taken. The initial volume ratio between the
corrosive fluid and all cement specimens was calculated to be 4:1,
but then was increased to 5:1 and finally 6:1 because some samples
were recovered after 1 and 3 months.
Testing and Evaluation Methodology. Thin-section petrography.
Each cement cylinder was cut in half, and one of the halves was
impregnated with blue epoxy resin under vacuum to enhance the
display of porosity. The sample was then attached to a glass slide
and ground to a final 30-µm thickness.
Scanning Electron Microscopy (SEM). All cement specimens
were prepared such that a freshly broken surface was presented
to the electron beam. For low magnifications of 1,000X or less,
samples were not coated and were viewed using the “wet mode”
(gaseous secondary electron detector—1.0-torr H2O pressure) of
the SEM. For higher magnification (5,000X), cement specimens
were dried at low temperature and subsequently sputter coated
with gold under vacuum. A secondary electron detector was used
for the high-magnification imaging.
Chemical Analysis. An energy-dispersive-spectrometry (EDS)
system from IXRF System Incorporated was used for all analyses.
The excitation voltage on the SEM was 20 kV.
Young’s Modulus, Poisson’s Ratio, and Compressive Strength.
These were determined from uniaxial and triaxial stress/strain
tests performed on cement cylinders under a confining pressure of
1,000 psi. Testing procedures and apparatus closely follow ASTM
D 7012-07 “Standard Test Method for Compressive Strength and

Fig. 2—(a) Modified HT/HP curing chamber connected with a CO2 bottle; (b) interior of the chamber; (c) cement-cylinder specimens
on the rack after 3-month exposure to CO2-loaded water.

