Cement and Concrete Composites 126 (2022) 104329

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Cement and Concrete Composites

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Carbonation model for concretes with fly ash, slag, and limestone calcined
clay - using accelerated and five - year natural exposure data
Sundar Rathnarajan, B.S. Dhanya, Radhakrishna G. Pillai *, Ravindra Gettu, Manu Santhanam
Department of Civil Engineering, Indian Institute of Technology Madras, Chennai, India

A R T I C L E I N F O A B S T R A C T

Keywords: Supplementary cementitious materials (SCMs) can be used in concrete to enhance sustainability and reduce the
Fly ash concrete industry’s carbon footprint. However, some negative perceptions about their long-term carbonation
Slag resistance are obstacles for large-scale implementation of such concretes. This study evaluated the carbonation
Limestone calcined clay
resistance of 34 concretes (with Ordinary Portland Cement, fly ash, blast furnace slag, and limestone calcined
Concrete
Carbonation
clay) in natural tropical exposure conditions (Open and Sheltered) for 5 years and in accelerated exposure
Service life conditions (1 and 3% CO2) for 112 days. Using these data and the square root of time function, the carbonation
coefficients (KCO2, natl and KCO2, accl) of these concretes were estimated and a good correlation between them
could not be observed. Hence, a more generic model (named as “A-to-N model”) to estimate the KCO2, natl using
the KCO2, accl, CO2 concentration, and mixture proportion of concrete was developed, for which the mean ab­
solute percent error is about 12% (reasonable accuracy). Using the A-to-N model, the carbonation depth at 50
years was estimated for various concretes. SCM concretes with low water-binder ratio and optimal binder content
showed high resistance against carbonation at later ages; such information along with the target cover depth
must be used while selecting materials for concrete design. Based on the model developed, a relatively simple
‘service life design chart’ was developed. This chart can be used by engineers to set the target KCO2, natl or KCO2,
accl, and select the cover depth and binder type to provide the target service life (i.e., corrosion initiation time).
This paper clearly shows that SCMs can be used to design concretes with comparable long-term carbonation
depth as OPC concretes.

SCMs is still debatable [8]. Moreover, studies related to long-term car­

1. Introduction
1.1. Carbonation-induced corrosion
A couple of decades ago, chloride ingress and subsequent corrosion
was considered as the primary threat to the service life of reinforced
concrete structures. Recently, with the increase in the use of blended
cements with high volume of clinker substitution, the risk of carbonation
and subsequent corrosion of reinforced concrete systems has gained
more attention [1–3]. Fig. 1 shows the trend in the number of publica­
tions in the areas of these degradation mechanisms over the last twenty
years. The need to produce low carbon-footprint binders necessitates the
use of supplementary cementitious materials (SCMs) in cement pro­
duction [4]. The partial substitution of clinker with SCMs at a higher
replacement level is reported to improve the ultimate strength as well as
the durability properties of concretes in terms of chloride and sulphate
resistance [5–7]. However, the carbonation resistance of concretes with
bon dioxide exposure of concretes, especially in the natural environ­
ment, are limited. This paper fills the gap in this area to some extent.
1.2. Influence of SCMs on carbonation
Binder type, replacement level of SCMs, binder content, and water-
to-binder ratio can influence the carbonation resistance of concrete
[9–11]. The use of fly ash and slag indicate a reduction in the OPC
clinker content; this can lead to a reduction in carbonation resistance
with increasing replacement level [12,13]. In addition to clinker
reduction, the pozzolanic reactions in concretes with SCMs consume a
significant amount of the available Ca(OH)2 and can reduce the upper
limit of the initial pH of hardened concrete to ≈12.5, as compared to
≈13.5 in OPC [14]. Among the SCMs, slag can result in higher carbon­
ation resistance than fly ash due to the presence of higher CaO buffer in
the former [15,16]. However, most of the studies [17–20] compared the
carbonation in concretes with similar binder content and

* Corresponding author.
E-mail address: pillai@civil.iitm.ac.in (R.G. Pillai).

