GRC Transactions, Vol.
36, 2012
Effects of CO2 on Geothermal Cements
Neil B. Milestone, Carl H. Bigley, Andrew T. Durant, and Matthew D. W. Sharp
Industrial Research Ltd., Lower Hutt, New Zealand
n.milestone@irl.cri.nz
Keywords
Dissolved CO2, carbonation, corrosion, CO2 attack, cement
durability
Abstract
The cements used to complete geothermal wells are required
to withstand temperatures in excess of 300oC. To avoid ongoing
strength degradation at these elevated temperatures, silica flour ad-
ditions of ~40% BWOC have been routinely used. This normally
leads to the formation of the low Ca/Si ratio phases of tobermorite
(Ca/Si = 0.83) at 150oC and xonotlite (Ca/Si =1) above 200oC.
These phases provide good compressive strengths and have low
permeability. However, when exposed to fluids containing high
levels of CO2 these phases have been shown to rapidly carbonate
and become porous, forming aragonite and calcite depending on
the temperature. If the level of dissolved CO2 is high enough so
the fluid becomes acidic, then the carbonated layer will readily
dissolve leading to corrosion and eventual loss of the protective ce-
ment sheath. By using lower additions of silica, the calcium silicate
hydrates that form (Ca/Si ≈ 1.5) expand on carbonation and provide
a carbonation sheath that offers some protection to corrosive fluids.
When fresh cement slurries are cured in the high CO2 fluids
they rapidly give rise to a carbonated layer which effectively re-
duces the availability of calcium so low Ca/Si ratio phases form,
such as tobermorite, which offer no protection to carbonation.
Ceramic cenospheres used as lightening agents for cement slur-
ries, react with the hydrating cement to give pockets of low Ca/Si
phases that readily carbonate, opening the matrix to further attack
and rapid carbonation throughout what becomes a porous binder.
Addition of additives containing aluminium such as slag
does give rise to calcium aluminosilicates, which while more
carbonation resistant make poor binders. However, even these
will ultimately carbonate under high CO2 conditions and if suf-
ficient CO2 is present, dissolve. The challenge for the industry is
to develop a whole new cementing system that is not based around
calcium that can be used to complete geothermal wells in a high
CO2 acidic environment.
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1. Introduction
1.1 Carbonation of Portland Cement
Carbonation of Portland cement systems is well known. In
construction concrete it is usually only the Ca(OH)2 that is carbon-
ated by atmospheric CO2. Carbonation is an expansive reaction
that occurs rapidly and in good concrete, only the first few mm
carbonate, forming a protective, low porosity sheath of CaCO3.
In modern concrete the use of siliceous additives known as poz-
zolans reduces the amount of Ca(OH)2 available in the matrix as
a pH buffer and excessive carbonation can become an issue, since
without Ca(OH)2 present, CO2 will attack the hydration product,
C-S-H, lowering the pH in the internal pore solution. The steel
reinforcement is then no longer protected by a highly alkaline
pore solution and it rusts, expanding and causing cracking and
subsequent loss in strength.
1.2 Carbonation of Well Cements
Onan (1984) examined the effects supercritical CO2 had on
well cements at ambient temperatures and recommended a for-
mulation that contained 50% addition of a pozzolan to ensure no
Ca(OH)2 remained and to avoid the worst effects of cracking at
low temperatures. This is in contrast to Bruckdorfer (1986) who
was the first to report potential corrosion in well cements when
examining the behaviour of carbonic acid on well cements also
at low temperatures. In his work he showed that not only did
carbonation of the Ca(OH)2 occur, but that the calcium silicate
hydrate could also be attacked. He also found greater depths of
carbonation in samples containing flyash where the Ca(OH)2 had
been removed by reaction.
1.2.1 CO2 Sequestration and Issues in Wells
One of the ways in dealing with CO2 that has been separated
is to store it underground in abandoned oil wells and porous
strata as a super-critical fluid. While the temperatures at which
carbonation occurs are lower than those in geothermal conditions
the problems associated with carbonation and dissolution are the
Milestone, et al.

