Advances in Cement Research, 2003, 15, No.

1, January, 35–44

Acid-resistant polydimethylsiloxane additive for

geothermal well cement in 1508C H2SO4 solution
T. Sugama,
L. E. Brothers† and L. Weber{

Brookhaven National Laboratory; Halliburton; Unocal Corporation

The resistance of sodium polyphosphate-modified fly ash/calcium aluminate blend (SFCB) geothermal cement to
H2 SO4 solution (pH 1·2) at 1508C is enhanced by incorporating an emulsion of silanol-terminated
polydimethylsiloxane (PDMS) into slurries. The crystalline phase composition of both 1508C-autoclaved
PDMS-modified and unmodified cements consisted of three hydration reaction products: hydroxyapatite (HOAp),
boehmite, and Na-P type zeolite; one carbonation product, calcite; and three unconsumed reactants:
monocalcium aluminate, perovskite and quartz from calcium aluminate cement and fly ash. When unmodified
cement was exposed for 20 days to hot acid, its surface was covered with the crystalline bassanite
(CaSO4:1=2H 2O) phase as the acid corrosion product of cement. Bassanite was formed not only by reactions
between H2 SO4 and calcite or monocalcium aluminate, but also by reaction of HOAp with acid. In contrast,
PDMS protected the cement against acid corrosion in two ways: it considerably reduced the formation of calcite
and it abated the rate of reaction of HOAp with acid.

Introduction
Sodium polyphosphate-modified fly ash/calcium alu-
minate blend (SFCB) cement was originally developed
by Brookhaven National Laboratory (BNL) in coopera-
tion with two industrial partners, Unocal Corporation
and Halliburton, for use as a CO2 -resistant cement for
1–4
geothermal wells. This SFCB cement hydrated by
exposure to geothermal brine environments at tempera-
tures of more than 1508C formed three crystalline
phases, hydroxyapatite, boehmite, and analcime, which
were essentially responsible for its resistance to carbo-
nation. In 1999–2002, SFCB cement was used to
complete many geothermal wells in Indonesia and
Japan, and is increasingly used in geothermal, oil and
gas wells worldwide. However, one particular concern
was its resistance to the highly concentrated H2 SO4
environments (pH ,2·0) encountered in near-surface
ground water at temperatures ranging from 90 to 1508C.

Brookhaven National Laboratory, Energy Resources Division,
Energy Science & Technology Department, Upton, NY 11973, USA.
† Halliburton, 2600 S. 2nd Street, Duncan, OK 73536-0442, USA.
{ Unocal Corporation, 1414 Southwest Freeway, Sugar Land, TX
77478, USA.
(ACR 417) Paper received 1 July 2002; last revised 16 November
2002; accepted 18 November 2002
In our previous study of the resistance of SFCB
5
cement to H2 SO4 at 908C, we reported that the
calcium aluminate cement (CAC) used as the solid
reactant in this cement system played an important role
in reducing the extent of acid erosion. The most effec-
tive reactant from among the various CACs tested was
one that contained both monocalcium aluminate (CA)
and calcium dialuminate (CA2 ), and a moderate
CaO=Al2 O3 mole ratio. When this particular CAC was
mixed with the three other chemical ingredients:
sodium polyphosphate (NaP), Class F fly ash and water,
the chemical and hydration reactions at room tempera-
ture between the Ca2þ ions liberated from CA and
CA2 , and the nNaHPO4  counter ions coming from
NaP led to the formation of amorphous dibasic calcium
phosphate hydrate. Concurrently, the decalcified CA
and CA2 were converted into amorphous aluminum
oxide hydrate. These amorphous reaction products
basically were responsible for strengthening the SFCB
cement at room temperature. Once this SFCB cement
was exposed to H2 SO4 at 908C, the non-reacted CA
and CA2 reactants were very susceptible to reactions
with H2 SO4, causing the deposition of surficial gypsum
scales as an acid corrosion product. This adherent scale
layer decreased further corrosion. With such protection,
the following phase transformations were completed in
35

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 Sugama et al.