https://doi.org/10.1016/j.cemconcomp.2021.104329
Received 16 March 2021; Received in revised form 7 September 2021; Accepted 2 November 2021
Available online 7 November 2021
0958-9465/© 2021 Elsevier Ltd. All rights reserved.
S. Rathnarajan et al.
List of symbols and abbreviations
Aw Tropical wet and dry climate
CCO2, accl Accelerated CO2 concentration
CCO2, natl Natural CO2 concentration
cd Cover depth
Δxd Change in carbonation depth (mm)
FaF Class F fly ash
FaC Class C fly ash
KCO2, accl Accelerated carbonation coefficient (mm/year0.5)
KCO2, accl Natural carbonation coefficient (mm/year0.5)
LC3 Limestone calcined clay cement
Fig. 1. Exponential increase in the number of publications in the field of
durability of concrete with the popularity of SCMs (Source: Web of Science).
water-to-binder ratio without considering the type of binder. The com­
parison between the carbonation in concretes with varying CaO buffer
undermines the long-term carbonation resistance of the concrete mixes
with similar strength grade. Also, most of the conclusions from the
literature are based on short-term accelerated tests in the laboratory,
which might not correspond well with the long-term carbonation
resistance of concretes with SCMs. Moreover, limited data [21–23] is
available on the long-term natural carbonation in SCM-based concretes
all over the world. Thus, further research on carbonation rate and
corrosion initiation mechanisms is needed to quantify the long-term
performance of steel at a particular depth in such SCM-based concretes.
1.3. Influence of climatic conditions on carbonation
The carbonation rate can vary between the natural ‘Open’ and
‘Sheltered’ conditions due to role played by the frequency of rain and the
degree of saturation of the macropores/capillary pores under the action
of alternate wet and dry exposure to moisture [24]. To be precise, the
internal relative humidity, temperature, and moisture levels can govern
the diffusion of CO2 and chemical reactions associated with carbonation.
In Open exposure, the macropores in concrete can get saturated during
seasonal rainfall, which in turn can reduce the rate of carbonation.
Sheltered exposure and an ambient relative humidity of 65–80% can
lead to partially-saturated pores and can accelerate carbonation
[24–26]. The influence of climate on carbonation of the concrete
structures located in Open exposure was found to be controlled by the
number of rainy days per year in addition to the prevailing relative
humidity and temperature in the region [27]. Literature suggests that
any day with more than 2.5 mm precipitation can be considered as a
rainy day to sufficiently wet the concrete and affect carbonation
2
Cement and Concrete Composites 126 (2022) 104329
MAPE Mean absolute percent error
OPC Ordinary Portland cement
RL Replacement level of SCMs
SCMs Supplementary cementitious materials
SgC Coarser slag
SgF Finer slag
TBC Total binder content (kg/m3)
tsl Target service life
wb Water-to-binder ratio
xd Carbonation depth (mm)
xd, ty Carbonation depth at ‘t’ years (mm)
xd, td Carbonation depth at ‘t’ days (mm)
progress [28].
As per the Koppen-Geiger climate classification, Chennai, India is an
‘urban industrial megacity’ with a tropical wet and dry climate (Aw). In
a broader perspective, tropical wet and dry climate prevails in many
developed and developing cities along the shaded region, as shown in
Fig. 2. The natural carbonation depth (xd, natl) observed in tropical wet
and dry climate are about two to three times more than that observed in
temperate climate with less wet period [29].
1.4. Accelerated and natural carbonation in various climates
Table 1 summarizes the models from literature on relationships be­
tween the KCO2, natl from KCO2, accl based on various natural and accel­
erated carbonation tests and modelling approaches [18,30–33]. One
approach is to obtain a linear equation between KCO2, natl and KCO2, accl
calculated using the square root of time model [18,31,32]. In another
approach, carbonation depth xd, accl observed at 7 days of exposure to
4% CO2 concentration was equated to the xd, natl observed in 1–1.5 years
of natural exposure, for different binder systems [34,35]. A third
approach is to obtain the ratio between KCO2, natl and KCO2, accl, the latter
being obtained using experimental data from accelerated tests and then
relating it to the former using Fick’s 1st law of diffusion, as shown in
Equation (1) [33].
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ √̅̅̅̅̅̅̅̅̅
KCO2,natl CCO2, natl 0.03
= √̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅ = √̅̅̅ = 0.1; ​ for ​ CCO2, accl = 3% (1)
KCO2,accl CCO2, accl 3
However, the lack of uniformity in the procedures and conditions of
accelerated carbonation tests and the variations in relative humidity,
temperature, and precipitation days in various natural carbonation tests
pose difficulties in the general adaptation of the equations in Table 1
[29,36]. Also, the experiments done at higher than 3% CO2 led to
different physico-chemical nature of the carbonated phases than that
observed in natural carbonation tests [37–39]. Hence, the validity of
results from tests conducted at higher than 3% CO2 concentration is
debatable [37,39]. The models to predict KCO2, natl using KCO2, accl should
consider variations in the CO2 concentrations in accelerated test and
could be calibrated with long-term natural carbonation data (say, at
least a couple of years). Furthermore, the available models are deficient
in terms of the size of the database and ability to incorporate the various
climatic conditions across the world. Moreover, these differences in
carbonation progress in concretes in different climate conditions in­
dicates the need for different models to convert accelerated carbonation
coefficient (KCO2, accl) to natural carbonation coefficient (KCO2, natl) for
tropical and temperate climates (say, A-to-N models).
The remainder of this paper presents the experimental carbonation
depth results from both accelerated and natural carbonation tests for
different periods. The KCO2 values were calculated in both natural and
accelerated carbonation using Tuutti’s square root of time function. A
regression model to predict the KCO2, natl of various concretes in tropical
S. Rathnarajan et al. Cement and Concrete Composites 126 (2022) 104329

Fig. 2. World map showing regions with tropical-monsoon climate conditions.