same. There has now been extensive work conducted in the field
and published papers are now starting to appear. Reports from
the Well Bore Integrity Workshops (2005 and 2007) have yielded
some interesting findings that mirror results from our own work
in geothermal cements. While the discussions in these workshops
are primarily based around issues with CO2 sequestration and low
temperatures, one of the main conclusions drawn is that Portland
cements will react with CO2 leading to cement degradation, and
that the corrosion of a Portland cement based system is thermo-
dynamically favourable. More than 50% of the wells examined
had major problems. The major reactions were identified as car-
bonation of portlandite and the calcium silicate hydrates. Discs
of hardened Portland cement were seen to dissolve in “days and
weeks.” Additions of certain forms of silica had some benefits but
only postponed the inevitable carbonation. In general, the use of
fly ash was not seen as a positive addition.
The formation of a hard calcite ‘ring’ around the outside of a
cement grout cylinder forming an ‘armour’ Jacquemet (2012) has
been identified by many of the parties at these workshops. This
hard and dense calcite ring gives high compressive strength results
and highlights the issues when comparing compressive strengths
between carbonated and non carbonated samples, something we
have identified in our own research.
Further interesting comments were that curing samples in
carbonate/bicarbonate solution at elevated temperatures did not
simulate curing in a CO2 over pressured environment such as
found in New Zealand geothermal fields.
1.3 Carbonation and Corrosion in Geothermal Wells
Milestone et al. (1986) showed that samples precured in a
laboratory autoclave at 150°C for 72 hours and then exposed
.down-hole in wells in the Ohaaki geothermal field in New Zea-
land, underwent both carbonation and corrosion at 150°C while
at 260°C, only carbonation occurred when they were exposed to
high CO2 containing fluids. (Figs. 1, 2).
One of the key features of that work and of the subsequent
laboratory work at Brookhaven National Laboratory by Milestone
et al. (1986, 1987a, b) was that the addition of around 40% silica
flour, normally added to counter strength retrogression due to the
formation of αC2SH and other high Ca/Si ratio phases, created a
matrix where carbonation was extremely rapid. The expected low
Ca/Si ratio phases of tobermorite and xonotlite, chosen to give low
porosity and high strength at elevated temperatures, carbonated
rapidly and became porous. In contrast, high Ca/Si ratio phases
such as αC2SH (at 150°C) and reinhardbrausite or kilchoanite (at
260°C), which form in association with Ca(OH)2 give low strength
binders, but form a dense protective carbonation sheath with low
permeability and high strength. At 150°C, Ca(OH)2 carbonates
to calcite while carbonation of calcium silicate hydrates gives
metastable aragonite so that mixtures of aragonite and calcite were
present in the carbonated layers which were thin.
Following the work at Brookhaven Laboratory, Milestone and
his co-workers (1990) in New Zealand undertook an extensive
period of work testing a wide variety of formulations based largely
on additions to Portland cement downhole in both the Ohaaki
and Rotokawa fields. This work was prompted by the discovery
that corrosion of the steel well casing had occurred in wells that
had been drilled and shut in for long periods of time. (Driver and
Wilson (1984), Bixley and Wilson (1985)).
It was clear from these studies that in any Portland cement
based system, the carbonation rate was very dependent on volume
of available Ca in any unit volume and particularly by any Ca(OH)2
present. Carbonation resistance was enhanced by low addition
rates of silica and low water/
solids ratio mixes. Addition
of bentonite, often added to
control bleeding proved det-
rimental as it stabilised any
tobermorite that was formed,
which rapidly carbonated and
became porous Milestone et
al. (1987b).