212 June 2011 SPE Drilling & Completion


Fig. 3—(a) Cylinders of the pozzolan and conventional cement systems after exposure to CO2-loaded water at 300°F and 3,000
psi for 1 month and sample preparation for evaluation. (b) Testing BH. (c) Profile of the pozzolan (left) and conventional (right)
cement systems with their determined BH and CaCO3 content.
Elastic Moduli of Intact Rock Core Specimens under Varying
States of Stress and Temperatures” recommended practices.
Tensile Strength. These data were determined from a direct
uniaxial tensile-strength method according to ASTM Standard
C-307 tensile strength using briquette specimens (dog bones) and
a United press model STM-20k.
Microindentation. Brinell hardness (BH) was determined by
forcing a hard steel sphere of a specified diameter under a specified
load into the surface of a material and measuring the diameter of
the indentation left after the test. BH is obtained by dividing the
load used, in kilograms, by the actual surface area of the indenta-
tion, in square millimeters. The result is a pressure measurement,
but the units are rarely stated.
Water Permeability. Cement cylinders were loaded into a
preheated (200°F) Hassler-style core holder, and a confining pres-
sure of 4,500 psi (1,500-psi net confining pressure) was applied.
Using an Isco syringe pump, deionized water was injected at con-
stant pressure into one end. Injection pressure was introduced in
500-psi increments to 3,000 psi. Water flow through the sample
was monitored by volume change in a pipette.
Quantitative Determination of CaCO3. Cement specimens
were dried under vacuum and ambient temperature for 5 days.
The amount of lost water during the drying process was taken
into account for the quantitative determination of the total CaCO3
content (sum of aragonite and calcite; vaterite was not found).
Intensities were acquired using a Phillips XRG 3100 X-ray diffrac-
tometer system equipped with a diffracted-beam monochromator
and MDI JADE 8 X-ray diffraction pattern processing and iden-
tification software. Corundum was used as a standard. Quantities
were determined by X-ray powder diffraction using the reference
intensity ratio method.
Results and Discussions. Comparison of the Testing Conditions
in the Laboratory With the Field Reality. During the laboratory
tests, the cement samples were completely soaked and exposed
from all sides (except the bottom) to the corrosive fluid; in the
wellbore, the cement sheath is sheltered by the formation and
casing (good cementing practices provided) so that only a small
area from one side is actually attacked. Also, the ratio of corrosive
fluid to cement and the availability of moisture (necessary to form
carbonic acid) were much higher during the laboratory tests than
they would be in a well, resulting in a stronger corrosive attack
and so simulating worst-case conditions. On the other hand, the
laboratory tests were performed under static conditions, whereas in
the field, certain scenerios (e.g., CO2 injection or CO2 gas flow) are
June 2011 SPE Drilling & Completion
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dynamic and so abrasion could become an important factor. These
differences have to be considered when extrapolating conclusions
from the laboratory results to the field.
Evaluation. Cement specimens were evaluated after 1-, 3-, and
6-month exposure to CO2-loaded water at 300°F and 3,000 psi.
The cement cylinder sets that were exposed for 1 month showed
no visual cracks or fractures (Fig. 3a). Cylinders were cut into
two pieces along the width. One part of each cut cylinder was
used for measuring water permeability and testing microindenta-
tion (BH). The other part of the cylinder was sliced into halves
along the length to determine the progress of CO2 attack with the
help of quantitative CaCO3 measurements. Phenolphthalein tests
(pH<10) indicated that no alkalinity was left along the specimens’
profiles for both systems (Fig. 3c), confirming that carbonic acid
completely penetrated the cement samples. Only the conventional
system (Fig. 3c right) had a distinct brownish rim, indicating
stronger alteration. BH could not be measured accurately at this
brownish rim because of shattering (Fig. 3b, Number 1), confirm-
ing a weaker or brittle zone. To give reliable numbers and to avoid
the impact of shattering, BH was tested 1 mm from the specimens’
edges defined as the outer zone (Fig. 3b, Numbers 2 and 3). Every
BH test was repeated at least three times on different sites and
the results were averaged (shattered data points were not taken
into account). The outer zone had a significantly lower hardness
(BH = 9) and lower CaCO3 content (38 wt%) than the interior of the
conventional cement specimen (BH = 20, CaCO3 = 60 wt%), con-
firming a softer zone because of the depletion of CaCO3 according
to the leaching mechanism described in Eq. 15. On the other hand,
the CaCO3 content (35–37 wt%) and the BH (15–17) between the
outer zone and the interior of the pozzolan cement specimen were
identical, indicating it was less affected by corrosion after 1 month.
(The darker color in the interior of the pozzolan cement specimen
is an artifact caused by sawing the cement cylinders.)
Both cement specimens (of the pozzolan and conventional sys-
tems) tested for 1, 3, and 6 months retained sufficient low water
permeabilities (< 0.01 md) and high compressive strengths >5,000
psi (under a confining pressure of 1,000 psi) to provide zonal isola-
tion (Fig. 4, left). Because both systems contained sufficient silica
(formal molar CaO/SiO2 ≈1.1; see Table 1), strength retrogression
(caused by the high temperature of 300°F) is not of concern. The
changes in sizes (length and diameter) for all specimens were
marginal, but both systems gained some weight (Fig. 4, right)
with hydration and carbonation. The increase in weight (+5% after
1 month to +7% after 6 months) of the pozzolan cement specimens
directly correlates with the steady increase in total CaCO3 content
213
 6000 1 35% 70%

30% 60%

Water Permeability (mD)

Compressive Strength (psi)

Total CaCO3 Content (%)

Weight Increase (%)
4500 0.1
25% 50%
conventional pozzolan
20% 40%
3000 0.01
15% 30%
conventional pozzolan
10% 20%
1500 0.001

5% 10%

0 0.0001 0% 0%
0 1 3 6 0 1 3 6

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Exposure time to CO2 loaded water (months) Exposure time to CO2 loaded water (months)

Fig. 4—Left: (Confined) compressive strengths (dotted line) and water permeabilities (solid line) of the pozzolan and conventional
cement systems as a function of exposure time to CO2. Right: Weight increase (dotted line) and total CaCO3 content (solid line)
of the pozzolan and conventional cement systems as a function of exposure time to CO2.

