Carbonation of Concrete Containing Mineral Admixtures

P. Sulapha1; S. F. Wong2; T. H. Wee3; and S. Swaddiwudhipong4

Abstract: This study deals with the carbonation of concrete incorporating ground granulated blast-furnace slag 共GGBS兲, fly ash 共FA兲,
and silica fume 共SF兲. It is observed that a decreased water-to-binder ratio and replacement level of GGBS, FA, or SF, or an increase in
GGBS fineness and curing age in water, led to better carbonation resistance. However, compared to a plain concrete, the concrete
incorporating mineral admixtures 共except GGBS with higher fineness and SF兲 generally showed lower resistance to carbonation, possibly
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due to the dominating effect of the reduction in calcium hydroxide over pore refinement. Hence, adequate curing is recommended for
enhancing the resistance of concrete containing GGBS, FA, and SF to carbonation. It is also found that both the carbonation coefficient
and compressive strength served as good indicators for the carbonation rate of concrete with and without mineral admixtures.
DOI: 10.1061/共ASCE兲0899-1561共2003兲15:2共134兲
CE Database subject headings: Carbonation; Concrete; Admixtures.

Introduction surface due to the highly alkaline environment of the surrounding

The importance of carbonation, which is a slow process under
natural conditions, has grown in recent years due to the aging of
a large number of structures and the associated risk of degrada-
tion. Although the concentration of carbon dioxide (CO2 ) present
in the atmosphere is rather low 共about 0.03–0.10% by volume for
indoor conditions in Singapore兲, it is highly reactive with cement
hydrates such as calcium hydroxide 关 Ca共OH) 2 ] and calcium sili-
cate hydrate 共C-S-H or 3CaO•2SiO2 •3H2 O), as well as nonhy-
drated cement phases such as tricalcium silicate (C3 S or
3CaO•SiO2 ) and dicalcium silicate (C2 S or 2CaO•SiO2 ). Among
these phases, CO2 has a greater affinity for reaction with
Ca共OH) 2 . The overall reactions can be represented as shown by
the following irreversible reactions 共Leberand and Blakey 1956;
Papadakis et al. 1989兲:
Ca共OH) 2 →Ca2⫹ 共 aq兲 ⫹2OH⫺ 共 aq兲 (1)
Ca2⫹ 共 aq兲 ⫹2OH⫺ 共 aq兲 ⫹CO2 →CaCO3 ⫹H2 O (2)
3CaO•2SiO2 •3H2 O⫹3CO2 →3CaCO3 •2SiO2 •3H2 O (3)
3CaO•SiO2 ⫹3CO2 ⫹␮H2 O→SiO2 •␮H2 O⫹3CaCO3 (4)
2CaO•SiO2 ⫹2CO2 ⫹␮H2 O→SiO2 •␮H2 O⫹2CaCO3 (5)
Steel embedded in concrete is usually protected from corro-
sion by a thin oxide layer that is formed and maintained on the
1
Graduate Student, School of Civil Engineering, Purdue Univ., West
Lafayette, IN 47907.
2 mixtures in concrete. First, the addition of mineral admixtures
Teaching Fellow, School of Civil and Environmental Engineering,
Nanyang Technological Univ., Singapore.
3
Associate Professor, Dept. of Civil Engineering, The National Univ.
of Singapore, Singapore.
4
Associate Professor and Deputy Head 共Academic兲, Dept. of Civil
Engineering, The National Univ. of Singapore, Singapore.
Note. Associate Editor: John S. Popovics. Discussion open until Sep-
tember 1, 2003. Separate discussions must be submitted for individual
papers. To extend the closing date by one month, a written request must
be filed with the ASCE Managing Editor. The manuscript for this paper
was submitted for review and possible publication on December 19,
2000; approved on January 3, 2002. This paper is part of the Journal of
Materials in Civil Engineering, Vol. 15, No. 2, April 1, 2003. ©ASCE,
ISSN 0899-1561/2003/2-134 –143/$18.00.
concrete 共pH value around 13兲. However, due to the reactions in
Eqs. 共1兲–共5兲, the pH of pore water drops to a value as low as 8.5
in the case of severe carbonation 共Gjorv 1989兲. The passive layer
on the steel surface will no longer remain stable when the alka-
linity of the concrete surrounding the steel drops to approximately
11.5.
Malhotra et al. 共2000兲 reported that after 10 years of outdoor
exposure, the carbonation depths of concrete 共water to total ce-
mentitious material ratios of 0.27–0.29兲, which include plain con-
crete and concrete with 28 –35% slag, 57% fly ash, or 7–12%
silica fume, were small 共in the range of less than 1–5 mm兲 and
almost similar. Schubert and Vom Berg 共1979兲, as well as
Mathews 共1984兲, also observed nearly equal rates of carbonation
in concrete with and without fly ash. However, Scholz and Wierig
共1984兲 found that if concrete mixtures were designed for equal
strengths, the water requirements of concrete containing mineral
admixtures would result in lower carbonation rates.
On the other hand, experiments by Lin and Fu 共1987兲 revealed
that compared to plain mortar, 20, 30, and 40% fly ash mortar
specimens were less permeable after 28 days of curing but more
permeable after carbonation. Nagataki et al. 共1987兲 and Osborne
共1999兲 also noted an increase in carbonation rate with an in-
creased slag replacement level of 30–70% in mortar and 50– 80%
in concrete.
From the literature review, it is clear that in the context of
carbonation, there is debate over the incorporation of mineral ad-
may have little influence on the rate of carbonation. Second, the
lower water requirement of concrete containing mineral admix-
tures 共except silica fume兲 coupled with pore refinement through
the formation of additional C-S-H may lead to a denser micro-
structure of the cement matrix, thus reducing the rate of diffusion
of CO2 . Third, the pozzolanic reaction consumes Ca共OH) 2 from
the cement paste and thereby reduces the amount of Ca共OH) 2
available per unit area to react with the available CO2 , which
may result in faster movement of the carbonation front. Hence, it
is the objective of the present investigation to address some of the
uncertainties over the carbonation of concrete containing mineral
admixtures.