the 908C acid solution; amorphous dibasic calcium Corporation, and consisted of 55 wt% of PDMS solid
phosphate hydrate ! crystalline hydroxyapatite; and and 45 wt% of water. Its molecular structure was
amorphous aluminum oxide hydrate ! crystalline represented as
boehmite. Meanwhile, the uptake of Naþ from NaP by CH3 CH3 CH3
the mullite reactant in the fly ash generated additional j j j
crystalline Na-P type zeolite phases. Hence, we thought HO Si ( Si O )n Si OH ,
that passivation of the surface of the cement by the j j j
deposition of gypsum following the formation of these CH3 CH3 CH3
crystalline reaction products, is the acid corrosion-
inhibiting mechanism of SFCB cements. and its average molecular weight ranged from 2:0 3
Concurrently, we also studied the effectiveness of 104 to 1:2 3 105 grams=mole.
water-borne organic polymer additives, such as styrene Secar 60, supplied by Lafarge Aluminates Corpora-
butadiene latex (SBR), carboxyl-modified butadiene- tion, was used as the calcium aluminate cement (CAC)
acrylonitrile (CBA), polyurethane (PU), and acrylic- reactant. Class F fly ash with a Blaine fineness of
styrene copolymer (ABS) to enhance the resistance of 10, 585 cm2 =g was supplied by Pozament Corp. The
6
the cements to hot acid. Among them, ABS was the x-ray powder diffraction (XRD) data showed that its
most effective additive in alleviating acid erosion of the crystalline components consisted mainly of two major
cements. Its role in retarding the rate of acid erosion of phases, mullite (3Al2 O3.2SiO2 ) and quartz (SiO2 ). The
the cements was due mainly to the formation of Ca- XRD data (Philips Electronic Instruments) were re-
complexed carboxylate derivatives from the interactions corded using nickel-filtered Cu-KÆ radiation at 40 KV
between the functional carboxylate groups in ABS and and 20 mA. A solution of 25 wt% sodium polyphos-
the Ca2þ from CA and CA2 reactants. Further, this phate –[-(-NaPO3 )n -, NaP] supplied by the Aldrich
complexed polymer film formed in the cement covered Chemical Company Inc., was used as the cement-
the unreacted CAC particles, which are very susceptible forming aqueous reactant to modify the CAC and fly
to the reactions with H2 SO4: Such coverage by ABS ash solid reactants. In this study, the composition of
significantly restrained the formation of gypsum during solid reactants, made up in a twin shell dry blender,
reactions between the H2 SO4 and the CAC, thereby had the constant ratio of CAC: fly ash of 60:40 by
inhibiting the acid erosion of the cements. weight. The amount of PDMS used as the solid state
However all these experiments documented the resis- used was 0, 5, 10 and 15% by total weight of CAC and
tance of the SFCB cements to acid at the relatively low fly ash. The formulations of the PDMS-modified
temperature of 908C. Our ongoing study of the acid cement slurries are shown in Table 1.
resistant cements has shifted to investigating their acid Using these formulations, test specimens were pre-
resistance to acid at 1508C. In this study, we added an pared in accordance with the following sequence. First,
emulsion of the water-borne silanol-terminated poly- an appropriate amount of the PDMS polymer emulsion
dimethylsiloxane (PDMS) polymer. As is well docu- (corresponding to the designed proportion of the solid
7–9
mented, the hybrid organic–inorganic solid PDMS polymer (P) in the emulsion to the sum of CAC and fly
film possessed an excellent thermal stability, high ash) was added to the CAC-blended fly ash: the
water-repellence, great flexibility and outstanding resis- polymer emulsion/CAC/fly ash mixture was thoroughly
tance to acid because of a particular chemical structure agitated by a hand-held tool for 3 minutes. Second, the
consisting of flexible Si-O-Si backbone chains, and the 25% NaP solution was slowly incorporated into the
methyl group-rich low-surface-energy configuration. PDMS-modified blend until the slurry attained a
Therefore, the current study was directed toward consistency suitable for pumping. Finally, the cement
validating whether PDMS additive adequately inhibits slurry was cast into cylindrical molds, 30 mm in
the acid erosion of SFCB cements in H2 SO4 at 1508C. diameter and 60 mm long, and allowed to harden for
The following factors were assessed to validate its 24 h at room temperature. The hardened cement speci-
usefulness: the thermal- and hydrothermal-decomposi- mens were removed from the molds, and autoclaved for
tion of PDMS itself, the loss in weight of PDMS-
modified cements as a function of exposure time, the
phase composition and transition of the modified ce- Table 1. Formulation of PDMS-modified SFCB cement
ments after exposure to acid, and the alteration of slurries
microstructure in the exposed cements. Solid PDMS CAC: Fly ash: 25 wt% PDMS
polymer (P)/ wt% wt% NaP: wt% emulsion:
CAC + fly ash wt%
(C) ratio: wt%
Experimental procedure
0 40·5 27·0 32·5 0·0
Materials 5 37·7 25·2 31·4 5·7
Silanol-terminated polydimethylsiloxane (PDMS) 10 35·7 23·8 29·7 10·8
15 33·9 22·6 28·2 15·4
emulsion, ‘LE-743HS’, was obtained from Crompton
36 Advances in Cement Research, 2003, 15, No. 1