(35 wt% after 1 month to 40 wt% after 6 months) and confirms that
carbonation has probably not been completed even after 6 months.
For the conventional cement system, the maximum increase in
weight (+8.3 wt%) and maximum carbonation (CaCO3 content =
60 wt%) were reached after 1 month. Afterward, the weight con-
tinuously dropped, indicating leaching of cementitious material.
After 6 months, the total CaCO3 content was significantly less for
the pozzolan (35–40 wt%) than for the conventional cement system
(56–60 wt%), even though both systems contained the same formal
CaO content from the beginning (Table 1). Obviously, there exist
certain CaO or C-S-H phases within the pozzolan system that are
less susceptible to carbonation than those formed in the conven-
tional system. A possible explanation for this behavior is given in
the Effect of the Pozzolan on the Formed C-S-H subsection.
After the cement cylinders from both cement systems were
trimmed for testing permeabilities, severe spallings were observed
only for the conventional cement system after 6-month exposure
to CO2 (Fig. 5a). The deterioration of the conventional system
increased when the cement cylinders were put back into tap water
because the brownish rim completely spalled all around the speci-
men (Fig. 5c for the conventional compared with Fig. 5b for the
pozzolan system). As a result, the cement cylinder’s diameter was
reduced by 0.6 mm (–2.4%); the spallings had an approximate
thickness of 0.3 mm. A gap of 0.3 mm along interfaces of the
cement sheath with the casing and formation is large enough to be
of serious concern as a potential channel and migration pathway
for corrosive fluids (e.g., CO2).
To verify the findings, a second specimen of each cement sys-
tem was recovered from the HT/HP curing chamber after 6-month
exposure to CO2 and was split along the length for analyses (Fig. 6,
top). The brownish rim was again found only for the conventional
system. SEM images confirmed a channel at the rim of the conven-
tional system caused by spallings, whereas integrity exists for the
pozzolan system (see Fig. 6, bottom). The observed spallings may
not occur naturally under confined pressure in the wellbore, but the
findings confirm a potential risk of losing effective zonal isolation
and barrier-system integrity over time. These results demonstrated
that for the conventional cement system, the corrosion process in
the presence of CO2 progressed faster than for the pozzolan cement
system. The latter did not show any indication of detrimental leach-
ing or loss of integrity after 6-month exposure to CO2.
Effect of Pozzolan on the Formed C-S-H. An examination of
the effect of the pozzolan on the formed C-S-H phases is necessary
to understand why the set pozzolan system shows less carbonation
than the conventional system and especially why it preserves
integrity after 6-month exposure to CO2, whereas the conventional
system does not.
SEM images were prepared from the pozzolan system after
4-day (Figs. 7a and 7b) and 3-month (Fig. 7c) curing at 300°F
and 3,000 psi in tap water. During the hydration of the pozzolan

Fig. 5—(a) Pozzolan (left cylinder) and conventional cement systems (right cylinder) after recovering from exposure to CO2-loaded
water at 300°F and 3,000 psi for 6 months; specimens were trimmed at the bottom and top for testing water permeability—only
the conventional cylinder showed detrimental spalling. (b) Pozzolan cement cylinder stored in fresh water without any changes;
(c) the rim from the conventional cement cylinder immediately spalled when exposed to tap water resulting in a decrease in
diameter of 0.6 mm (–2.4%).