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J. Mater. Civ. Eng., 2003, 15(2): 134-143

 Table 1. Chemical Compositions and Physical Properties of Cementitious Materials
Oxide Composition 共weight %兲 Fineness Specific
Material CaO SiO2 Al2 O3 Fe2 O3 MgO SO3 Na2 O K2 O 共cm2/g兲 gravity
OPC 64.39 21.10 5.24 3.10 1.10 2.52 0.23 0.57 3,170a 3.15
GGBS 42.65 32.40 13.90 0.40 5.90 — — — 4,500a 2.90
42.40 32.30 14.00 0.60 6.00 — — — 6,000a 2.90
42.40 32.70 13.80 0.20 5.90 — — — 8,000a 2.90
FA 3.37 49.30 28.30 13.01 1.37 0.14 0.21 0.76 9.2%b 2.41
SF 4.15 93.00 0.20 0.05 0.51 0.05 0.20 0.22 250,000c 2.00
Note: OPC⫽ordinary portland cement; GGBS⫽ground granulated blast-furnace slag; FA⫽fly ash; SF⫽silica fume.
a
Using the Blaine method.
b
Using sieve analysis 共9.2% retained on 45 ␮m sieve兲.
c
Using the nitrogen adsorption method.
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Experimental Details Specimen Preparation

Materials
The cementitious materials used were ordinary portland cement
共OPC兲, ground granulated blast-furnace slag 共GGBS兲, fly ash
共FA兲, and silica fume 共SF兲. The chemical compositions and physi-
cal properties of these materials are presented in Table 1. The fine
and coarse aggregates used were natural sand and crushed granite,
respectively. The maximum size of the coarse aggregate was 20
mm and the fineness modulus of sand was 2.70. The aggregates
complied with the requirement of ASTM C 33-93. Fourteen mix-
tures consisting of four 100% or plain OPC concrete 关water-
binder ratio (w/b)⫽0.3, 0.4, 0.5, and 0.6兴, as well as nine binary
blended and one ternary blended concrete, were cast. The mixture
proportions of these materials are summarized in Table 2. A
naphthalene-based high range water-reducing admixture comply-
ing with the requirement of ASTM C 494-92, Type F was used to
achieve a target slump of 100⫾25 mm.
To investigate the effect of partial replacement of OPC with
different types of mineral admixtures, 100% OPC concrete of
w/b⫽0.5 was selected as a reference mixture. The replacement
percentages of GGBS 共having 4,500 cm2/g fineness兲 were 30, 50,
and 65%; the replacement level of GGBS 共with 6,000 or 8,000
cm2/g fineness兲 was 65%. Only two replacement percentages
were used for FA 共15 and 30%兲 and SF 共5 and 10%兲.
All concrete mixtures were prepared in a twin-shaft mixer. A con-
sistent mixing sequence was adopted in which fine and coarse
aggregates were first mixed with half of the mixing water for 2
min. After this initial premixing, mineral admixtures were
blended with the aggregates and mixed for 5 min. The cement and
remaining liquids were added in small increments and the mixing
process was continued for another 3 min. The mixer was stopped
for 2 min before a final 2 min of mixing was performed. After
casting the mixture was placed in the molds in two lifts, com-
pacted on a vibrating table, and moist cured for 24 h. For each
mixture, 100⫻100⫻400 mm prisms and 100 mm cubes were cast.
To study the pore structure and change in Ca共OH) 2 content, ad-
ditional specimens of 40⫻40⫻160 mm were prepared using the
mortar collected from the wet sieving of concrete. All of the
specimens were demolded after 24 h and cured in lime-saturated
water at 30⫾2°C to prevent possible leaching of Ca共OH) 2 from
these specimens.
Accelerated Carbonation Test
After a scheduled period of water curing, the concrete specimens
were stored in an ambient environment 共temperature of 30⫾2°C
and relative humidity of 75⫾5%兲 for a minimum of two weeks to
stabilize the internal relative humidity of concrete for different