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 Acid-resistant polydimethylsiloxane additive for calcium aluminate/fly ash phosphate geothermal well cement
24 h at 1508C to develop a PDMS film in the cement
bodies. Afterwards, the autoclaved specimens were
immersed for up to 20 days in the 2 wt% H2 SO4
solution (pH 1·2) at 1508C. To maintain the pH at
1·2, the H2 SO4 solution was replenished with a new
fresh solution every 5 days. The volume proportion of
the cement specimens to the acid solution was 1 to 25.
Measurements
Thermogravimetric analysis (TGA) was use to assess
the thermal decomposition of the PDMS films. Fourier
transform infrared spectroscopy (FT-IR) and XRD gave
information on the changes in polymer configuration as
a function of temperature, on the phase compositions
and on their changes after exposure to hot acid.
Scanning electron microscopy (SEM) coupled with
energy-dispersive X-ray spectrometry (EDX) was em-
ployed to explore the microstructure developed in the
modified and unmodified cements after exposure. The
EDX quantitative data on the respective chemical
elements were obtained by comparing the EDX k-ratios
for the elements in the cements. The k-ratio is the ratio
between the number of x-rays counted in the net peak
for that element and the number of x-rays counted for
10
the same element under the same conditions. Com-
puter programs were prepared to calculate theoretical
k-ratios and to give us the atomic fraction of each
element present in the cements.
Results and discussion
Thermal and hydrothermal stability of PDMS polymer
Before assessing the effects of PDMS additive on the
resistance of cements to a hot acid, we investigated the
thermal- and hydrothermal-stability of PDMS polymer
films, prepared by heating the PDMS emulsion in an
air oven at 1508C for 48 h.
100
80
60
Weight: %
40
20
0
0 200
Temperature: °C
Fig. 1. TGA curve for the 1508C-made PDMS film
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Fig. 1 plots the TGA thermodynamic curve of the
dry films, showing that its thermal decomposition
begins at a temperature of around 3008C. The weight
loss of 4% gradually occurs between 3008 and 4308C,
followed by large reduction of 96% in weight be-
tween 4308 and 6008C.
Next, we determined the hydrothermal stability of
PDMS films formed at 1508C, after exposure for 24 h
in an autoclave at temperatures of 150, 200 and 3008C
by FT-IR. Fig. 2 illustrates the FT-IR spectra of the
exposed films over the two frequency ranges, 4000–
2000 and 1800–600 cm1 . The spectrum of 1508C-
autoclaved films includes the eight major absorption
bands with assignments as follows: at 3448 cm1 ,
revealing OH stretching vibration in the silanol group
and adsorbed water; at 2966 and 2908 cm1 , reflecting
CH stretching vibration in the CH3 group; at 1261, 861
and 797 cm1 , ascribed to the Si-C band in the Si-CH3
group; and at 1096 and 1014 cm1 , corresponding to
11,12
the Si-O band in the Si-O-Si linkage. Also, the
bending vibration of the Si-O band in the SiOH group
and the bending vibration of O-Si-O unite overlap the
13
bands at 861 and 797 cm1 , respectively. The features
of the spectrum from the 2008C-autoclaved film closely
resembled that obtained at 1508C, demonstrating that
hydrothermal decomposition does not occur up to
2008C. When the temperature was increased to 3008C,
the spectral feature of the film dramatically changed.
Among the changes were the elimination of the CH3 ,
Si-CH3 and Si-O-Si band-related frequencies and the
appearance of four new absorption bands at 1279,
1220, 1100 and 810 cm1 . According to the litera-
ture.
14,15
these new bands can be attributed to the
formation of silica gel, (SiO2 )n xH2 O. This information
strongly verified that PDMS decomposes at 3008C,
with formation of silica gel. However, there is no
experimental evidence on the exact temperature be-
tween 2008C and 3008C at which the PDMS ! silica
433.61°C
400 600 800
37
 Sugama et al.

