Journal of Colloid and Interface Science 343 (2010) 162167

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Journal of Colloid and Interface Science

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Cementepoxy/water interfaces Energetic, thermodynamic, and kinetic

parameters by means of heat-conduction microcalorimetry
Antonio R. Cestari *, Eunice F.S. Vieira, Andra M.G. Tavares, Marcos A.S. Andrade Jr.
Laboratory of Materials and Calorimetry, Department of Chemistry/CCET, Sergipe Federal University, CEP 49100-000, So Cristvo, Sergipe, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Hydration phenomena at cement/water interfaces drive the characteristics of oil-well cement slurries. In
Received 23 September 2009 this study, new epoxy-modied cement slurries were synthesized. The slurries characterization has sug-
Accepted 5 November 2009 gested the presence of low amounts of portlandite in the slurry with the higher content of polymerized
Available online 18 November 2009
epoxy resin. The hydration processes of the cement slurries were studied by heat-conduction microcal-
orimetry. The energetic and enthalpic hydration data were all exothermic in nature. The cumulative heat
Keywords: release curves have shown the presence of multilinearity of the kinetic processes. The hydration micro-
Cement/water interfaces
calorimetric data were well tted to the multistep Avrami kinetic model. It was found that the epoxy-
Oil-well cement slurries
Epoxy resins
modied cement slurries present a good potential to be used in environmental-friendly oil-well
Microcalorimetry operations.
Thermodynamics 2009 Elsevier Inc. All rights reserved.
Kinetics

1. Introduction
Portland cement is used in large quantities to grout oil-wells.
The cement slurry is placed between a metal liner and the walls of
the borehole to provide support for the liner and a seal to prevent
the migration of gas and loss of zonal isolation along the outside of
the liner [1]. Long-term performance of the cement slurries is of
great concern. If the cement slurry does not provide a good seal,
loss of zonal isolation leads to safety and environmental problems
[13].
Portland cements withstand chemical (dissolution and precipi-
tation) and physical (occulation and coagulation) changes when
in contact with water [4]. Such changes have signicantly affected
the rheology of hydrating cementitious materials since the early
ages, even during the induction period, when the hydration reac-
tions are still incipient. When chemical admixtures are present,
the system becomes even more complex due to physicalchemical
interactions with the hydrating cement [5]. The protective charac-
teristics of oil-well cements are in practice controlled by the addi-
tion of polymeric additives [6].
Water-soluble polymers are frequently added to cement mor-
tars in order to improve the fresh mixture properties [7]. Epoxy
resins are used to provide a good wettability of the cementitious
substrate. Polymeric epoxy resins have been useful in promoting
the physico-chemical interactions and ensure an optimal level of
adhesion between the mineral and the organic phases of cement
* Corresponding author. Fax: +55 79 21056684.
E-mail address: cestari@ufs.br (A.R. Cestari).
slurries [8]. Currently almost 90% of the world production of epoxy
resins is based on the reaction between bisphenol A (2,2-bis(40 -
hydroxyphenyl)propane and epichlorohydrin 24 [9]. Epoxy ce-
ment mortars are composed of emulsied bisphenol A epoxy resin,
cement, and ne aggregates. In some cases, the epoxy cement mor-
tars with hardeners, which are Lewis bases in nature (generally, or-
ganic acids or amines), have some properties that are better than
the mortars without a hardener. The conventional epoxy cement
mortars with a hardener must have a polymer content higher than
40% to achieve good mechanical properties and durability. The
epoxy resins can also harden in the presence of alkalis formed from
the hydration of cement [10].
The hydration of cementitious materials is exothermic, with en-
ergy of up to 100 J/g of cement being liberated [11]. The knowledge
of the heat-producing properties of different cementitious materi-
als is required in order to choose a suitable cementitious system
for a given specic project. The kinetic and thermodynamic fea-
tures of the early hydration stages are essential for the perfor-
mance of hardened cements and can be monitored by isothermal
microcalorimetry [12]. However, there is relatively little research
on early cement hydration, that is, the initial hours after adding
water.
In this work, two epoxy-modied cement slurries and an epoxy-
free cement slurry were obtained and characterized. Heat-conduc-
tion microcalorimetry was used to obtain and to compare the fea-
tures of heat evolution evolved in the early stages of hydration of
the epoxy-modied cement slurries, with the objective of increas-
ing the understanding of the hydration processes at cement/water
interfaces.