Table 2. Mixture Proportions of Concrete with and without Mineral Admixtures

Mineral Admixtures Mixture Proportions 共kg/m3兲
Blaine Replacement
Mixture fineness percentage GGBS,
number Type 共cm2/g兲 共weight %兲 w/b OPC FA, or SF Water Aggregate
N30 — — 0 0.3 500 — 146 1,765
N40 — — 0 0.4 400 — 157 1,823
N50 — — 0 0.5 350 — 172 1,826
N60 — — 0 0.6 300 — 178 1,855
B430 GGBS 4,500 30 0.5 245 105 172 1,819
B450 GGBS 4,500 50 0.5 175 175 172 1,813
B465 GGBS 4,500 65 0.5 123 227 172 1,810
B665 GGBS 6,000 65 0.5 123 227 172 1,810
B865 GGBS 8,000 65 0.5 123 227 172 1,810
FA15 FA 9.2%a 15 0.5 298 52 172 1,817
FA30 FA 9.2%a 30 0.5 245 105 172 1,816
SF5 SF 250,000 5 0.5 333 17 172 1,820
SF10 SF 250,000 10 0.5 315 35 172 1,814
TBC GGBS/SF 4,500/250,000 55/10 0.5 123 204/23 172 1,810
a
Using sieve analysis 共9.2% retained on 45 ␮m sieve兲.

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Fig. 1. Accelerated carbonation test chamber: 共a兲 photograph; 共b兲 schematic diagram

mixtures. This will help to reduce the variation in the internal
relative humidity between the concrete samples before subjecting
them to accelerated carbonation tests, and will minimize its effect
on the carbonation depth results. The specimens were then trans-
ferred to a specially designed and fabricated accelerated carbon-
ation test chamber 关Fig. 1共a兲兴 with CO2 , temperature, and humid-
ity control. A schematic diagram showing the dimensions of the
test chamber 共side and front views兲 is presented in Fig. 1共b兲. The
CO2 supply ranged from 0 to 10% by volume; the temperature,
from 25 to 80°C; and the relative humidity, from 30 to 95%. Due
to the corrosive test environment, the internal and external walls
of the chamber were made from stainless steel. On both sides of
the chamber, there were two racks, each having eight adjustable
heavy-duty shelves made of pipes with rollers 关Fig. 1共b兲兴 that
allowed the exposure of all surfaces of the concrete prisms 共100
⫻100⫻400 mm兲 to the test environment.
In this study, the environment in the chamber had a CO2 con-
centration of 6.5⫾0.2%; it was set at a temperature of 30⫾0.5°C,
which simulates the local average ambient temperature. In con-
formity with the recommendations by RILEM 共‘‘Measurement’’
1987兲, the relative humidity within the chamber was maintained
at 65⫾1% to accelerate the carbonation of concrete.
Carbonation Depth
The carbonation depth of the specimens was monitored every two
weeks in the first two months, and thereafter once a month up to
12 months. After a certain exposure period, the specimens were
split and freshly broken surfaces were sprayed with a standard

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J. Mater. Civ. Eng., 2003, 15(2): 134-143

 exposure period. A similar trend was also observed 共Sulapha
2000兲 for all of the other mixtures in Table 2.