1261

861
2966
2908
3448
150°C

797
1096
1014
200°C
Transmittance

300°C

810
1279
1220

1100
0.1 %

4000 3000 2000 1800 1400 1000 600

Wavenumber: cm⫺1

Fig. 2. FT-IR spectra for the PDMS films after exposure for 24 h in an autoclave at 150, 200 and 3008C

gel conformational change took place, nor the time
needed to complete this change. Nevertheless, the
PDMS is likely to be persistent at temperatures up to
2008C.
Weight loss
Based upon this information, the cement specimens
modified with the solid PDMS polymer (P)=CAC þ fly
ash (C) ratios of 0, 5, 10 and 15 wt% were immersed in
H2 SO4 solution at 1508C for up to 20 days: weight loss
of the cements was measured to evaluate the protective
capability of PDMS. Acid corrosion products formed
on the surfaces of the exposed cements were brushed
off before measuring weight. Fig. 3 plots the loss in
weight for these cements as a function of exposure
time. During the first five days, the loss of weight was
16
14
12
Weight loss: %
rapid; beyond that time, loss increased gradually. For
unmodified cements, loss was a 14·7% in five days;
increased exposure, 20 days, only increased loss to
16·5%. Compared with this, the loss in weight was
strikingly less in cements modified with the P=C ratio
of 5%. In fact, the recorded weight loss of 10·8% for
these specimens after 20 days exposure was 35%
lower than that of the unmodified cements at the same
exposure time. Increasing the P=C ratio to 10% further
enhanced the resistance of the cements to acid. Corre-
spondingly, their weight loss in 20-day-exposed speci-
mens was only 7·8%, which is less than half of the
unmodified ones. The P=C 15% cements showed no
significant improvement on acid resistance compared
with 10%. Accordingly, 10% seems to be the most
effective P=C ratio in retarding acid erosion. Thus, no
further study was made on the phase compositions and
their transitions, and on the development of microstruc-
ture in the P=C 5%- and 15%-modified cement speci-
mens.
Phase composition and transition

10
We focused on understanding the acid erosion-retard-
8 ing mechanisms of the PDMS-modified cements. To
6 obtain this information, XRD and FT-IR were used to
P/C ratio ⫽ 0% identify the phase compositions and their transitions in
4 P/C ratio ⫽ 5%
P/C ratio ⫽ 10% the superficial layer of P=C 10%-modified and unmo-
2 P/C ratio ⫽ 15%
dified cements before and after exposure for 20 days.
0 The powder samples for these tests were prepared by
0 5 10 15 20
Exposure time: days
physically abrading the cement surfaces.
Figure 4 depicts the XRD traces. Before exposure,
Fig. 3. Weight loss of the PDMS-modified and unmodified the XRD pattern of the surfaces of the unmodified
cements as a function of exposure time cements showed that their superficial layer was com-
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 Acid-resistant polydimethylsiloxane additive for calcium aluminate/fly ash phosphate geothermal well cement
: Ca3(PO4)3(OH)
: γ-AlOOH
For the exposed specimens, the XRD pattern of the
X: Na3Al3Si5O16.6H2O unmodified cements was characterised by the appear-
C: CaCO3 ance of an additional crystalline phase: bassanite
R: CaO.Al2O3
T: CaTiO3
(CaSO4.1/2H2 O), while the CA reactant, calcite, and
Q: SiO2 C HOAp phases had vanished. Since bassanite is an acid
: CaSO4.1/2H2O
T
corrosion product formed by the interactions between
Q the cement and H2 SO4, it is possible to assume that
X
X three phases that were eliminated are implicated in the
R
P/C ratio ⫽ 0 formation of bassanite. We previously reported that, of
before exposure these three phases, two-CA and calcite- are very
susceptible to reactions with H2 SO4 at 908C with
5
formation of gypsum. The HOAp phase also seems to
R be vulnerable to acid attack. Thus, unlike the acid
attack at 908C, the reaction of these three phases with
P/C ratio ⫽ 10
before exposure H2 SO4 at 1508C led to the formation of bassanite, but
not gypsum. On the other hand, the other two hydration
products, zeolite and boehmite, remained unchanged,
demonstrating that their reactivity to acid is negligible.
To support this information, these three minerals,
HOAp, zeolite, and boehmite, were exposed for 3 days
to H2 SO4 solution at 1508C. In this study the HOAp
and boehmite minerals were obtained from the Aldrich
P/C ratio ⫽ 0
after exposure
Inc. and the Sasol North America Inc. respectively. The
zeolite was synthesized by autoclaving at 1508C for 24
h an aqueous-based slurry containing 70 mole % SiO2,
20 mole % Na2 O and 10 mole % Al2 O3. Fig. 5 shows