2.0 Mechanism of
Carbonation
Carbonation of cement
grouts proceeds via a ‘through
solution’ mechanism. This
was initially described by
(a) (b) (a) (b) Milestone et al. (1986)where
Figure 1. Exposure of grout cylinders in BR23 Ohaaki Figure 2. Exposure of grout cylinders in BR17, Ohaaki Ca2+ ions migrate through a
(150oC, [CO2] 0.35moles/l, pHT 4.59) for 4 months. (260oC, [CO2] 0.064 moles/l, pHT 6.49) for 4 months. saturated matrix leaving a
(a) Pure cement, The centre core is α-C2SH plus (a) Pure cement. Inner core – High Ca/Si phases leached zone and then rap-
Ca(OH)2,middle orange layer is calcite, with an in- kilchoanite and reinhardbraunsite, outer rim – cal- idly precipitate as CaCO 3
ner layer of calcite and aragonite, outermost layer cite. No corrosion. when they meet the dissolved
is silica gel. Minor corrosion. (b) Cement plus 40% silica flour: Inner core – xonot-
(b) Cement plus 40% silica flour. Inner core is arago- lite and calcite, Outer core – calcite and xonotlite. CO2 (‘carbonic acid’). This
nite, middle layer is aragonite/calcite, outer layers Outside layer – calcite. No corrosion. reaction can lead to a discon-
corroded silica gel. Sample is extensively corroded. tinuity as the precipitation

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 Milestone, et al.

reaction occurs faster than the rate at which the Ca2+ions can
migrate. The discontinuity is obvious in Fig 3 where a sample
of pure cement exposed in an Ohaaki well (BR17, [CO2] 0.064
moles/kg) at 260°C for 4 months shows the formation of a calcite
skin which is only weakly attached and will readily separate, par-
ticularly if the sample is recovered from the well too quickly and
dried out. The pHT in this well is 6.49, above the neutral pHT of
5.82 so there is no acid dissolution or corrosion. Carbonation of
Ca(OH)2 is an expansive reaction so the carbonated layer occupies
more volume than that from where it has come and can separate.
A petrographic thin section prepared from the same sample (Fig
4) clearly shows the leached region along with the discontinuity.
Ca2+ ions migrate from the sparingly soluble Ca(OH)2 leaving a
leached zone in which the loss of Ca(OH)2 is clearly visible just
inside the discontinuity. Ultimately the skin of CaCO3 will grow
and penetrate to the centre with an increase in the volume of the
cylinder but after 1 year of downhole exposure, the carbonated
layer is only around 12mm thick.
This has important issues if compressive strength or perme-
ability of cylinders are being used as measures of determining
potential durability. The carbonate skin has high strength so what
is measured for strength is due to a composite structure with a
Figure 5. Sample containing 40% silica flour exposed at 260°C for 4
months in BR17. Outer grey zone calcite, pale middle zone calcite with
traces of xonotlite, central dark grey zone xonotlite with calcite.

discontinuity. The same applies in measuring permeability where

Figure 3. Exposure of pure cement samples in BR17 at 260°C for 4 months.
water is likely to flow down the discontinuity rather than through
the sample.
The calcium silicate hydrates are much less soluble than
Ca(OH)2 meaning there are limited Ca2+ ions to migrate so the
carbonation attack appears to occur directly on the matrix as seen
in Figure 5 for a sample containing 40% silica exposed in the same
well where there is no obvious leached zone. The carbonation of
xonotlite, the stable low Ca/Si ratio phase at 260°C, results in a
reduction of solid volume causing an increase in porosity so no
distinct carbonation layer occurs.
Initial models of the downhole conditions were based on the
assumption that the downhole fluids were saturated with respect
to calcite as this was the phase reported by Kennerley (1961) as
occurring in a failed geothermal well. However, testing in BR17
using limestone and marble alone showed that not to be the case
and a new field diagram was drawn up by Hedenquist and Stewart
(1985). This identified the presence of a cooler aquifer in which
gases which boiled off from depth. Similar zones have since been
identified in other fields where a cooler flow of water is heated by
up risings from deeper fluids. (Clearwater et al. (2012))

3.0 Available Ca2+ Per Unit Volume

Figure 4. Photomicrograph of carbonated geothermal cement sample from
Figure 3. Scale bar is 1mm. Brown colour is calcite, white crystals αC2SH,
grey is Ca(OH)2. Discontinuity is ~0.7mm, leached zone ~1.2mm.
The concentration of Ca per unit volume has a marked ef-
fect on the rate of carbonation. One of the issues in cementing
a geothermal well is that it is usually drilled through a weak
formation, often with zones where lost circulation is a problem.
As a consequence slurries with low density are sought to ensure
the weight of the column of cement slurry does not collapse the
formation.

