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Carbonation of concretes in the Mexican Gulf

P. Castro
a,
*, M.A. Sanjua n
b
, J. Genesca
c
a
Centro de Investigacion y de Estudios Avanzados del IPN, Unidad Merida, km 6 Ant Carr.a Progreso, CP 97310, Merida, Yucatan, Mexico
b
Instituto Espanol del Cemento y de sus Aplicaciones, C/Jose Abascal, 53-28, 28033, Madrid, Spain
c
Facultad de Qumica de la UNAM, Edicio D, 04510, DF Mexico
Accepted 21 January 1999
Abstract
Carbon dioxide penetration into concrete leads to reinforcing depassivation and onset of the corrosion process. Thus, a deep
knowledge on the parameters aecting such a process will allow denition of the most suitable mixture design to provide
adequate durability. Experimental results show the eect of an exposed location in a coastal area on the carbonation process of
ve qualities of concrete. The carbonation depth was checked by spraying phenolphthalein. The results generally showed that
the more distance from the coast, the greater the carbonation rate. The results also showed the greater the strength, the lower
the carbonation coecient when specimens are located at 50 m from the seaside. Whereas, in those located at 100 m and 780 m,
such a trend is unclear for concretes of 28-day compressive strength higher than 22 MPa. # 1999 Elsevier Science Ltd. All
rights reserved.
1. Introduction
Atmospheric carbon dioxide diuses into concrete
through the pore network and microcracks, and then
reacts with the alkaline compounds of the pore sol-
ution and the hydrated cement phases. Such reactions
lower the typical alkalinity of the pore solution. This
reduction of pH within the concrete cover destroys the
passivation layer on the reinforcement and initiates the
corrosion. The importance of the moisture content in
the pores is crucial in the diusion process. It is gener-
ally recognized that the environment is an important
factor in the carbonation process [1], due to the depen-
dence of the carbonation rate on the moisture state of
the concrete. It is also well known that at moisture
contents close to saturation, the transport phenomena
diminishes due to an insucient presence of empty
pores [2].
On the other hand, permeability values calculated
from data obtained via accelerated carbonation of the
sample can not be interpreted as actual coecients of
permeability, as the assumption of ow through an
inert material is invalid. As known, carbonation can
signicantly aect permeability of cover concrete
because the reaction modies the pore structure of the
cement paste [3]. The test methods involving carbona-
tion are often used for the purpose of testing natural
carbonation however, as they are more rapid than this
one. In addition, the methods resemble many of the
environmental conditions concrete is exposed to. This
draws on the importance of getting actual eld data [4]
in order to assess reliable carbonation coecients,
which then allow the required concrete mixture design
to be made for a required service life. Field studies
necessarily correspond to real structures. This paper
examines the carbonation process at three coastal
microclimates that lead to a clearer picture of carbona-
tion in a marine atmosphere. In this paper the eect of
the environment on the concrete carbonation is
addressed.
Building and Environment 35 (2000) 145149
0360-1323/00/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S0360- 1323( 99) 00009- 8
www.elsevier.com/locate/buildenv
* Corresponding author. Tel.: +52-99-81-29-60; fax: +52-99-81-
29-17.
E-mail address: pcastro@kin.cieamer.conacyt.mx (P. Castro)
2. Experimental program
2.1. Specimen description
Concrete specimens consisting of 07.5 cm
dia. 15 cm length cylinders were prepared. They
were exposed to a marine atmosphere at three dierent
locations: 50, 100 and 780 m from the seaside. Fifteen
pairs of concrete cylinders were exposed in each lo-
cation, as shown in Fig. 1. Each pair consisted of a
determined w/c ratio and duration of curing (ve w/c
ratios and three durations of curing). The w/c ratios
tested were 0.76, 0.70, 0.53, 0.50 and 0.46 and the dur-
ations of curing 1, 3 and 7 days under water. An
ordinary Portland cement (ASTM Type I) was used
with 65% CaO. Crushed natural limestone was used as
aggregate to construct the cylinders and came from a
bank close to the coast which supplies most of the
construction projects in Northern Yucata n (Me xico).
The sieve analysis showed good gradation for the
coarse aggregate (maximum size of 20 mm) but an
excess of nes in the sands. Tap water was used for
mixing and, in the case of the curing process, a 2% of
lime was added to the potable water in order to
increase its pH and thus avoid the loss of alkalinity
during the concrete setting. Concrete specimens con-
sisting of 15 cm dia. 30 cm length cylinders were
also prepared for compressive strength tests according
to ASTM-C-39. The selection and characteristics of
these materials were done based on real and common
situations observed in this zone.
2.2. Carbonation testing
Prior to exposure, the specimens faces were sealed
with epoxy in order to have only radial inuence of
the environment. A slice was cut on each of them at
dierent ages. They were diametrically broken and a
solution of ethyl alcohol at 1% of phenolpthalein [5]
was applied in order to know the carbonation depth
(purple where uncarbonated and colorless where car-
bonated). Results after 31 months of natural carbona-
tion are reported here.
The carbonation depth was the data needed to cal-
culate the carbonation constant, K, according to Eq.
(1).
x K

t
p
1
where K = carbonation constant (mm/yr
0.5
),
x = carbonation depth (mm) and t = time (yr).
Table 1 shows approximately the characteristic
values of K for good, average and poor quality con-
crete.
3. Results
Concrete quality can be related to cement content
and strength, among others, and high levels of either
are associated with smaller depths of carbonation. The
carbonation constant was calculated by means of the
square-root law from Eq. (1). This parameter was
plotted in function of the 28-day compressive strength
at the three exposure locations of 50 m, 100 m and
780 m from the seaside for the curing times of 1, 3
and 7 days as shown in Fig. 2. A general trend of low-
ering the carbonation coecients when increasing the
compressive strength is observed. However, at higher
strengths (>22 MPa), the carbonation process seems
not to be inuenced signicantly by the concrete
strength (with the exception of concretes at 50 m from
the seaside).