P/C ratio ⫽ 10
after exposure (a)

25 30 35
CuKa 2θ

Fig. 4. XRD patterns for the PDMS-modified and unmodi-

(b)
fied cements before and after 20 days of exposure

(c)

(d)
posed of three crystalline hydration reaction products:
hydroxyapatite [Ca5 (PO4 )3 (OH), HOAp], boehmite
(ª-AlOOH), and Na-P type zeolite (Na3 Al3 Si5 O16.
Transmittance

6H2 O). There also was one carbonated product, calcite

(CaCO3 ), and three remaining unreacted precursors:
monocalcium aluminate (CaO.Al2 O3, CA), quartz
(SiO2 ), and perovskite (CaTiO3, CT). Calcite was (e)
formed by the carbonation of cement surfaces during (f)
exposure autoclaving. The unreacted CA and CT
reactants arise from the CAC; quartz is one of the
major mineral constituents of fly ash. In contrast, the
0.5%
XRD pattern of the modified cements differed some-
what from those of the unmodified ones; in particular,
there was a weak line intensity of calcite; boehmite was 2000 1500 1000 500
Wavenumber: cm⫺1
present and an increased line intensity occurred for CA
and quartz. This finding suggests that the incorporation Fig. 5. FT-IR spectra for: (a) unexposed HOAp; (b) exposed
of PDMS into the cement not only restrained the HOAp; (c) unexposed zeolite; (d) exposed zeolite; (e)
chemical and hydration reactions of CA reactant but unexposed boehmite; ( f ) and exposed boehmite to 1508C
also prevented carbonation of the cements. H2 SO4 solution for 3 days
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 Sugama et al.
the FT-IR spectra of the powder samples with a particle
size of ,20 m for each of the minerals before and
after exposure. By comparison with those of these
unexposed minerals, the characteristics of the spectral
features for each one exposed were as follows. For the
HOAp, the spectrum (b) of the exposed samples
revealed an entirely different feature, which represents
15
the formation of bassanite. This striking change
inspectrum clearly demonstrated that most of the HOAp
mineral was transferred into the bassanite during the
three days exposure period. The spectrum (d) of the
exposed zeolite encompassed three additional bands as
shown by the arrow. These new bands can be ascribed
15
to the formation of sodium sulfate compounds. If this
interpretation is valid, some Na in the zeolite structure
reacted with the H2 SO4 to form sodium sulfate. In
contrast, no significant change in any spectral feature
was observed from the exposed boehmite mineral.
Hence, this result strongly supported the earlier find-
ings; namely, the HOAp was very vulnerable to the
reaction with H2 SO4, meanwhile the extent of suscept-
ibility of the zeolite to acid was much less than that of
the HOAp. Literally, the beohmite appears to have far
greater resistance to acid in this short-term exposure.
Hence, the zeolite and boehmite phases might play an
important role in abating the rate of H2 SO4 -associated
erosion of the 1508C autoclaved cements, but not the
HOAp phase. The XRD trace of the modified cements
revealed some differences in the patterns compared
with that of the unmodified ones; among the differ-
ences were the reduced line intensity of bassanite and
the presence of HOAp phases. Referring to the former
result, this reflects a reduction in the acid corrosion
product. Thus, the PDMS appears to offer some degree
of protection to the cements against acid corrosion.
Further, there were no lines related to the CA and
calcite, seemingly suggesting that these phases are
much more sensitive to reactions with acid than HOAp.
FT-IR analyses were also carried out on the same
Before exposure
3103
3312
After exposure
3610
3556
Transmittance
0.1%
4000 3000
Wavenumber: cm⫺1
Fig. 6. FT-IR spectra for unmodified cements before and after 20 days of exposure
40
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samples as those used in the XRD study. Fig. 6
compares the FT-IR spectral features of the unmodified
cements before and after exposure. The spectrum of the
unexposed cements had ten absorption bands at 3312,
3103, 1637, 1459, 1420, 1061, 1042, 979, 736 and
667 cm1 . The first two bands together with the band
at 736 cm1 can be ascribed to the O-H stretching
16
vibration in the boehmite phase and in water. The
1
band at 1637 cm is the H-O-H bending vibration in
water. The CO3 -related absorption bands in the calcite
phase generate the three frequencies at 1459, 1420, and
15
667 cm1 . The major contributor to the bands at
1061, 1042, and 979 cm1 is the P-O stretching mode
17
in the HOAp phase. However, the band at 1061 cm1
also encompasses the stretching of the oxygen-bridged
18
Si-O-Si and Si-O-Al in the quartz and zeolite coexist-
16
ing with the Al-O-H bending mode in the boehmite.
Further, the oxygen-nonbridged Si-O stretching of the
SiO- -Naþ bond in the zeolite generates the frequency
19
around 979 cm1 . Compared to the spectral feature of
the cements before exposure, there were striking
changes in the exposed cements. All the bands related
to calcite and HOAp were eliminated, while the
boehmite-related bands at 3312, 3103 and 740 cm1
remained. The spectrum also included six new absorp-
tion bands at 3610, 3556, 1620, 1158, 1096 and