provided based on KCO2, natl or KCO2, accl was developed. This design
Table 1
chart is expected to enable practicing engineers to choose necessary
Relationships between natural and accelerated carbonation in various climate
cover depth and binder type to achieve target service life (tsl).
conditions.
Equation [Reference] Exposure conditions
3. Materials and methodology
0.56
C √̅̅ • Natl: CO2% - 0.03–0.06; RH -
xd,natl,t = 0.22 xd, accl t; where, xd,
RH 72–83%; Climate - Tropical This paper presents the development of a model to estimate KCO2, natl
natl, t is the natural carbonation depth (in (Bangkok); Duration - 2 years
mm) at age, t (in months), xd, accl is the
using KCO2, accl. For this, accelerated and natural carbonation tests were
• Accl: CO2% - 4; RH - 55%; Duration -
accelerated carbonation depth (in mm) 112 days conducted on 34 concretes with different SCMs, binder composition, and
at 28 days, and C is the natural CO2 concrete mixture proportions. The nomenclature, test variables, and
concentration (in ppm) [30] mixture proportions, and properties of various concretes are shown in
KCO2, natl = 0.2 KCO2, accl [31] • Natl: CO2%:0.03% CO2; Temperate Fig. 3 and Table 3. This section describes the materials used, the
climate – Spain; Duration: 10 months carbonation tests, and the adopted statistical modeling approach.
• Accl: 5% CO2; Duration 40 days

KCO2, natl, Sheltered = 0.21 KCO2, accl • Natl: 0.03% CO2; Temperate climate 3.1. Materials used
KCO2, natl, Open = 0.083 KCO2, accl [18] – Switzerland; Duration: 2 years
• Accl: 4% CO2 and RH: 57%;
Duration: 126 days Ordinary Portland Cement (OPC) of 53 Grade, procured from two
sources (CmA, CmP) and conforming to IS 269 (2015) [40] and ASTM
KCO2, natl = 0.45 KCO2, accl [32] • Natl: 0.02–0.09% CO2; RH: 18–60%;
Tropical climate – Brazil; Duration:
C150 Type I cement [41], was used as the primary binder in this study.
150 days The four SCMs used for partial substitution of OPC were coarser slag
• Accl: 4% CO2 and RH: 65%; (SgC), finer slag (SgF), Class C fly ash (FaC), and Class F fly ash (FaF).
Duration: 150 days The coarser and finer slag (SgC and SgF, respectively) used in the study
KCO2, natl = 0.1 KCO2, accl [33] • Accl: 3% CO2 and RH: 65%; are blast furnace slag obtained from steel manufacturing industry. Also,
Duration: 150 days the limestone calcined clay cement (LC3) produced as a ternary blend of
clinker (50%), limestone (15%), and calcined clay (30%) was used in
this study [42]. Table 2 provides the oxide compositions and physical
wet and dry climate using accelerated test results is developed. Subse­
properties of OPC, four SCMs, and LC3. The coarse aggregates were
quently, a design chart to determine the required cover depth so that
crushed granite with maximum particle sizes of 10 and 20 mm. The
various concretes in the Sheltered condition can achieve the target
specific gravity values of fine river sand and crushed granite coarse
service life is developed. Following this, the limitations of this work and
aggregates were found to be 2.53 and 2.76 at saturated surface dry (SSD)
conclusions made are presented.
condition, and the corresponding water absorption capacities were 0.43
and 0.71%, respectively. All the concretes were designed to achieve a
2. Research significance
slump between 80 and 150 mm. For concretes with LC3, poly­
carboxylate ether (PCE) based high-range water-reducing admixture
With this study, the negative perception on carbonation resistance of
was used, whereas, for other concretes sulphonated naphthalene form­
concretes with SCMs based on accelerated tests and early-age (say, 1 or 2
aldehyde (SNF) based high-range water-reducing admixture was used.
years) natural carbonation data can be countered with the carbonation
Tap water available in the laboratory was used for the preparation of
depth data collected for about 5 years of natural carbonation exposure.
concretes.
The study demonstrated the improvement in later-age carbonation
resistance in concretes with SCMs compared to the OPC concretes. An
Accelerated-to-Natural model (A-to-N model) to estimate KCO2, natl from 3.2. Specimen preparation
KCO2, accl was developed considering the differences in mixture pro­
portions and CO2 concentrations used in accelerated tests. The futuristic Prism specimens (size: 100 × 100 × 500 mm) were used to ensure
estimates of concretes exposed to urban tropical climate can be made that carbonation depth at various exposure periods was measured on the
with A-to-N model. With experimental results and estimations from A- same concrete specimen – by fracturing the same specimen at various
to-N model, a simple design chart to decide the cover depth to be cross-sections, as shown in Fig. 4 (a). Concrete mixes as given in Table 3
were prepared using a pan mixer (mixing capacity: 200 kg), and prism

3
S. Rathnarajan et al. Cement and Concrete Composites 126 (2022) 104329

Fig. 3. Summary on the mix proportions of the concretes in this study.

Table 2
Oxide composition and physical properties of binder materials used.
Oxide/Parameter OPC Slag Fly ash LC3

CmA CmP SgC SgF FaF FaC

Oxide composition (%)

Al2O3 4.7 4.2 17.4 21.1 29.9 31.5 10.8
CaO 65.1 64.6 35.6 31.5 1.3 13.8 41.8
Fe2O3 3.9 3.9 1.0 1.9 4.3 6.2 3.7
K2O 0.5 0.6 0.6 0.9 1.4 0.1 0.2
MgO 1.2 0.9 8.0 8.6 0.6 2.3 1.8
Na2O 0.5 0.2 0.4 0.4 0.2 0.6 0.2
SiO2 19.4 19.0 33.8 32.4 59.3 39.9 31
SO3 – 1.7 – – 0.2 3.2 –
Physical properties
γ 3.18 3.2 2.9 2.9 2.5 2.5 3.1
SSA (m2/kg) 320 340 360 430 330 390 480