Carbonation Coefficient
The X versus 冑t data 关e.g., in Fig. 2共b兲 for 100% OPC concrete兴
were fitted to various forms of equations, such as those repre-
sented by linear, square root, exponential, and logarithmic func-
tions. It is found that the relationship in Eq. 共6兲 gave the best
correlation coefficient 共R兲. The values of C, a, and R 2 for all of
the mixtures investigated are tabulated in Table 3
X⫽C 冑t⫹a (6)
where X⫽carbonation depth 共mm兲; C⫽carbonation coefficient
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共mm/冑weeks兲; t⫽exposure period to accelerated carbonation

共weeks兲; and a⫽empirical constant 共mm兲. The formulation in Eq.
共6兲 had been agreed upon by numerous researchers 共Hamada
1969; Tuutti 1982; Richardson 1988兲, especially when the carbon-
ation tests were performed under controlled indoor conditions.
The values of C and a in Eq. 共6兲 were calculated for different
concrete mixtures by linear regression based on the experimental
X versus 冑 t data. In this study, the value of a for all mixtures was
small compared to the measured carbonation depth X; therefore, it
is discarded. This implies that Eq. 共6兲 can be simplified to X
⫽C 冑t, which is similar to Fick’s first law of diffusion that de-
scribes the carbonation depth 共Kropp 1995兲. Since C is inversely
Fig. 2. Effect of water-binder ratio on carbonation depth plotted proportional to the ability of concrete to resist the diffusion of
against: 共a兲 exposure period; 共b兲 square root of exposure period CO2 , it becomes an important single parameter to directly com-
pare and assess the resistance of different mixtures to carbonation
in this study.
solution of 1% phenolphthalein in 70% ethyl alcohol 共‘‘Measure-
ment’’ 1987兲. In the noncarbonated region with pH values above
9.2, the indicator turned purple-red; in the carbonated portion Mercury Intrusion Porosimetry
with pH less than 9.2, the solution remained colorless. The dis-
Mercury intrusion porosimetry 共MIP兲 was performed to study the
tance between the color change boundary and the concrete surface
pore structure of concrete. After curing in water for 28 days,
was measured as the carbonation depth. The depths at the corners
fragmented samples from mortar specimens 共wet sieved from
of each sample and behind the coarse aggregate were excluded.
concrete兲 were immersed in acetone to stop further hydration,
Eight readings were recorded from the two side faces of a
oven dried at 105⫾1°C for 24 h, and stored in a vacuum desic-
sample at 20 mm intervals. The average of these readings from
cator until testing. In the present study, specimens were oven
two samples was taken to represent the carbonation depth 共X兲 of
dried at 105⫾1°C to remove all of the evaporable water from the
the specimen after a certain exposure period to accelerated car-
pores to allow the complete intrusion of mercury during the MIP
bonation 共t兲. For instance, the X versus t data for 100% OPC
test. Complete drying of the samples was required to get results
concrete of different w/b are plotted in Fig. 2共a兲, indicating that a
without error in the MIP test. Many researchers have used this
parabolic relationship exists between the carbonation depth and
method to investigate the pore structure of concrete 共Abdel-Jawad
and Hansen 1989; Chan et al. 2000; Collins and Sanjayan 2000;
Table 3. Regression Parameters for Different Mixtures Dongxue et al. 2000兲. No significant difference was observed in
the pore volume obtained by the nitrogen desorption and adsorp-
Regression Parameters
Mixture tion method and MIP method, suggesting that the pore structure
number C a R R2 was virtually unaffected by the drying method 共Abdel-Jawad and
N30 0 — — — Hansen 1989兲. The maximum applied pressure was 200 MPa; the
N40 0.782 0.323 0.840 0.706 contact angle and surface tension of the mercury used were 117°
N50 2.624 0.673 0.993 0.986
and 0.480 N/m, respectively.
N60 4.829 0.393 0.993 0.986
B430 2.469 0.778 0.985 0.970 Thermogravimetric Analysis
B450 2.932 0.624 0.993 0.986
B465 3.248 0.827 0.994 0.988
After 28 days of water curing, the mortar specimens 共wet sieved
from concrete兲 were crushed into fragmented samples and im-
B665 2.068 0.664 0.995 0.990
mersed in acetone. To limit the absorption of CO2 , the samples
B865 1.678 0.430 0.995 0.990
were stored in tightly stoppered glass containers and all handling
FA15 2.667 0.394 0.995 0.990
in the air was carried out as quickly as possible. Subsequently, the
FA30 3.105 0.792 0.993 0.986
samples were oven dried at 105⫾1°C and kept in a vacuum des-
SF5 2.325 0.355 0.998 0.996
iccator. Prior to testing, the fragmented samples were further
SF10 2.534 0.421 0.997 0.994
crushed into powder with a mortar and pestle. The powdered
TBC 2.918 0.529 0.995 0.990
samples were then passed through a 150-␮m sieve and used for