662 cm1 , revealing bassanite as the acid corrosion
15
product of the cement. This finding strongly sup-
ported the results from the XRD; namely, that calcite
and HOAp react while bassanite forms during exposure
to H2 SO4.
Figure 7 illustrates the spectra of the modified
cements before and after exposure. For the unexposed
ones, the distinctive features of spectrum, compared
with that of the unmodified cements before exposure,
were as follows. The first was the appearance of the
CH3 group-related bands at 2966 and 2908 cm1 and
the Si-CH3 -related shoulder bands at 1261 and
797 cm1 , signifying the incorporation of PDMS into
1637
1459
1420
736
1061
667
1042
979
1620
740
662
1158
1096
1800 1400 1000 600
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 Acid-resistant polydimethylsiloxane additive for calcium aluminate/fly ash phosphate geothermal well cement
2966
2908
3103
Before exposure
3312
After exposure
3610
3556
Transmittance
0.1%
4000 3000
Wavenumber: cm⫺1
Fig. 7. FT-IR spectra for modified cements before and after 20 days of exposure
the cements. Second was the strikingly intensity de-
crease in CO3 -related bands, reflecting a reduction in
the rate of carbonation of the cements due to PDMS,
while the third was the pronounced growth of a wide
absorption band between 1100 and 979 cm1 . The
latter is due to the superposition of the Si-O-Si linkage-
associated bands of PDMS on the original HOAp-,
boehmite- and zeolite-related band region. As expected,
the spectrum of the exposed cements was characterised
by the appearance of several additional bands related to
bassanite, with the concurrent disappearance of the
calcite-related bands. This finding can be taken as
evidence that all of the calcite was transformed into
bassanite by reaction with acid during the 20-day
exposure. Also, the spectrum contained absorption
bands originating from the HOAp, boehmite, and
zeolite phases, reflecting the excellent performance of
PDMS in protecting the hydration products of cement
from acid attack.
Microstructure development
The development of microstructure at the surface
and subsurface areas for the 20-day-exposed cements
with and without PDMS was explored. For exposed
unmodified cements, we visually observed that their
entire surfaces were covered with H2 SO4 -induced cor-
rosion products shown in Fig. 8. To identify the
chemical state of the crystals, they were removed and
analyzed by XRD (Fig. 8): this crystalline corrosion
product is bassanite, together with some non-reacted
perovskite. Of particular interest is to determine how
deeply acid corrosion occurs in the unmodified ce-
ments, and also to explore the alterations in microstruc-
ture caused by its penetration. Fig. 9 shows a cross-
sectional area of the cements by SEM-EDX. The SEM
microphotograph taken from the secondary electron
image disclosed formation of dual-rim layers. The first
rim was a bright-colored layer extending to depths of
240 m from the top surfaces. The second interior
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1637
1459
1420
1261
797
667
736
1620
979
1042
1061
740
1158
602
1096
1800 1400 1000 600
layer was a darker color 390 m thick. Thus the
unchanged layer began at a distance of .630 m from
the surface. The SEM cross-examination (not shown)
revealed that the bright-colored rim denoted as ‘A’ had
a relatively porous microstructure, caused by a severe
acid corrosion of the cement. Its EDX atomic fractions
indicated the presence of large amounts of oxygen,
sulfur, and calcium and four minor elements: alumi-
num, silica, titanium and sodium. These principal
elements appear to be associated with the bassanite as
corrosion product of the cement. In conjunction with
some oxygen, the other elements detected in this
surface layer may originate from boehmite, quartz,
perovskite and zeolite. No phosphorous was found in
this layer, suggesting that the HOAp reaction product
dissolved and leached from the top surface layer. The
microstructure of the dark-colored rim designated as
‘B’ was much denser than that of in rim ‘A’, but still
included 5·1% sulfur. Although this value is 76% less
than the sulfur content of in the rim ‘A’, we assumed
that some bassanite phases were incorporated into the
rim ‘B’. Also, the atomic composition of this rim
revealed two new elements, phosphate and iron, which
were not detected in the rim ‘A’. The former reflects
the formation of HOAp, and the latter may arise from
an iron-related chemical compound present in the
CAC. Hence, ‘B’ consisted of a mixture of bassenite,
HOAp, boehmite, zeolite, quartz, perovskite, and an
iron compound. Location ‘C’ in the non-rim layer had
a denser microstructure. Sulfur was not found at this
location, nor did acid corrosion products exist at a
depth of 714 m. Therefore, only the subsurface
layers of 630 m thick underwent acid corrosion
during the 20-day exposure.
Figure 10 gives the SEM-EDX data of cross sec-
tional profile of the PDMS-modified cement after
exposure for 20 days. The SEM image markedly
differed from that of the unmodified one; namely, only
one rim layer of 400 m thick was observed. En-
41
 Sugama et al.