Notes: CmA: OPC 53 grade from Source A; CmP: OPC 53 grade from Source P; SgC – Coarser slag; SgF – Finer slag; FaF – Class F fly ash; FaC – Class C fly ash; CC –
Calcined clay; LS – Limestone; SSA - Specific surface area; γ – Specific gravity.

specimens and companion cube specimens were cast and covered with
impervious (plastic) sheets. After one day, specimens were demoulded
and moved to a moist curing room with a temperature of 30 ◦ C. At a total
of 28 days of moist curing, the specimens were moved out of the curing
room and upon natural drying, two layers of anti-carbonation coating
were applied on both the end faces (see Fig. 4 (a)) and allowed to cure
for 24 h. This was done to ensure that only the four side faces were
exposed to carbon dioxide.
3.3. Natural carbonation tests
A total of 68 concrete prism specimens (from the same batch of
concrete as used in accelerated carbonation tests) were exposed to
‘Natural – Open’ and ‘Natural – Sheltered’ exposure (denoted as O and S)
on a rooftop in Chennai, India as shown in Fig. 4 (b). As per EN 206
(2000), these represent the XC3 (moderate humidity) and XC4 (cyclic
wet and dry) exposure classes for carbonation [43]. For Open exposure,
the specimens were exposed to direct rain and sunlight. For Sheltered
exposure, the specimens were kept in the Stevenson screen to protect
them from direct exposure to rain and sunlight [27]. The specimens
were placed with at least 5 cm clear spacing in between to ensure good
air flow and avoid shadowing. Fig. 5 shows the monthly average of
ambient temperature (T: 27 to 34 ◦ C), relative humidity (RH: 65–80%),
number of precipitation days (P), and CO2 concentration at the exposure
site (Chennai, India) in a calendar year. At about 1, 2, 3, and 5 years of
natural exposure, specimens were fractured transversely and phenol­
phthalein indicator was sprayed on the fresh fractured surface, and
carbonation depth (xd, natl) was measured - as recommended in RILEM
CPC 18 [44]. The phenolphthalein indicator solution was made by
mixing 1% by wt. of indicator in a 70–30% blend of ethanol and distilled
water. Four measurements were taken at each face of the specimen – a
total of 16 measurements at one test age, as shown in Fig. 4 (c). Then, the
fractured end surface of the remainder of the specimen was coated with
an acrylic based anti-carbonation coating and allowed to cure for a day.
These specimens were then moved back to the open and sheltered
conditions for further exposure until 5 years.

4
S. Rathnarajan et al.
Fig. 4. Test program: Details of the specimen cast, exposure site, and approach to measure carbonation depth.
3.4. Accelerated carbonation tests
The cured prism specimens were preconditioned by placing in the
controlled laboratory conditions (25 ± 2 ◦ C, and 65 ± 5% RH) for 14
days. Then, they were moved to carbonation chambers with 1 and 3%
CO2 (both at 25 ± 2 ◦ C, and 65 ± 5% RH), as shown in Fig. 4 (d).
Specimens from a total of 34 concretes were kept in the 1% CO2
chamber, and from seven concretes were placed in both 1% and 3% CO2
chambers. At 28, 56, 90, and 112 days of exposure, each prism specimen
was fractured transversely using a shear cutter, and carbonation depth
was measured by following the same procedure as described in the case
of natural carbonation tests. Then, the tested surfaces were coated with
anti-carbonation coating and specimens were placed back in the
chamber for further exposure. The tests were continued until 112 days of
exposure.
3.5. Modeling approach and design chart
A schematic representation of the modelling approach adopted in
this paper is presented in Fig. 6. The square root of time model (Eq. (2))
is widely used to estimate the service life of concrete [45].
√̅
xd = KCO2 t (2)
Recent research articles have adapted Eq (2) for estimating KCO2 as a
performance indicator of concretes made with different binders [21,
46–48]. In the present study also, Eq (2) was calibrated with the 5-year
data on natural carbonation depth (xd, natl) for both Open and Sheltered
5
Cement and Concrete Composites 126 (2022) 104329
conditions, and the corresponding KCO2, natl were determined for the 34
concretes under study. However, such estimations cannot be easily
extrapolated to other concretes with different mixture proportions.
Hence, the ‘Accelerated-to-Natural’ model (denoted as A-to-N model,
herein) that estimates the KCO2, natl by using its KCO2, accl was developed
as follows. First, the difference between the 5-year Open and Sheltered
data were compared to identify the more severe case – to develop con­
servative models for design purposes. Then, the KCO2, accl was estimated
by calibrating the square root of time model with the accelerated
carbonation data from both 1 and 3% CO2. The A-to-N model was then
developed by regressing the calculated KCO2, natl from Sheltered expo­
sure (more conservative approach) with the mixture proportion of the
paste in concrete, CO2 concentration, and KCO2, accl. The Mean Absolute
Percentage Error (MAPE) was calculated to assess the accuracy of the
developed model. Also, for practical use, a service-life based design
chart was developed to determine the required cover depth (cd) with
inputs from designers on KCO2, accl and target service life of the
steel-concrete system. The end of service life in carbonation-induced
corrosion in the current approach is defined as the time taken for
carbonation depth to exceed cover depth (xd > cd).
4. Experimental results
Table 4 and Fig. 7 show the measured xd under natural and accel­
erated conditions for the 34 concretes. In Fig. 7, the black numbers at the
end of the bars are the final xd and the white numbers are the estimated
values of KCO2 calculated by regressing the corresponding xd with the
S. Rathnarajan et al. Cement and Concrete Composites 126 (2022) 104329