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J. Mater. Civ. Eng., 2003, 15(2): 134-143

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Fig. 3. Effect of: 共a兲 water-binder ratio; 共b兲 GGBS, FA, or SF replacement; 共c兲 GGBS fineness; 共d兲 ternary blends on carbonation coefficient
thermogravimetric analysis 共TGA兲. The height of the endothermic
peak at about 400°C 关that corresponds to the dehydroxylation of
Ca共OH) 2 ] was considered for comparing the amount of Ca共OH) 2
present in different mixtures. The peaks at 0–100°C 共indicating
the evaporable water content兲 were not included in the compari-
son.
Compressive Strength
Compressive strength tests were carried out to correlate the car-
bonation coefficient of concrete to the corresponding compressive
strength at the end of water curing and before exposure to accel-
erated carbonation. Immediately after 1, 3, 7, or 28 days of cur-
ing, 100 mm cubes were tested in accordance with Singapore
Standard 78, Part A16 共Singapore 1987兲. The average compres-
sive strength of three cubes cured at a certain age was then deter-
mined for each concrete mixture.
Results and Discussion
Effect of Water-binder Ratio
Fig. 3共a兲 shows the effect of w/b on the carbonation rate 关based
on the carbonation coefficient calculated using Eq. 共6兲兴 of 100%
OPC concrete water cured for 28 days. The carbonation coeffi-
cient of N60 共concrete with w/b⫽0.60, C⫽4.83) was found to be
the highest, followed by N50 共concrete with w/b⫽0.5, C
⫽2.62), N40 共concrete with w/b⫽0.40, C⫽0.73), and N30 共con-
crete with w/b⫽0.30, C⫽0). As can be seen in Figs. 2共a and b兲,
N30 showed excellent resistance to carbonation without any sig-
nificant carbonation depth, even after nearly one year of exposure
to accelerated carbonation.
In Fig. 4共a兲, it is observed that a lower w/b generally led to a
decrease in cumulative pore volume and amount of pores, espe-
cially in the larger pore size range of more than 100 Å. For
example, N30 (w/b⫽0.30) with the lowest cumulative pore vol-
ume and finest pore size distribution 共only one peak of differential
138 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MARCH/APRIL 2003
J. Mater. Civ. Eng., 2003, 15(2): 134-143
pore volume at a smaller pore radius of about 40 Å兲 showed
superior resistance against carbonation with no measurable car-
bonation coefficient. Thus, it can be deduced that concrete of a
lower w/b had better resistance against the diffusion of CO2 ,
possibly due to the denser pore structure of these mixtures. Simi-
lar findings in relation to the effect of w/b on carbonation have
also been reported in the literature 共Houst and Wittmann 1994;
Wee et al. 1999兲.
The comparison of the endothermic peak for Ca共OH) 2 at about
400°C, as indicated by the first derivative of TGA curves 共e.g.,
DrN40 for mixture N40兲 in Fig. 5共a兲, shows that the amount of
Ca共OH) 2 increased as the w/b increased. This may have been due
to the relatively greater quantity of mixing water available for
cement hydration in mixtures with higher w/b, or it may have
been due to a large size and a greater number of pores available
for Ca共OH) 2 to grow.
Effect of Mineral Admixtures
The effect of mineral admixtures on the carbonation coefficient of
concrete having w/b of 0.5 and with 28-day water curing is pre-
sented in Figs. 3共b–d兲. It can be seen in Fig. 3共b兲 that a higher
replacement percentage of GGBS 共4,500 cm2/g fineness兲, FA, and
SF led to a greater carbonation coefficient, which is consistent
with the trend observed by Osborne 共1999兲, Ohga and Nagataki
共1989兲, and Papadakis 共2000兲, respectively. For GGBS replace-
ment of 65%, increasing the fineness of GGBS caused a reduction
in the carbonation coefficient, as shown in Fig. 3共c兲.
Among the blended cement concrete in Fig. 3共d兲, the carbon-
ation coefficient was the lowest for SF10, followed by N50, ter-
nary blends 共TBC兲, and B465. This suggests that the use of
GGBS and SF in TBC was effective in reducing the carbonation
coefficient compared to B465, but was not as effective as SF
addition by itself 共in SF10兲.
Fig. 4共b兲 shows the pore size distributions of concrete with and