0021-9797/$ - see front matter 2009 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2009.11.017
 A.R. Cestari et al. / Journal of Colloid and Interface Science 343 (2010) 162167
2. Materials and methods
2.1. Materials and reagents
Water was double-distilled before use. Powder cement (200
325 mesh, Class A) from Cimesa (Laranjeiras-SE, Brazil) was used.
The characteristics of the cement powder were shown earlier
[10]. The bisphenol F epoxy resin, commercially available as Aral-
dite PY340, and its hardener (Versamid 125) were supplied by
The Huntsman Co. Special Resins. The chemical structures of the
resin and the hardener are shown in Fig. 1.
2.2. Preparation of the cement slurries
The mixing procedure adopted was in accordance with the Amer-
ican Petroleum Institute (API) practice, and consisted of mixing the
cement, epoxy resin, and hardener at 4000 rpm for 20 s, and then
mixing for 30 s at 12,000 rpm [10,13]. Two epoxy-modied slurries
were synthesized using 10% and 30% of the epoxy resin in relation to
the cement mass. In order to avoid uncompleted polymerization, the
proportion of epoxy resin/hardener was 1/2. The cement and water
were used to obtain the standard cement slurry. The amounts of the
components of the slurries were calculated in relation to a nal den-
sity of the cured slurries from 1.50 to 2.00 g cm3 [10,13]. The ce-
ment slurries were cast into cylindrical molds with each
10.0  20.0 mm for 6 h at room temperature before use. The slurries
are hereafter denominated, for simplicity, as standard slurry (ce-
ment and water), PY340-1 (30% of Araldite PY340 + hardener), and
PY340-2 (10% of Araldite PY340 + hardener).
2.3. Characterization of the slurries
The thermogravimetric analyses (TG and DTG) were made using
about 10 mg of material, under oxidative atmosphere from 25 to
800 C, in a SDT 2960 thermoanalyzer, from TA Instruments. DSC
analyses were performed in sealed Al pans, using about 10 mg of
material, under oxidative atmosphere from 25 to 600 C. DRX-ray
analyses were performed in a Rigaku diffractometer, in the 2h
Fig. 1. Chemical structures of the epoxy resin (above) and the hardener (below).
163
range from 5 to 80 (accumulation rate of 0.02 deg min1), using
Cu Ka radiation.
2.4. Microcalorimetric experiments
Microcalorimetric measurements of the hydration processes of
the slurries were performed at 25 C in a SETARAM C80 heat-con-
duction calorimeter (France). Specic characteristics of the heat-
conduction calorimetric system have been previously described
[13,14]. In a typical experiment, a cementitious conical sample
was put into the lower part of the calorimetric cell closed by a cir-
cular PTFE thin membrane. Into the upper part of mixing cell, a vol-
ume of 3.0 ml of water was added. After complete stabilization of
the calorimeter base line, a movable rod enables water to be
pushed into the container with the cementitious sample. Each indi-
vidual experiment yields a thermal effect, Qr. Data acquisition was
continued for nearly 160 h. The thermal effect of membrane break-
ing for the empty cell was found to be negligible compared to Qr
values. The detectable calorimeter signals (power versus time), as
well as the cumulative heats of hydration were performed using
the SETSOFT software (SETARAM). Each experiment was repeated
at least in duplicate. Statistical calculations (t tests, F tests, analysis
of variance (ANOVA), and multiple regressions) were carried out
with ORIGIN and Statistica softwares, both releases 7.0.
3. Results and discussion
3.1. Some initial considerations
The compositions of oil-well cement slurries are usually based
on four principal mineral phases [1]: tricalcium silicate (Ca3SiO5),
dicalcium silicate (Ca2SiO4), tricalcium aluminate (Ca3Al2O6), and
a calcium aluminoferrite of more variable composition. The cal-
cium silicate hydrate formed, known as CSH, is a very poorly
crystalline nonstoichiometric material consisting principally of di-
meric units at rst, but which subsequently slowly polymerize
after a few days to give higher linear units like pentamer and
thence octamer.
Tricalcium silicate is the principal cementing phase, whereas
dicalcium silicate (usually in the b-form) reacts at a much slower
rate to form similar hydration products. The hydration products
from the tri- and b-dicalcium silicate phases at up to 100 C do
not differ essentially from those formed at ambient temperature.
The rate of hydration of Portland cement increases with increasing
temperature, especially at lower degrees of hydration, whereas this
effect becomes less pronounced as the hydration progresses [1,4].
Only the hydration of dicalcium silicates was found to be acceler-
ated signicantly even months after mixing with water. No
changes in the mechanism of hydration have been reported in
the temperature range from ambient to 90 C. At elevated temper-
atures the hydration of b-dicalcium silicate is accelerated in rela-
tion to that of tricalcium silicate, which could be related to the
high solubility of silica and low solubility of calcium hydroxide un-
der these conditions.
Some calcium hydroxide is present at the beginning of hydra-
tion, where the aqueous phase of the cement slurry can be consid-
ered for simplicity as essentially a limewater medium, being
derived from some hydration of the small free lime content
[1,4,15] as follows:
CaO H2 O ! CaOH2 1
The alkali metal ions from the sulfates readily enter the solution
when the cement is mixed with water and accelerate the early
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Cementepoxy/water interfaces Energetic, thermodynamic, and kinetic parameters by means of heat-

609423 6
conduction microcalorimetry

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