Table 3
Mixture proportions and properties of concretes used in this study.
Mix ID Notation Quantity (kg/m3) Properties

(OPC-%SCM-w/b-Total binder content- Cement SCM FA (<4.75 CA (<10 CA (<20 Water Comp. strength Slump
Curing type) content content mm) mm) mm) (MPa) (mm)

INM CmA-NoSCM-0.65-280-M 280 0 760 499 749 182 35 80

01
INM CmA-NoSCM-0.55-340-M 340 0 735 483 725 187 43 85
02
INM CmA-NoSCM-0.50-310-M 310 0 759 498 748 155 55 85
03
INM CmP-NoSCM-0.50-310-M 310 0 695 496 744 155 46 100
04
INM CmP-NoSCM-0.40-360-M 360 0 703 477 716 144 57 90
05
INM CmP-NoSCM-0.45-360-M 360 0 719 463 695 162 49 70
06
INM CmA-30SgC-0.65-280-M 196 84 763 512 768 182 29 90
07
INM CmA-15SgC-0.60-310-M 263 47 756 498 745 186 42 100
08
INM CmA-15SgC-0.55-340-M 289 51 756 498 745 187 41 80
09
INM CmP-15SgC-0.50-310-M 263 47 759 498 748 155 53 85
10
INM CmA-30SgF-0.65-280-M 196 84 760 499 749 182 29 140
11
INM CmA-15SgF-0.60-310-M 263 47 747 491 736 186 39 90
12
INM CmA-15SgF-0.55-340-M 289 51 735 483 725 187 46 80
13
INM CmA-15SgF-0.50-310-M 263 47 759 498 748 155 48 90
14
INM CmA-30SgF-0.50-310-M 217 93 759 498 750 155 52 100
15
INM CmA-50SgF-0.50-310-M 155 155 759 498 751 155 59 80
16
INM CmA-30FaF-0.65-280-M 196 84 760 499 749 182 29 80
17
INM CmA-15FaF-0.60-310-M 263 47 760 498 745 186 44 80
18
INM CmA-15FaF-0.55-340-M 289 51 735 483 725 187 46 80
19
INM CmA-15FaF-0.50-310-M 263 47 759 498 748 155 50 85
20
INM CmA-30FaF-0.50-310-M 217 93 759 498 748 155 40 85
21
INM CmA-50FaF-0.50-310-M 155 155 759 498 748 155 31 90
22
INM CmP-30FaF-0.45-310-M 217 89 723 491 737 140 46 100
23
INM CmP-30FaF-0.45-360-M 252 108 696 474 712 158 51 120
24
INM CmA-15FaC-0.60-310-M 263 47 747 491 736 186 39 90
25
INM CmA-15FaC-0.55-340-M 289 51 735 483 725 187 46 95
26
INM CmP-15FaC-0.50-310-M 264 46 759 498 748 155 44 80
27
INM CmA-30FaC-0.50-310-M 217 93 759 498 748 155 44 90
28
INM CmA-20SgB20FaF-0.50-310-M 186 124 759 498 748 155 52 80
29
INM CmA-20SgB20FaC-0.50-310-M 186 124 748 494 746 155 41 85
30
INM CmA-20FaF20FaC-0.50-310-M 186 124 759 498 746 155 46 85
31
INM LC3-NoSCM-0.50-310-M 170 140 705 489 733 155 52 80
32
INM LC3-NoSCM-0.40-340-M 187 153 713 495 742 136 61 120
33
INM LC3-NoSCM-0.45-360-M 198 162 682 473 709 180 55 70
34

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S. Rathnarajan et al. Cement and Concrete Composites 126 (2022) 104329

3rd year) and the hatched extension bar show the difference between the
average xd at 5 and 3 years [i.e., Δxd = (xd, 5y − xd, 3y)]. Based on the
data collected during the 5 years of exposure, the calculated KCO2, natl for
Natural Open exposure is between 3 and 7.7 mm/year0.5. For concretes
made with OPC, this is about 4 mm/year0.5; for concretes with OPC +
Sg, this is between 3.3 and 6 mm/year0.5; for concretes with OPC + Fa
this is between 3 and 7.4 mm/year0.5; and for concretes with LC3, this is
between 6.2 and 7.7 mm/year0.5. Fig. 7 (b) shows similar data for
Natural Sheltered exposure condition. For this, the KCO2, natl ranges
between 3.6 and 9.2 mm/year0.5 (as opposed to 3 and 7.7 for Open
exposure condition). It should be noted that the calculated KCO2, natl is a
function of both concrete type and exposure condition. For the Sheltered
condition, it is about 20% higher than that for the Open exposure con­
dition. This could be attributed to the relative humidity of > 80% for
Fig. 5. Typical climatic conditions at the exposure site in Chennai, India
(Source: www.accuweather.com).
more than nine months in a year in Chennai and the slower drying of
Sheltered specimens (inside Stevenson chamber during the daytime)
than the Open specimens. Hence, the Sheltered condition is considered
square root of time function.
as more conservative than the Open condition. Hence, the xd data and
estimated KCO2, natl from only the Sheltered condition are used for
4.1. Natural carbonation test data further discussion, analysis, and modeling in this paper. Fig. 8 (a)
summarizes the increase in the average carbonation depth (Δxd)
In Fig. 7 (a) and (b), filled grey bars show the average xd, 3y (i.e., xd at

Fig. 6. Statistical approach to develop A-to-N model and use of design chart.