without GGBS. For all replacement levels of GGBS except 30%,
the cumulative pore volume was smaller than that of 100% OPC
concrete. The differential pore volume curves indicate that pore
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Fig. 4. Effect of: 共a兲 water-binder ratio; 共b兲 GGBS replacement; 共c兲 GGBS fineness; 共d兲 FA replacement; 共e兲 SF replacement; 共f兲 ternary blends
on cumulative and differential pore volumes 共⫺c⫽cumulative; ⫺d⫽differential兲
size modification due to the pozzolanic reaction of GGBS with a
high replacement level of 65% 共B465兲 had the smallest pore vol-
ume and hence the densest pore structure, especially in the pore
size range of less than 200 Å. It is also observed that a higher
GGBS fineness gave rise to a denser pore structure, as indicated
by a decrease in cumulative pore volume and a shift in the peak of
the differential pore volume toward a smaller pore radius in Fig.
4共c兲. Although the pore structure of B450 and B465 was denser
than that of N50, the carbonation coefficients of these GGBS
mixtures were higher than that of the plain concrete. This sug-
gests that pore structure is not the only parameter that controls the
rate of carbonation—but also the amount of Ca共OH) 2 present
within the hydrated cement paste.
To determine the Ca共OH) 2 content in concrete containing
GGBS, FA, SF, and GGBS/SF, TGA was performed; the results
are presented in Figs. 5共b–f兲. Fig. 5共b兲 shows that the amount of
Ca共OH) 2 decreased with increasing replacement percentage of
OPC by GGBS. The height of the Ca共OH) 2 peak at about 400°C
for GGBS mixtures 共as indicated by DrB430, DrB450, and
DrB465兲 was significantly reduced due to the pozzolanic reaction.
These results may well explain the higher carbonation rate with
increasing GGBS replacement level for concrete containing low
fineness GGBS of 4,500 cm2/g in Fig. 3共b兲. Although the amount
of Ca共OH) 2 decreased with increasing fineness of GGBS 关Fig.
5共c兲兴, the decrease in pore volume and finer pore size 关Fig. 4共c兲兴
appeared to counteract the effect of the reduced Ca共OH) 2 content;
hence, the resistance against carbonation was not reduced, but
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J. Mater. Civ. Eng., 2003, 15(2): 134-143
increased, as can be seen in Fig. 3共c兲. This suggests that one way
to reduce the rate of carbonation in GGBS concrete is to increase
the fineness of GGBS.
For specimens containing FA and SF, the cumulative pore vol-
umes were greater than those of 100% OPC concrete 共N50兲, as
depicted in Figs. 4共d and e兲, respectively. However, silica fume
concrete 共SF5 and SF10兲 in Fig. 4共e兲 showed excellent pore modi-
fication by shifting the peak of the differential pore volume sig-
nificantly toward a smaller pore radius. This indicates that after
28 days of water curing, though the cumulative pore volumes of
SF5 and SF10 were slightly higher than that of N50, the pore
structure was denser. Only FA concrete 共FA15 and FA30兲 in Fig.
4共d兲 showed a less dense structure than 100% OPC concrete.
The comparison of TBC with N50, B465, and SF10 in Fig.
4共f兲 indicates that the cumulative pore volume of TBC was the
smallest and that of N50 was the greatest for pore radii larger than
50 Å. It is also found that TBC had the lowest differential pore
volume in the range with pore radii of about 200 Å. This suggests
that the use of a ternary blend 共TBC兲 containing GGBS and SF
was highly effective in densifying the pore structure of concrete.
The Ca共OH) 2 peak of concrete with 15% FA replacement,
marked as DrFA15 in Fig. 5共d兲, had nearly the same height as the
control mixture 共DrN50兲. However, for 30% FA concrete
共DrFA30兲, the reduction in the height of the Ca共OH) 2 peak was
significant. These results correlated well with the rise in carbon-
ation coefficient as the FA content increased 关Fig. 3共b兲兴. It is also
observed from Fig. 4共d兲 that even after 28 days of water curing,
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Fig. 5. Effect of: 共a兲 water-binder ratio; 共b兲 GGBS replacement; 共c兲 GGBS fineness; 共d兲 FA replacement; 共e兲 SF replacement; 共f兲 ternary blends
on calcium hydroxide content