O: CaSO4.1/2H2O O
T: CaTiO3 O

20 25 30 35
CuKa 2θ

Mag:100 kV:17 WD:39 100 µm

Fig. 8. SEM image and XRD pattern of the acid corrosion products formed on unmodified cement’s surfaces during the 20-day
exposure

Element Atomic
Surface
fraction: %
O 41.1
Al 6.9
Si 7.4
S 21.5
Ca 14.1
Ti 6.2
Na 2.8

A
Element Atomic
fraction: %
B
O 52.7
Al 13.9
Si 7.2
P 6.9
S 5.1
Ca 10.5
Ti 0.4
Fe 0.1 C
Na 3.2

Element Atomic
fraction: % Mag:50 kV:17 WD:39 100 µm
O 48.3
Al 24.2
Si 11.3 A B
P 4.5
S 0.0 Rim structure
Ca 7.5
Ti 0.7
Fe 0.4
Na 3.1

Fig. 9. SEM microphotograph and EDX atomic fractions for cross sectional area of the unmodified cement after 20 days of
exposure
42 Advances in Cement Research, 2003, 15, No. 1

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 Acid-resistant polydimethylsiloxane additive for calcium aluminate/fly ash phosphate geothermal well cement

Element Atomic
fraction: %
C 2.1 Surface
O 24.2
Al 20.9
Si 11.0
P 6.7
S 8.7
Ca 19.8
Ti 2.5
Fe 2.3 A
Na 1.8

Mag:500 kV:17 WD:39 10 µm

B

Element Atomic
fraction: %
C 1.2
O 46.5
Al 20.0
Si 9.5
P 8.9
S 0.0 Mag:50 kV:17 WD:39 100 µm
Ca 10.4
Ti 0.5
Fe 0.1
Na 2.9 Rim structure