214 June 2011 SPE Drilling & Completion


Fig. 6—Top: Pozzolan (left cylinder half) and conventional cement systems (right cylinder half) after recovering from exposure
to CO2-loaded water at 300°F and 3,000 psi for 6 months. Bottom: SEM images taken from the rim (arrow) of each recovered
cement system.
cement system, a dublex film (Huettl 2000; Diamond et al. 1980)
out of C-S-H phases (blue arrow in Fig. 7b) forms on the surface
of the pozzolan according to the pozzolanic reaction (Eq. 2). This
dublex film serves as a crystal nucleus for epitaxial growth of fur-
ther C-S-H phases, resulting in a sheath of densified C-S-H phases
around the pozzolan spheres (green arrows in Fig. 7). C-S-H phases
within the cement matrix are generally nanocrystalline or roentgen
amorphous and so cannot be detected by X-ray diffraction analy-
ses. However, the chemical analyses of the sheath by EDS confirm
its nature to be out of C-S-H phases. After 6-month exposure to
CO2-loaded water at 300°F and 3,000 psi, sheaths of densified
C-S-H phases can be still found (Fig. 7d) throughout the speci-
men, seemingly unaltered by the CO2 exposure. This may explain
the lower CaCO3 content or carbonation, respectively, found for
the pozzolan compared with the conventional system. The densi-
fied C-S-H phases in the spherical sheaths around the pozzolans
are compact (lower surface area), resulting in better integrity and
higher durability under CO2 exposure.
Testing Mechanical Properties. The effects of CO2 attack on
the mechanical properties of the pozzolan and the conventional
cement systems were also studied. Young’s modulus, Poisson’s
ratio, compressive strength, and tensile strength were determined
before and after 1-month exposure to CO2-loaded water (Table
2). The differential in mechanical properties of set cement usu-
ally decreases over time because, after setting, cement hydration
is diffusion controlled. Thus, changes in mechanical properties
significantly decrease after a curing time of 96 hours at 300°F
and 3,000 psi. This might not be exactly correct for the pozzolan
system because cement/pozzolan blends typically develop strength
slowly but continuously over time. The gain in weight caused
by carbonation and further hydration resulted in an increase in
density from 15.0 to 16.1 ppg (+4.8 wt%) for the pozzolan and to
16.5 ppg (+8.3 wt%) for the conventional system. Water perme-
June 2011 SPE Drilling & Completion
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abilities of both systems increased from 0.00021 to 0.00442 md
(pozzolan) or 0.00032 md to 0.00375 md (conventional), but are
still sufficiently low to provide zonal isolation. At the same time,
the Young’s modulus (approximately –40% for both systems)
and Poisson’s ratio (approximately –20% for the pozzolan and
–40% for the conventional) decreased significantly. As mentioned
earlier, cement carbonation results in higher compressive and
tensile strengths. Compressive strengths were initially relatively
high for both systems and remained greater than 5,800 psi after
exposure to CO2. Tensile strengths increased from the original
354 psi (pozzolan) and 258 psi (conventional) to 468 psi (+30%)
or 438 psi (+70%), respectively. The mechanical properties of the
conventional cement system are more affected after 1 month of
CO2 exposure because of stronger carbonation than the properties
of the pozzolan cement system.
Evaluation of the Wellbore Stress Modeling. Portland cement
is a brittle material by nature, basically because of a high Young’s
modulus and a relatively low tensile strength (compared to com-
pressive strength). Therefore, the cement sheath in the wellbore is
more likely to fail in tension than in compression. The pozzolan
cement system has generally higher tensile strengths and lower
Young’s moduli (before and after CO2 exposure) than the conven-
tional cement system. On the basis of its more-favorable mechani-
cal properties, the pozzolan cement system tends to withstand
wellbore stresses better than the conventional cement system.
A numerical wellbore-stress model was run to illustrate the
different performances of each cement system for an identical
well scenario. The model predicts likely cement sheath failure
as a pass/fail feature on the basis of maximum calculated stress
compared to the known strength of the cement as described by
Mueller et al. (2004) and Myers et al. (2005). The model assumes
that casing, cement, and formation are linear elastic, isotropic,
and homogeneous as well as mechanically coupled. Furthermore,
215
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Fig. 7—SEMs of the set pozzolan cement system. (a and b) After curing for 4 days in tap water at 300°F and 3,000 psi. (c) After
curing for 3 months in tap water at 300°F and 3,000 psi (pozzolan remained on the opposite fragment). (d) After 6-month exposure
to CO2-loaded water at 300°F and 3,000 psi (pozzolan remained on the opposite fragment). EDS analyses reveal the chemical
composition of the sheath.