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S. Rathnarajan et al. Cement and Concrete Composites 126 (2022) 104329

Table 4
Carbonation depths measured at natural and accelerated conditions.
Mix ID (OPC-%SCM-w/b-Total binder content-Curing type) Carbonation depth (mm)

Open exposure period Sheltered exposure 1% CO2 exposure period 3% CO2 exposure period
(year) period (year) (day) (day)

2y 3y 5y 2y 3y 5y 28d 70d 112d 28d 70d 112d

INM 01 CmA-NoSCM-0.65-280-M 5 7 9 – 10 13 5 7 8 – – –
INM 02 CmA-NoSCM-0.55-340-M 4 6 8 – 8 11 4 6 7 – – –
INM 03 CmA-NoSCM-0.50-310-M 4 6 9 – 7 8 3 5 6 – – –
INM 04 CmP-NoSCM-0.50-310-M 6 7 10 6 8 10 1 3 5 5 7 10
INM 05 CmP-NoSCM-0.40-360-M 4 6 8 5 7 9 – – – – – –
INM 06 CmP-NoSCM-0.45-360-M 6 7 8 7 8 10 1 3 4 2 5 6
INM 07 CmA-30SgC-0.65-280-M 9 11 15 9 12 16 6 8 9
INM 08 CmA-15SgC-0.60-310-M 6 9 11 7 10 12 4 7 8 – – –
INM 09 CmA-15SgC-0.55-340-M 5 7 9 6 10 12 4 8 11 – – –
INM 10 CmP-15SgC-0.50-310-M 4 6 8 – 6 8 3 5 7 – – –
INM 11 CmA-30SgF-0.65-280-M 7 11 13 9 13 14 6 9 10 – – –
INM 12 CmA-15SgF-0.60-310-M 5 8 10 8 10 11 4 7 8 – – –
INM 13 CmA-15SgF-0.55-340-M 5 7 10 7 9 11 4 7 8 – – –
INM 14 CmA-15SgF-0.50-310-M 4 7 8 – 7 8 3 5 6 – – –
INM 15 CmA-30SgF-0.50-310-M 6 8 9 – 6 9 4 6 7 – – –
INM 16 CmA-50SgF-0.50-310-M 7 10 12 – 8 13 5 6 8 – – –
INM 17 CmA-30FaF-0.65-280-M 7 10 12 – 11 14 7 10 11 – – –
INM 18 CmA-15FaF-0.60-310-M 4 7 10 – – – 5 7 8 – – –
INM 19 CmA-15FaF-0.55-340-M 6 8 13 7 9 13 4 7 8 – – –
INM 20 CmA-15FaF-0.50-310-M 4 6 7 3 8 10 3 6 11 – – –
INM 21 CmA-30FaF-0.50-310-M 6 8 10 6 9 11 3 7 11 – – –
INM 22 CmA-50FaF-0.50-310-M 7 13 18 – 15 20 7 11 13 – – –
INM 23 CmP-30FaF-0.45-310-M 8 9 11 8 10 12 3 6 7 6 11 12
INM 24 CmP-30FaF-0.45-360-M 7 8 10 8 11 12 4 7 8 7 10 11
INM 25 CmA-15FaC-0.60-310-M – 9 12 – 11 15 4 7 9 – – –
INM 26 CmA-15FaC-0.55-340-M – 7 9 – 11 13 4 8 9 – – –
INM 27 CmP-15FaC-0.50-310-M 5 7 9 – – – 3 5 6 – – –
INM 28 CmA-30FaC-0.50-310-M – 10 12 – 11 14 4 7 11
INM 29 CmA-20SgB20FaF-0.50-310-M 4 6 11 – 9 14 4 8 9 – – –
INM 30 CmA-20SgB20FaC-0.50-310-M – 8 12 – 14 17 4 8 9 – – –
INM 31 CmA-20FaF20FaC-0.50-310-M – 12 14 – 9 12 6 10 11 – – –
INM 32 LC3-NoSCM-0.50-310-M 11 15 17 10 16 18 5 9 10 9 16 18
INM 33 LC3-NoSCM-0.40-340-M 8 11 13 9 13 14 3 6 7 4 10 12
INM 34 LC3-NoSCM-0.45-360-M 8 13 14 9 13 14 3 7 8 9 14 15