303
Milestone, et al.
This was originally addressed in New Zealand by using
formulations with higher water/cement ratios with addition of
bentonite. However, Milestone et al. (1987b) showed that additions
of bentonite to a mix caused greater amounts of carbonation. With
silica flour additions it enhanced and stabilised the formation of
tobermorite which is not carbonation resistant.
The use of hollow ceramic cenospheres or microspheres to
obtain lightweight slurries is now wide spread. These are ob-
tained from flyash and have the same overall composition so are
pozzolanic. They allow slurry densities as low as 1.55g/cc (13.5
ppg) to be easily obtained. In a recent study, a slurry of Class G
plus 25% hydrothermal silica BWOC and 15% of cenospheres
BWOC (14lb/sack) was mixed at a water/solids ratio of 0.41 to
give a density of 1.65g/cc (13.8 PPG) and cured at 165°C for 28
days in a geothermal brine (15.8 g NaCl, 4.1g KCl, 0.2g Na2SO4,
0.05g CaCl2, 15.6g CB8 colloidal silica (50% solids) dissolved
in 20 litres distilled water) under 6 bars CO2 pressure. While
compressive strength was maintained (25.7 MPa), there was a
distinct carbonation rim of ~5mm which increased with time.
A photo-micrograph of the core (Fig 6) shows distinct reaction
rims around the cenospheres, many of which are filled with ara-
gonite and calcite. An X-ray of the carbonation rim showed it to
be totally carbonated with largely calcite present whereas in the
core, tobermorite and a trace of xonotlite were the crystalline
calcium silicate hydrates present with large amounts of aragonite
and a smaller amount of calcite. The added silica reacts with any
Ca(OH)2 formed from cement hydration removing the Ca(OH)2
so it is not found. The cenospheres are also siliceous and readily
react with Portland cement hydration products to give pockets of
low Ca/Si ratio phases which crystallise as tobermorite/ xonotlite
but which carbonate readily. In a Class G plus 25% hydrother-
mal silica slurry without cenosphere addition giving a density of
1.89g/cc (16.5 PPG) there is no carbonation beyond the first mm
or so. Thus in the lightened samples where the amount of Ca per
unit volume is low, carbonation is rapid as no protective sheath
is formed.
Figure 6. Photomicrograph of Class G cement plus 25% hydrothermal
silica and 15% cenospheres and mixed at w/s of 0.41 cured for 28 days in
CO2 saturated brine at 160°C.
This is further highlighted in a recent study where the slurry
density of a Class G cement plus 25% hydrothermal silica was
controlled with water addition and additives and the samples were
cured under the same conditions. In the lighter weight slurries
carbonation through to the core has occurred. (Fig 7). Interest-
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(a) 15.0 PPG (b) 12.4 PPG (c) 11 PPG
Figure 7. Grout formulations containing 20% silica at different densities
cured at 150°C .
ingly, the use of the chemical additives in these samples, which
contain significant amounts of sulfate, has changed the expected
range of products.
In the 15 PPG sample the major phase is an amorphous C-S-H
with small amounts of xonotlite and afwillite (C3S2H3), with traces
of calcite. The Class G plus 25% hydrothermal silica slurry with
a density of 1.89g/cc discussed above, is completely amorphous
after 28 days curing. As the density decreases, the 12.4 PPG sample
still contains a large amorphous component but the amounts of
xonotlite and afwillite have increased while the unhydrated cement
decreases and there is a small amount of gismondine, C2A2S4H9,
present in the core, while the skin contains aragonite and calcite.
Finally, with the 11 PPG sample carbonation has penetrated to
the centre of the sample giving a mixture of calcite and aragonite
along with xonotlite and the addition of anhydrite. No silicates are
present in the middle layer which is a mixture of aragonite, calcite
with a small amount of anhydrite, while the skin is principally
calcite along with some aragonite.
The addition of only 20% silica does not normally allow the
formation of the low Ca/Si ratio phases of tobermorite (which
usually only forms with quartz) or xonotlite as the ratio is not
low enough. However, carbonation removes available Ca from
the matrix and allows the formation of these lower Ca/Si ratio
phases. The anhydrite found arises from the interaction of Ca2+
ions and sulfate from the additives needed to prevent settling in
the higher w/s mixes.
4.0 Corrosion Mechanism
As pointed out by Bruckdorfer (1986), the corrosion mecha-
nism is one of dissolution of the CaCO3 that forms by carbonation
of the cement by ‘carbonic acid’ to give soluble Ca(HCO3)2 which
is lost (Eq 1). The dissolved CO2 concentration in the well fluid
in which the samples in Figure 1 were exposed (0.34 moles/litre)
was sufficient to create a mildly acidic liquid environment of pH
4.59. Neutral pH at 150°C is estimated at 5.82 (Bandura and Lvova
(2006)) so the pH is dictated by the dissolved CO2. This is unlike
the pH in the surface regions where it is dictated by sulphuric
acid formed from oxidized sulphur species and pHs of 2 or lower
 Milestone, et al.