it assumes that the casing is centered in the annulus, the cement
sheath is defect free, and all horizontal stresses are equal. A change
in temperature (ΔT = –50 °F) and pressure (Δp = +600 psi) caused
by an injection fluid (e.g., CO2 flooding) was simulated to exer-
cise mechanical stresses on each cement sheath (surrounding a
13.375-in. casing in a 17.5-in. hole) at a reference depth of 6,000
ft. Induced stresses, applied to the cement sheath, have both radial
and tangential components. Radial stress occurs from the center
of the wellbore outward. Tangential stress is perpendicular to the
radial stress component. A cement-sheath failure is more likely to
occur if the calculated stresses (in tension or compression) exceed
the found tensile or compressive strength of the cement system.
In the graphs of Fig. 8, stresses in tension and compression
are shown as positive and negative values, respectively. For the
simulated decrease in temperature and increase in pressure, all
mathematical models show that the highest radial and tangential
stress values are in tension rather than compression. (Figs. 8a
through 8d). The cement sheath made from the pozzolan cement
system before CO2 exposure (Fig. 8a) has adequate tensile strength
(354 psi; Table 2) to withstand the maximum calculated stress in

TABLE 2—MECHANICAL PROPERTIES OF THE POZZOLAN AND CONVENTIONAL CEMENT SYSTEMS BEFORE AND AFTER
CO2 EXPOSURE

Young’s Modulus Compressive

(Mpsi) Poisson’s Ratio Strength (psi) Tensile
Density Permeability Confining Stress: Confining Stress: Confining Stress: Strength (psi)
Cement System (ppg) (md) 1,000 psi 1,000 psi 1,000 psi Unconfined

After 96 hours curing at 3,000 psi/300°F and before CO 2 exposure

Pozzolan 15.0 0.00021 1.52 0.32 >5,800 354

Conventional 15.0 0.00032 2.07 0.33 >5,860 258
After 30 days exposure to CO 2 loaded water at 3,000 psi/300°F

Pozzolan 16.1 0.00442 0.85 0.26 >5,850 468

Conventional 16.5 0.00375 1.17 0.23 >5,850 438

216 June 2011 SPE Drilling & Completion

 Radial Stress Radial/Tangential Stress Field Tangential Stress
194 64
200
A 60

Tangential Stress (psi)

Radial Stress (psi) 50
210

40
220

30
230

20
240 pozzolan cement system
8 7 6.6 before CO2 exposure 7 8 8.8
Dist from Borehole Axis (in) Dist from Borehole Axis (in)

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Radial Stress Radial/Tangential Stress Field Tangential Stress
195 40
200 B

Tangential Stress (psi)

Radial Stress (psi)

20
220

0
240

conventional cement system -20

8 7 6.6 7 8 8.8
Dist from Borehole Axis (in)
before CO2 exposure Dist from Borehole Axis (in)

Radial Stress Radial/Tangential Stress Field Tangential Stress

156 44
160 C 40

Tangential Stress (psi)

Radial Stress (psi)

170 30

180 20

190 10

pozzolan cement system after

8 7 6.6 CO2 exposure 7 8 8.8
Dist from Borehole Axis (in) Dist from Borehole Axis (in)

Radial Stress Radial/Tangential Stress Field Tangential Stress

160
D 15
Tangential Stress (psi)

0
Radial Stress (psi)

180

-20

200

8 7
Dist from Borehole Axis (in)
-40
conventional cement system
6.6 7 8 8.8
after CO2 exposure
Dist from Borehole Axis (in)

Fig. 8—Numerical wellbore-stress model for (a) pozzolan cement system before exposure to CO2, (b) conventional cement system
before exposure to CO2, (c) pozzolan cement system after exposure to CO2, and (d) conventional cement system after exposure
to CO2. Radial (left) and tangential (right) stresses simulate a change in temperature (ΔT = –50°F) and pressure (Δp = +600 psi)
because of the injection of a fluid. Stresses in tension appear as positive and in compression as negative values. Different
shadings in color reflect the stress as a portion of the cement strength: blue = <25%, green = 25–50%, yellow = 50–75%, orange =
75–100%, and red = >100%.