between 3rd and 5th year in all the binder types exposed to Natural
Sheltered conditions. From the results, the concretes with higher water-
to-binder ratio and ternary mixes with 40% clinker substitution showed
high xd at 5 years. However, the increase in xd at later ages is similar or
comparable in concretes with OPC, OPC + Sg, and OPC + Fa. Also, the
limited LC3 concretes studied showed a negligible increase in xd from 3
to 5 years. This shows that in high resistive binder systems like LC3, the
depletion of calcium hydroxide influences the rate of carbonation more
at early ages and less at later ages. The combined effect of this decrease
in calcium hydroxide and pore refinement due to pozzolanic reaction in
highly resistive binders should be considered for estimating carbonation
resistance of concretes at later ages. Hence, the concretes with SCMs can
show higher later-age carbonation resistance, and it is possible to design
concretes with SCMs to meet the target service life of multiple decades.
rate of changes in the humidity conditions inside the concrete. In
addition, the low penetrability of concretes with SCMs, especially at a
depth inside the concrete than at the surface, could be another reason for
the reduction in the carbonation rate at the later ages [21]. The calcu­
lated KCO2, accl (using Tuutti’s model) from the early accelerated
carbonation data (say, about 28 or 58 days of exposure) can underesti­
mate the potential high resistance of SCM-based concretes against
carbonation-induced corrosion of steel with typical cover depths. It is
important to consider an xd that is similar to the cover depth of
steel-concrete systems to assess the resistance against
carbonation-induced corrosion, especially in case of SCM based
concretes.
5. Carbonation models and design chart

Fig. 6 provides the flowchart of the entire approach for statistical

4.2. Accelerated carbonation test data
Fig. 7 (c) and (d) show the measured xd and calculated KCO2, accl for
concretes with accelerated carbonation at 1 and 3% CO2, respectively.
The lengths of the grey and hatched bars indicate the average xd at 70
days and the difference between xd at 112 and 70 days [i.e., Δxd = (xd,
112d − xd, 70d)]. Fig. 8 (b) shows the increase in xd in accelerated
carbonation exposure between 70 and 112 days for different binder
types. Similar trend (as in natural exposure) of significant reduction in
carbonation at later ages was observed between the binder types. Hence,
the concretes with SCMs despite showing higher carbonation depths at
early ages could have a reduction in rate of change of carbonation rate
with an increase in the test duration [48]. This can be attributed to the
more refined microstructure of the interior concrete and the favourable
modeling and the design chart. The KCO2, natl and KCO2, accl were calcu­
lated using the square root of time function and the corresponding xd
data from the experiments. As discussed in the previous section, only the
data from Sheltered case was considered - for being conservative in
service life estimations. In this section, two models to estimate KCO2, natl
from KCO2, accl (for two cases of 1 and 3% CO2 test data) are presented.
Then, a more generic A-to-N model with CO2 concentration and mix
proportion parameters also as predictor variables is developed for wider
applications – say, with accelerated tests at any CO2 concentration.
Hence, the A-to-N model is developed by regressing the data on concrete
mixture proportion, CO2 concentration, and KCO2, accl against KCO2, natl.
Then, the xd, 50y (i.e., xd at 50 years) for all 34 concretes were estimated
using the derived KCO2, natl from A-to-N model and the square root of

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S. Rathnarajan et al. Cement and Concrete Composites 126 (2022) 104329

Fig. 7. Average carbonation depth in concretes under natural and accelerated conditions.

Fig. 8. OPC and SCM based concretes exhibiting similar later-age carbonation resistance.