With regard to the exposure location, it can be
observed that the lowest carbonation coecients were
registered in the concretes nearest to the sea as seen in
Fig. 2a. In these concretes, located at 50 m from the
Fig. 1. Sketch and photo of the exposure sites.
Table 1
Typical values of K for poor, average and good concrete
Poor concrete Average concrete Good concrete
K (mm/yr
0.5
) > 9 9 > K > 6 < 6
P. Castro et al. / Building and Environment 35 (2000) 145149 146
seaside, it is also clearly observed that the more
strength, the lower the carbonation. On the contrary,
when concretes are exposed to larger distances, this
trend is only found in concretes presenting compressive
strengths lower than 22 MPa, as shown in Figs. 2b
and 2c. Concretes with higher strengths did not exhibit
a signicant dierence increasing the resistance.
In relation to the eect of the curing time, it can be
established from the results obtained at 50 m and
780 m from the seaside that in concretes of 22 MPa or
higher, low carbonation rates are found when the time
of curing is extended; whereas for lower strength con-
cretes, this parameter seems not to have any inuence.
On the contrary, it is mentionable that concretes
exposed at 100 m did not present any peculiar trend
regarding the curing.
Fig. 3 shows the carbonation depth vs the curing
time for 14, 19 and 31 months of exposure. Plots of
the 15 MPa and 21 MPa are shown only for simplica-
tion. A trend line was drawn for each concrete
strength with the only purpose of comparing the
increasing or decreasing tendency of the carbonation
depth with the curing time. For lower strength con-
cretes the carbonation depth increases with the curing
time, as seen in Fig. 3a. This tendency is reversed at
higher strength concretes (from 21 MPa), as observed
in Fig. 3b. In both cases, and as expected, the prole
becomes atter with the exposure duration.
Fig. 2. Carbonation constant, K, vs 28-day compressive strength: a, 50 m; b, 100 m; and c, 780 m from the seaside.
P. Castro et al. / Building and Environment 35 (2000) 145149 147
4. Discussion
Field data are discussed in relation to the likely pro-
gress of carbonation. In experimental research on gas
transport characteristics of concrete, it is normally the
study of the ow of one single aggressive element in
order to derive transport coecients according to the
underlying theoretical model of such process. This pro-
cedure presents some limitations because in most cases
concrete does not behave as an inert material. Thus,
simplifying assumptions must be taken into account
when results are discussed.
The higher humidity and salt content in the air clo-
sest to the seaside are, apparently, contributing to
block the carbon dioxide access to the pore network of
the concrete. These specimens are highly chloride con-
taminated [6] and their hygroscopicity help to maintain
the saturation of the pore network [7]. For this reason,
these specimens show carbonation coecients that cor-
relate well with the concretes' strength. On the other
hand, for specimens at 100 m and 780 m from the sea-
side the carbonation coecients were higherpossibly
due to the partially wet pores that promote higher car-
bonation rates [8]. However, the concrete strengths
higher than 22 MPa show no clear inuence on the
carbonation rate. This is contrary to what was
expected and no explanation for this contradiction was
found.
In concretes with strengths higher than 22 MPa the
eect of the curing time is appreciable at 50 m and
780 m from the seaside. This is possibly due to the
fact that both microenvironments are surrounded by
brackish water or marsh water, as shown in Fig. 1,
that promote saturation of the pores. The specimens at
100 m from the seaside are exposed to a more complex
environment that impede the observation of the
expected dependencies. It is important, for these
reasons, not to generalise recommendations based on
eld results of a single microclimate
In specimens exposed in the seaside (50 m, Fig. 3a)
the carbonation depth is higher at extended curing
times and at low compressive strength (very porous
material, 15 MPa) due to the pore solution leaching
during the curing time [8] that allows a loss of alka-
linity and therefore a carbonation facility. This did not
happen in specimens with normal or high strength con-
cretes (Fig. 3b, 21 MPa) and for that reason the carbo-
nation depth is higher at the shortest curing times.
5. Conclusions
The results show the importance of evaluating the
carbonation in marine microenvironments. Strong
dierences in the carbonation behaviour can be found
at a few metres from the seaside. This necessarily pre-
vents general recommendations based on the exposure
of specimens in a single microenvironment. The evalu-
ation made here, suggests adequate concrete covers
will depend on the microclimate, the w/c ratio and the
curing time to protect the rebar against depassivation.
Several aspects on the carbonation behavior on each
of the evaluated microclimates need more studies to be
completely understood. The results also showed that,
in general, the more distance from the coast the
greater carbonation rate, the more strength the lower
carbonation coecient when specimens are located
50 m from the seaside. In specimens located at 100 m
and 780 m such a trend is unclear for concretes of 28-
day compressive strength higher than 22 MPa.
Acknowledgements
The authors gratefully acknowledge the support for
this research provided by CINVESTAV Me rida Unit,
the National Council of Science and Technology
(CONACyT through the contracts 0527-A9109,
F051I9110, 211085-5-2186PA and E130-1332) and the
Fig. 3. Carbonation depth vs curing time: a, 15 MPa of compressive
strength; and b, 21 MPa of compressive strength.
P. Castro et al. / Building and Environment 35 (2000) 145149 148
Superior Council of Scientic Investigations (CSIC-
Spain). One of the authors, P. Castro, wish to thank
CONACyT for a postdoctoral grant and M. Balanca n
for her support with the carbonation tests. The
authors are also indebted to Dr C. Andrade and Dr C.
Alonso for their helpful recommendations and co-op-
eration.
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