tension (241 psi; Fig. 8a, left). The conventional cement system
sheath before CO2 exposure has lower tensile strength (258 psi;
Table 2), nearly the same as the calculated stress in tension (254
psi; Fig. 8b). Therefore, the cement sheath made out of the pozzo-
lan system is more likely than the conventional system to withstand
the simulated stresses without failures.
After 1 month of exposure to CO2, the mechanical properties
for both cement systems changed (Table 2) as did the calculated
stresses exercised on each cement sheath during the simulation
(Figs. 8c and 8d). The measured tensile strengths (468 and 438 psi,
respectively, for the pozzolan and conventional systems) increased
significantly because of carbonation during exposure to CO2. At
the same time, the maximum calculated (radial) stresses in tension
after exposure to CO2 dropped to 198 and 214 psi, respectively, for
the pozzolan and conventional systems. These effects combined to
reduce the negative impacts of mechanical stresses on each cement
sheath during the simulated temperature and pressure fluctuations.
The cement sheath made out of the pozzolan system is expected

June 2011 SPE Drilling & Completion 217

to have better durability because of the lower experienced (radial)
stresses in tension at highest tensile strength.
Cementing Guidelines for Corrosive Well
Environments
The published field studies (Crow et al. 2009; Carey et al. 2007)
revealed that corrosion occurred mainly along the cement/forma-
tion interface and to lesser extent through the cement matrix.
Consequently, defects in the cement sheath, existing annuli, and
leakage pathways for migration allowed an increase of contact time
and area between the corrosive fluid and the cement, enhancing the
corrosion process. On the basis of the findings from the literature
survey about cement corrosion, the following cementing guidelines
were composed:
• Follow good cementing practices for a successful primary
cement job. This requires well preparation and properly designed
cement slurry for the well conditions. Engineered spacers, central-
izing the pipe, rotating, and reciprocating, in combination with the
use of simulation software for the cement-pumping process, help
to maximize mud displacement efficiency.
• Improve cement bonding and reduce permeability of the
formation. Newhall (2006) reported that a preflush with a sodium
silicate system will improve cement bond. An aqueous film of
silicates on the surface of the formation and the pipe will form
calcium silicate precipitation when in contact with the cement
slurry. Furthermore, the permeability of formations containing
calcium and magnesium will be reduced because of the precipita-
tion reaction. The sealing of formations containing corrosive fluids
is beneficial to minimize chemical attacks on the cement sheath.
However, this method is not applicable for every section in the
well (e.g., perforation zone).
• Design the cement system with suitable mechanical proper-
ties. Mathematical wellbore-stress simulations help to predict if
the cement sheath will withstand induced tensile and compressive
forces created by changing wellbore conditions without failures
over the life of the well.
• Use fit-for-purpopse cement systems designed to counteract
all corrosion attacks expected. The literature survey revealed that
different corrosion types can occur and must be simultaneously
and selectively mitigated. In particular, expansion caused by
magnesium- and sulfate-containing fluids results in a stronger
damage of the cement sheath than a dissolving attack from acids.
In addition, chemical reactions are normally accelerated with
increasing temperatures. As a rule of thumb, an increase of +10°C
in temperature doubles chemical reactions and so doubles the cor-
rosion rate. Increasing pressure also enhances the penetration rate
of corrosive fluids into the cement pores, and so enhances their
corrosive effect.
Cement designs should be developed on the basis of chemi-
cal composition of downhole fluids and any potential injection
operations with corrosive fluids. The use of API cements is recom-
mended to meet minimum quality standards while avoiding initial
issues during cement hydration. A reduced C3A content improves
the sulfate resistance. The addition of sufficient silica to reduce
the CaO/SiO2 ratio in the cement system to approximately unity is
necessary to prevent strength retrogression above 230°F.
Portlandite is a general weak point in the set cement and
must be minimized because it is sensitive toward most chemical
attacks (see Eqs. 8, 9, and 10). It might be true that CO2 converts
portlandite into calcium carbonate (see Eq. 13), which temporarily
seals cement pores and so slows down further CO2 attack. But at
the same time, portlandite will also be easily leached out of the
cement matrix in the presence of acids or will react with magne-
sium or sulfates causing destructive expansion. The latter results
in more-severe corrosion than that caused by CO2 attack alone.