the pore structure of FA concrete was not as dense as that of plain able to react with CO2 is lower, for two reasons. First, less CaO is
OPC concrete. This suggests that changes in pore structure were added to the concrete. Second, some of the Ca共OH) 2 reacts with
not adequate in FA concrete to counteract the reduction in added GGBS, FA, or SF. If the pore structure modification does
Ca共OH) 2 content, and hence the carbonation rate increased. The not govern over the reduction in Ca共OH) 2 , the carbonation may
morphology of hydrated products formed on the surface of FA proceed faster due to the less amount of carbonatable materials
particles in mortar samples after 90 days of curing was studied by available per unit area for CO2 to react with. This explains why
Lin and Fu 共1987兲. They concluded that samples with FA had a carbonation tends to proceed faster in concrete containing mineral
low free lime content and the greater amount of hydrated products
formed after the pozzolanic reaction were noncrystalline low al-
kaline C-S-H with a large specific surface area; hence, these
samples were easily carbonated.
Fig. 5共e兲 depicts the Ca共OH) 2 peak for SF concrete after 28
days of water curing. As compared to GGBS or FA concrete, the
reduction in Ca共OH) 2 was much smaller for SF concrete due to
the lower replacement percentages of 5–10%. As a result, con-
crete containing SF generally showed better carbonation resis-
tance than concrete with GGBS or FA, as observed in Fig. 3共b兲.
This could be explained by the dominating effect of pore structure
modification in Fig. 4共e兲 over the influence of the reduction in
Ca共OH) 2 content in Fig. 5共e兲.
The presence of Ca共OH) 2 results from the hydration reaction
of C2 S and C3 S, which are the main components of cement. In
Fig. 6. Effect of curing age on carbonation coefficient
the presence of GGBS, FA, or SF, the amount of Ca共OH) 2 avail-