have been recorded. These rapidly dissolve cementing materials
and precipitate gypsum. Corrosion of the carbonates formed by
carbonation follow the high school reaction of limewater and CO2
(Equations 1 and 2).
Ca(OH)2 + CO2(aq) → CaCO3 + H2O (1)
m, close to that estimated for the corrosive fluid at Ohaaki (Ellis
1959). Samples were examined for carbonation depth and phase
analysis by X-ray diffraction. Carbonation depths are given in
Figure 8 and phases in Table 1.

CaCO3 + CO2(aq) + H2O → Ca2+(aq) + 2HCO3-(aq) (2)

This corrosion reaction cannot occur in dry steam as there is no

liquid for the ions to dissolve and be leached although carbonation
does occur. When the [CO2] is such that the fluid is not acidic, as
in BR17, then only carbonation occurs.

5.0 Carbonation During Curing

In many samples we have prepared that have been subjected
to carbonation during curing, the presence of phases such as to-
bermorite and xonotlite has been regularly noticed in formulations
where the Ca/Si ratio is high enough that these phases should not Figure 8. Carbonation depths with differing percentages of slag.
form. These samples are invariably those where there is a high
w/s ratio such as Fig 7 (b) and (c) or they contain porous additives
(Fig 6). These low Ca/Si ratio phases are always accompanied by The samples containing low levels of slag addition perform
the presence of CaCO3. This removal of Ca2+ ions as insoluble reasonably well at 150°C with low carbonation depths, but car-
CaCO3 effectively produces a low Ca/Si ratio environment and bonation depths steadily increase at 260°C. At slag levels above
phases such as tobermorite or afwillite can form. 65%, the normal construction level addition, carbonation depths
A similar effect was noticed in studying the formation of tober- rapidly increase with age so that by 21 days the 260 100% slag
morite in autoclaved fibre cement boards. In investigating the effects addition is fully carbonated.
steam curing has on the cellulose fibres in these boards (Milestone Part of the reason for the carbonation pattern can be seen in
and Suckling (2004)) an unusual effect was noticed. In the com- Table 2 of phases that have formed and undergo carbonation. At
mercial manufacture of these boards a Portland cement/40% silica 150°C with low slag additions the phases expected are formed,
flour blend is slurried with ~8% cellulose fibre and using a Hatsheck αC2SH and CH although most has been used up at 30% addition.
machine, a modified paper making machine, thin multiple layers These carbonate to give a mixture of calcite and aragonite and are
are built up on a moving felt band to give a board. This board is still able to give a protective carbonation sheath. At 65% the sheath
allowed to hydrate, usually with atmospheric ‘steam curing’ around is sufficiently permeable to start allowing CO2 to penetrate. But
50-60°C to provide green strength before autoclaving overnight at with 80% addition the sheath cannot be built up and carbonation
170°C. This time is not sufficient for all the quartz to react and form becomes increasingly rapid until at 120% the carbonation front
tobermorite. However, tobermorite readily forms around the board has reached the centre of the cylinder. The phase that forms as
edges where carbonation has taken place. increasing amounts of slag are added, katoite, a silica substituted
hydrogarnet, C3AS2H4, does not appear in these short tests to have
carbonated but in the absence of CO2, a sample with large amounts
6.0 Addition of Aluminous Additives of katoite is very soft. At 260°C, αC2SH and CH form initially
As has already been mentioned (Milestone et al. (1987b), addi- but convert to reinhardbraunsite, C5S2H with time. These phases