Field studies have proved that cement corrosion caused only by
CO2 attack seems not to be of great concern but is accelerated in
the presence of defects caused, for example, by other corrosion
types. Consequently, the elimination of portlandite and the addition
of sufficient silica help to mitigate the worst corrosion attacks
first.
218
All chemical attacks within the cement are diffusion-controlled
processes, and so the corrosion rate can be effectively reduced with
decreasing permeability of the set cement. A cement system with
initial minimal permeability contributes to improve durability. The
partial substitution for cement with pozzolanic materials at same
slurry density can be an elegant “all in one” solution because this
reduces the total C3A content, decreases the CaO/SiO2 ratio to pre-
vent strength retrogression at temperatures above 230°F, eliminates
the portlandite, and decreases the permeability of the set cement.
Conclusion
API-cement-based systems can be a practical solution for corrosive
well environments, as demonstrated in the literature about field
studies and laboratory tests. Following good cementing practices is
of utmost importance to minimize corrosion of the cement sheath.
Downloaded from http://onepetro.org/DC/article-pdf/26/02/208/2092236/spe-132228-pa.pdf/1 by Universidad Industrial De Santander, Javier Salamanca on 30 July 2021
The literature survey furthermore revealed that properly designed
API cement systems containing selected pozzolanic materials gen-
erally improve the durability in contact with corrosive fluids.
In the present comparison study, the evaluation of a pozzolan
and a conventional API cement system exposed to CO2-loaded
water at 300°F and 3,000 psi results in the following: Under the
given HT/HP test conditions, CO2-loaded water completely pene-
trates all specimens within 1 month. Therefore, this test method can
serve to predict long-term effects within a reasonable time frame.
Carbonation of both cement systems increases their water perme-
abilities and compressive and tensile strengths, whereas Young’s
moduli and Poisson’s ratios are reduced. Because of these changes
of mechanical properties, mathematical wellbore models predict
lower stresses on each cement sheath than before CO2 exposure.
Therefore, the durability of each cement sheath improves in regard
to stresses induced by temperature and pressure changes—as long
as no chemical leaching or spalling occurs.
After 6 months of exposure to CO2, the tested pozzolan API
cement system maintains better integrity than the conventional
system: Significantly less carbonation is found for the pozzolan
system, and only the specimens of the conventional system show
severe spalling effects that may risk the loss of zonal isolation in the
wellbore. The better performance of the pozzolan cement system
appears to be linked to the observed formation of sheaths of densified
C-S-H phases around the selected pozzolans.
Acknowledgments
The authors wish to thank the management of Baker Hughes
Incorporated for permission to publish this paper.
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Andreas Brandl joined the Cementing Technology group
of Baker Hughes Incorporated “BHI” (formerly BJ Services
Company) in Tomball, Texas in 2009. He started his career as
a scientist with BJ Services in Hambühren (Germany) in 2007
and worked as a cementing specialist in Asia Pacific during
2008. Brandl holds a diploma in chemistry from the Technische
Universität München, from which he also received a Doctor
of Science for his studies about additives for well cementing.
Jennifer Cutler is a senior research scientist with BHI with over 30
years of experience in the petroleum industry. She has worked
for and with industry leaders at major oil companies and service
companies in domestic and international assignments. Since
joining BJ Services in 2004, Cutler’s responsibilities include regu-
larly consulting with domestic and international personnel to
address their field requirements as well as with research person-
nel to provide information toward their projects. Amanda Seholm
is a geologist with BHI in Tomball, Texas. She holds a BA in geology
from Trinity University in San Antonio, Texas, and an MS in geology
from the University of Aarhus in Aarhus, Denmark. Seholm spe-
cializes in formation evaluation and materials characterization
studies to identify potential completion problems and to cre-
ate reservoir stimulation and remedial treatment recommenda-
tions. She joined the Geological Services Group in 2006. Michelle
Sansil joined BHI in 2007 and works as an associate chemist in
the geomechanics group at Baker Hughes Technology Center
in Tomball, Texas. Gerald Braun is a senior research scientist with
BHI in Tomball, Texas with 30 years’ experience in quantitative
phase analysis and electron microscopy. Braun holds BS and MS
degrees in geology from the University of Arizona and a PhD in
mineralogy-petrology from the University of Minnesota.
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