Mag:500 kV:17 WD:39 10 µm

Fig. 10. SEM image analysis and EDX atomic fractions for cross sectional profile of the modified cement after 20 days of
exposure

largement of location ‘A’ in the rim disclosed a very
rough surface texture. As is evident from the EDX
atomic composition accompanying this SEM image,
this rim included all the reaction products of the
cement together with bassanite because of the presence
of a certain amount of aluminum, phosphate, sulfur,
calcium and sodium. Also, this rim contained 2·1%
carbon, which was not detected in the unmodified
cement: we assume that the carbon arises from the CH3
groups within the PDMS. The presence of residual
HOAp validated our conclusion that the PDMS additive
can improve the resistance of the cement to acid. Below
the rim at location ‘B’, 480 m from the surface, the
typical microstructure of the original SFCB cement can
be seen from the SEM image. The image shows that
cement hydration products bind together the non-
reacted spherical fly ash particles into a cohesive mass.
Thus, although the extent of vulnerability of PDMS-
modified cement to acid corrosion was considerably
less than that of unmodified cement, it did allow the
acid solution to permeate through a surface layer of
400 m thick within 20 days.
Conclusion
Based upon the information described above, the
following statements can be demonstrated. Silanol-
terminated polydimethylsiloxane (PDMS) emulsion,
Advances in Cement Research, 2003, 15, No. 1
used as the high-temperature anti-acid corrosion addi-
tive, enhances the resistance of sodium polyphosphate-
modified Class F fly ash/calcium aluminate blend
(SFCB) cements to a 1508C H2 SO4 solution (pH 1·2).
Thermal decomposition of the PDMS film, formed by
heating the emulsion at 1508C, began around 3008C in
air. When the film was exposed in an autoclave, it
sustained a hydrothermal temperature of 2008C, but
raising the temperature to 3008C led to the conforma-
tional transformation of the PDMS macromolecule into
silica gel amongst other phases. The SFCB cements
were modified with solid PDMS polymer (P)/calcium
aluminate-fly ash (C) ratios of 0, 5, 10 and 15 wt%.
The modified and unmodified cements then were
autoclaved at 1508C before exposure to hot acid. The
crystalline phase composition of the surfaces of 1508C-
autoclaved cements without PDMS consisted of three
hydration reaction products: hydroxyapatite (HOAp),
boehmite, and Na-P type zeolite, and one carbonated
product, calcite. In addition, some non-reacted reactants
such as moncalcium aluminate, perovskite and quartz,
which are the major chemical constituents of calcium
aluminate cement (CAC) and fly ash, still remained in
the superficial layer. Incorporating PDMS into the
cement significantly reduced the rate of carbonation,
while the same hydration reaction products as those of
the unmodified cements are formed. The surfaces of
unmodified cement were vulnerable to hot H2 SO4
attack, thereby resulting in the massive formation of
43

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 Sugama et al.
the bassanite as the corrosion product. The bassanite
phase was formed not only by the interactions between
calcite or monocalcium aluminate and H2 SO4, but also
was due to the susceptibility of the HOAp to reactions
with H2 SO4. However, the reactivity of the other
hydration reaction products to acid, such as boehmite
and zeolite, was very little, if any. As a result, a
subsurface layer of 630 m thick underwent some
acid corrosion during the 20-day exposure; in particu-
lar, the superficial layer at depth of 240 m suffered
severe acid damage. In contrast, PDMS greatly pro-
tected the cements from destruction by hot acid. In
fact, although the modified cements allowed the acid
solution to penetrate through a subsurface layer of
400 m, some HOAp phases still remained in the
superficial layer, validating the effectiveness of PDMS
in alleviating acid corrosion. This correlates with the
lower rate of acid erosion of the PDMS-modified
cements compared with the unmodified ones. The
cements modified with P=C ratio of 10% showed a
relatively low weight loss of 7·8% after exposure for 20
days, and this value was equivalent to a reduction of
more than 50% over that of unmodified ones.
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Discussion contributions on this paper should reach the editor by
1 June 2003
Advances in Cement Research, 2003, 15, No. 1