140 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MARCH/APRIL 2003

J. Mater. Civ. Eng., 2003, 15(2): 134-143


Fig. 7. Effect of curing age on cumulative and differential pore
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volumes
admixtures. Due to the slower pozzolanic reaction, porosity can
be expected to be higher during the initial stage, thus allowing
more rapid diffusion of CO2 共Montemor et al. 1999兲.
Effect of Curing Age in Water
Fig. 6 shows the curves of carbonation coefficient versus curing
age for concrete with and without mineral admixtures. It can be
seen that a longer curing age generally resulted in a lower car-
bonation coefficient. For N50, the carbonation coefficient de-
creased with curing age within the first seven days. With more
than seven days of curing, the carbonation coefficient leveled off
such that the improvement in carbonation resistance with curing
age became insignificant. In the case of concrete containing
GGBS 共B465兲, FA 共FA30兲, and SF 共SF10兲, the carbonation coef-
ficient continued to decrease even after 28 days of curing. These
results suggest that a curing duration of at least seven days is
necessary to improve the carbonation resistance of plain OPC
concrete, whereas a prolonged curing age is advisable for GGBS,
FA, and SF concrete.
The development of pore size distributions for N50 with in-
creasing curing ages of 1, 3, 7, and 28 days is shown in Fig. 7.
For a longer curing age, a reduction in cumulative pore volume
and a shift in the differential pore volume curves toward smaller
pore radii were observed due to the progress of cement hydration.
Hence, it can be seen that an increase in curing age generally led
to a denser pore structure, and thereby better resistance against
the diffusion of CO2 . Fig. 7 also reveals that regardless of the
curing age, the differential pore size distributions exhibited one
maximum at smaller pores of about 40 Å and the second at larger
Fig. 8. Relationship between carbonation coefficient and
compressive strength
JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MARCH/APRIL 2003 / 141
J. Mater. Civ. Eng., 2003, 15(2): 134-143
pores in the range of 150– 400 Å. The peaks corresponding to the
larger pores decreased with prolonged curing of up to 28 days.
Relationship between Carbonation Coefficient and
Compressive Strength
Fig. 8 shows the relationship between the carbonation coefficient
共C兲 of concrete specimens and their corresponding compressive
strength 共S兲 before exposure to accelerated carbonation 共which
was just after 1, 3, 7, or 28 days of water curing兲. Irrespective of
w/b, mineral admixtures, and curing age, the value of C in-
creased with a decrease in S, with the line of best fit represented
by a linear relationship
C⫽⫺0.0831S⫹7.5127 (7)
where C⫽carbonation coefficient 共mm/冑weeks兲; and
S⫽compressive strength 共MPa兲.
The calculated correlation coefficient R is 0.949 共or R 2
⫽0.9005). This indicates that the C and S data are well corre-
lated, and thus compressive strength may serve as a good indica-
tor for the carbonation rate of concrete with and without mineral
admixtures.
Practical Applications
The rate of carbonation is usually slow under natural exposure
conditions due to the low CO2 concentration in the atmosphere.
Hence, the accelerated carbonation test methodology and equip-
ment developed in this study enable the carbonation resistance of
concrete to be assessed within a reasonably short time 关e.g., as
early as two weeks in Fig. 2共a兲兴.
In comparison to the plain OPC mixture, concrete containing
mineral admixtures 共except for GGBS with higher fineness values
of 6,000 and 8,000 cm2/g and SF兲 was found to be less resistant to
carbonation. Hence, adequate curing must be emphasized, as it is
deduced from this study that increasing the curing age in water to
28 days led to an improvement in the resistance of GGBS, FA,
and SF concrete to carbonation. For plain concrete, water curing
needs to be extended to at least seven days.
The results from the present work will also be potentially use-
ful in the development and formulation of mixtures based on
different w/b, replacement level, and fineness of mineral admix-
tures, as well as in the prediction of the extent of carbonation for
in situ concrete. The carbonation coefficients obtained, together
with their correlation with compressive strength data, have impor-
tant design implications on the selection of a combination of con-
crete grades and concrete cover that can protect the reinforcement
from carbonation-induced depassivation during the design life of
a concrete structure or element.
Conclusions
Based on the mixture proportions, cementitious materials, and test
conditions adopted in this study, the following conclusions can be
drawn:
• A lower w/b 共in the range of 0.3–0.6兲 and a prolonged curing
age in water 共from one to 28 days兲 generally led to a slower
rate of carbonation, possibly due to pore structure densifica-
tion, as indicated by a decrease in cumulative and differential
pore volumes.
• To improve the carbonation resistance of concrete, sufficient
water curing of at least seven days is necessary for plain OPC
 concrete, whereas an extended curing age in water is required
for GGBS, FA, and SF concrete.
• The carbonation rate of low fineness GGBS 共4,500 cm2/g兲 and
FA concrete increased with an increase in OPC replacement
level. In the case of SF, both replacement percentages 共5 and
10%兲 led to a lower carbonation rate compared to that of OPC.
However, 5% replacement showed a better performance than
10% replacement.
• Concrete containing low fineness GGBS 共4,500 cm2/g兲 and FA
exhibited higher rates of carbonation than plain OPC concrete.
The reduction in Ca共OH) 2 content seemed to have more influ-
ence over pore refinement, and hence led to faster rates of
carbonation.
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• For concrete incorporating GGBS of higher fineness 共6,000
and 8,000 cm2/g兲 and silica fume, the carbonation rates were
lower than that of plain OPC concrete. The pore modification,
being more dominant than the change in Ca共OH) 2 content,
appeared to control the carbonation rate.
• The ternary blended concrete containing 35% OPC, 55%
GGBS, and 10% SF showed a higher carbonation rate than the
plain OPC mixture and 10% SF concrete. Compared to 65%
GGBS concrete, the ternary blended concrete exhibited a
lower rate of carbonation.
• The Ca共OH) 2 content of concrete decreased with an increased
OPC replacement percentage by GGBS 共30– 65%兲, FA 共15–
30%兲, or SF 共5–10%兲, due to the pozzolanic reaction. As com-
pared to GGBS or FA concrete, the reduction in Ca共OH) 2 was
much smaller for SF concrete due to its lower replacement
levels. Hence, SF concrete generally showed higher carbon-
ation resistance, since pore refinement was likely to dominate
over the change in Ca共OH) 2 content.
• The carbonation coefficient increased with a decrease in com-
pressive strength, as described by a linear relationship. The
good correlation between these parameters demonstrated that
in addition to the carbonation coefficient, compressive strength
served as a good indicator for the carbonation rate of concrete
with and without mineral admixtures.
Acknowledgments
The financial support 共under Project GR6171兲 and supply of ce-
mentitious materials by Blue Circle Materials Singapore Pte Ltd.
as well as the NUS Research Scholarship awarded by the Na-
tional University of Singapore to the first writer are gratefully
acknowledged. The assistance given by Lim Huay Bak and the
technical staff of the Concrete Technology Laboratory, Depart-
ment of Civil Engineering, the National University of Singapore
is also deeply appreciated.
Notation
The following symbols are used in this paper:
a ⫽ empirical constant 共mm兲;
C ⫽ carbonation coefficient 共mm/冑weeks兲;
R ⫽ correlation coefficient;
S ⫽ compressive strength at end of water curing and
before exposure to accelerated carbonation 共MPa兲;
t ⫽ exposure period to accelerated carbonation 共weeks兲;
and
X ⫽ carbonation depth 共mm兲.
142 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING © ASCE / MARCH/APRIL 2003
J. Mater. Civ. Eng., 2003, 15(2): 134-143
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