tion of the aluminosilicate clay bentonite at levels around 5% gives all form the impermeable carbonation sheath. As slag contents
rise to the formation of ‘anomalous tobermorite’. The aluminium increase, katoite along with hibschite, C3AS4H2 form along with
in the clay substitutes into the silicate structure of tobermorite the zeolite analcime. While these phases do not readily carbonate,
stabilising it but does not improve the carbonation resistance. they form very poor binders so the samples are soft.
Slag is often used in construction to provide a cement with add-
ed chemical resistance. This is usually achieved through reduced Table 1. Phases formed in slag/cement blends.
permeability as the Ca(OH)2 activates the hydration of the slag. % Slag
150°C 28 days 260°C 4 days 260°C 21 days
A different pattern emerges with slag at geothermal temperatures. BWOC
In a laboratory study, a series of formulations using Class G 0 αC2SH, CH αC2SH, CH R, CH
cement plus various additions of slag were mixed. These were 10 αC2SH, CH αC2SH, CH R, Hb, xo
mixed according to API RP 10 and cast as 50mm cubes and cured 20 αC2SH, CH αC2SH, CH R, katoite,
in water at 90° for 48 hours. The cubes were cored and 25mm 30 αC2SH, sm CH αC2SH, sm CH R, katoite, Hb
cylinders obtained which were autoclaved at 150° and autog- 65 αC2SH, katoite αC2SH, katoite R, katoite, tr xo
enous pressure for a further 48 hours. These were then exposed 80 αC2SH, katoite katoite, Hb, αC2SH, R, katoite, Hb, xo
in autoclaves at 150°C and 260°C with CO2 pressures of 27 and 120 katoite, sm αC2SH katoite, Hb R, Hb, Anal,
33 bar respectively to give a dissolved CO2 concentration of 0.5 R = reinhardbraunsite, Hb = hibschite, Anal = analcime, xo = xonotlite

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7.0 Concluding Remarks
In the liquid dominated New Zealand geothermal fields,
carbonation is the overriding reaction that occurs throughout the
length of a cemented well. This reaction overrides any reactions
that have designed to overcome the phenomenon of strength ret-
rogression through use of additional silica flour (quartz). The low
Ca/Si phases such as tobermorite and xonotlite, normally sought
to provide strength, carbonate readily and do not provide a pro-
tective carbonation sheath to slow or prevent further carbonation.
Where silica additions are limited to around 20% or less, a dense,
impervious carbonation sheath forms around samples, slowing
further carbonation and limiting corrosion.
Carbonation which occurs during curing before the final
silicate phases are formed removes Ca2+ ions as CaCO3. These
ions are usually from Ca(OH)2 reducing the available Ca which
allows the low Ca/Si phases to form readily. These then carbonate
further and can corrode.
In several of the New Zealand geothermal fields [18], a cor-
rosive zone has formed where CO2 boiled off at depth is trapped
and dissolves in a lower temperature liquid under an impermeable
cap. Concentrations can reach the level where the fluid is mildly
acidic. Under these conditions it will readily carbonate and then
dissolve or corrode any protective carbonation sheath which will
offer no protection to the steel casing.
In the Ohaaki, Rotokawa and Tauhara fields, CO2 induced
corrosion of the steel casings has been noted which implies the ce-
ment has been completely dissolved. Downhole testing of cement
samples in these fields confirmed the cement corrosion (Milestone
and Aldridge (1990). It was recommended that 15% of silica flour
be used as a compromise between strength degradation and rate
of carbonation/corrosion.
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