9
S. Rathnarajan et al.
time function. Further, using this A-to-N model, a design chart was
developed to enable quick decision on the required cover depth to
achieve an intended service life of 50 years in the tropical climate. The
following paragraphs provide discussions on these approaches and the
models developed.
5.1. Accelerated-to-Natural carbonation model (A-to-N model)
Fig. 9 (a) and (b) indicate a linear relationship between the KCO2, natl
and KCO2, accl at 1 and 3% CO2 concentrations, respectively - for all
binder types. The scatter observed along the linear fit can be attributed
to the changes in test conditions across the specimens and seems
reasonable considering the inherent variability in the concrete material
properties. Fig. 9 (a) does not reveal good correlation between KCO2, natl
and KCO2, accl for individual binder groups (shown with different
markers). This could be attributed to the possible variations in the
mixture proportions (such as water-to-binder ratio (w/b) and replace­
ment level of SCMs (RL)) among the mixes in each group. Also, incor­
porating CO2 concentration at natural and accelerated tests as a variable
in conversion model proved to be useful in developing a generic model
applicable to different exposure conditions [49]. Hence, the more
generic A-to-N model was developed to estimate the KCO2, natl from KCO2,
accl considering the concrete mixture proportion (say, wb and RL) and
CO2 concentration (CCO2) as predictor variables, as explained next.
Based on the earlier finding that the Sheltered case would give more
conservative estimates of carbonation resistance (Fig. 7(a)), the Open
exposure data was not used in this A-to-N model development. The A-to-
N model was formulated by understanding the influence of each pre­
dictor variable on KCO2, natl in Sheltered exposure. The wb, RL, CCO2, and
KCO2, accl are the predictor variables. Scatter plots between these vari­
ables and their interaction terms and the dependent variable (KCO2, natl)
were diagnosed and possible model formulations were identified.
Among those, a three-way interaction term with wb, RL, and KCO2, accl
was found to be suitable (see Fig. 10 (a)). Note that the RL was
normalized to range between 0 and 1. Similarly, a two-way interaction
term with CCO2 and KCO2, accl was also found suitable for A-to-N model
formulation, see Fig. 10 (b). The dashed lines in Fig. 10 (a) and (b)
indicate that the KCO2, natl increases gradually with an increase in these
interaction terms. For the modelling purpose, a power function was used
– if a linear fit is better, the power would become equal to 1; else, a
suitable coefficient is determined by the regression process. Hence, the
A-to-N model to estimate the KCO2, natl was formulated with the power
function of these two interaction terms, as shown in Eq. (3).
KCO2, natl = 3.7KCO2, accl 9.6
[( )9.7 ]
CCO2, natl
× + KCO2, accl − 9.4
× (w/b × SCM)0.13
CCO2, accl
where, KCO2, accl, CCO2, natl, CCO2, accl, wb, and RL are the predictor
Fig. 9. Relationship between Sheltered and accelerated carbonation.
Cement and Concrete Composites 126 (2022) 104329
variables. The likelihood estimates of the model coefficients were ob­
tained by optimizing the regression process using a MATLAB program;
the mean and coefficient of variation of the model coefficients are pro­
vided in Table 5. Fig. 11 represents the model validation plot with 1:1
line and the ±σ lines (i.e., ± one standard deviation) between the pre­
dicted and experimental KCO2, natl. The mean absolute percent error
(MAPE) for the developed A-to-N model was found to be 12% - indi­
cating a reasonable estimation.
5.2. Estimation of carbonation depth at a future time
The KCO2, natl estimated using the A-to-N model and the square root of
time function can be used to estimate xd at future time instants as
follows:
xd, ty = KCO2, natl (t)0.5 Eq. (4)
where, KCO2, natl can be obtained using Eq. (3) and t is the age of the
structure or exposure period in years. Fig. 12 shows the xd, 50y for con­
cretes with different binder types and estimated using Eq. (4). In general,
carbonation-induced corrosion is expected to initiate when xd exceeds
the cover depth cd (xd > cd). The material selection for meeting a target
service life can be done based on assessing if a concrete system meets
this criteria. The estimated xd, 50y values for many mixes in this study are
less than 40 mm, which could be acceptable for many structures with a
target service life of 50 years and with cover depth of 40 mm. A couple of
mixes with very high water-to-binder ratio and more than 50% fly ash
substitution exhibited very high carbonation. However, the estimated
values for many other cases are between 35 and 40 mm (see Fig. 12).
Note that all the mixes shown in Fig. 12 are with w/b greater than 0.45;
for mixes with SCMs and lower w/b the carbonation resistance could be
more. The concretes with low water-to-binder ratios and superplasticers
are quite common in today’s construction. Hence, such SCM-based
concretes with lesser water-to-binder ratio can exhibit similar carbon­
ation resistance exhibited by OPC concretes with equal strength. A
design chart that enables such material choices to meet the target service
life is developed next.
5.3. Design chart for concretes with SCMs in the tropical climate
Fig. 13 shows the design chart where the input parameters are KCO2,
natl or KCO2, accl-1% and the target service life, and the output is the type of
binder and the required cover depth. The estimated service life in the
chart was plotted against a range of cover depths (10–80 mm) for every
KCO2, natl from 2 to 8 mm/year0.5 using Tuutti’s square root of time
function. The possible extent of KCO2, natl for each binder is reported in
Table 6 with mean and coefficient of variation (COV). The concretes
(3)
made with coarse and fine slag (say, SgC and SgF) are grouped into the
same category (OPC + Sg) as they have similar chemical composition.
Similarly, Class F and Class C fly ash (FaF and FaC) are grouped into the
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S. Rathnarajan et al. Cement and Concrete Composites 126 (2022) 104329

Fig. 10. Diagnostic plots between interaction of independent variables and dependent variable (KCO2, natl-S).

Table 5
Posterior statistics of the A-to-N model parameters.
Likelihood estimates

Symbol Mean COV (%)

θ0 3.7 26
θ1 9.62 12
θ2 9.68 12
θ3 − 9.37 13
θ4 0.13 4

Fig. 12. xd, 50y estimated using the KCO2, natl from A-to-N model and the square
root time function.

achieving a target service life of 50 years. However, the necessary cover

Fig. 11. Validation of A-to-N model.
same category OPC + Fa. With the mean and COV of KCO2, natl for each
binder type, the estimated range of KCO2, natl for every binder type is
shown in Fig. 13. The expected range of KCO2, natl or KCO2, accl for each
binder type can be used to calculate the required cover depth for
achieving target corrosion-free service life. The cover depth compen­
sation required for the worst-case scenario of OPC and fly ash mix with
the high-volume replacement (say 50%) is observed to be 17 mm for
depth compensation for concretes with the lowest KCO2, natl in fly ash and
slag substituted concretes against the best OPC concrete in this study is
less than 5 mm. Fig. 13 shows that KCO2, natl between 4.5 and 5 mm/
year0.5 can be achieved in any binder type by lowering the water-to-
binder ratio and marginally increasing the binder content. Hence,
proper mix proportioning can produce similar carbonation resistance in
concretes made with any binder. The design chart enables the engineer-
in-charge to design the suitable cover depth for concretes with any KCO2,
natl for achieving the target service life using various binder types. The
synergy between increasing cover depth and specifying maximum and
minimum limits on the concrete mix proportion parameters can help to
achieve the equivalent carbonation resistance in concretes with and
without SCMs. Also, the material selection should be based on xd in the
long-term and considering if it is going to be less than the cover depth,
instead of xd in the short-term and without considering the cover depth –
as in the current practice. The possible variability of cover depth in
structures also needs to be considered. The developed design chart is
expected to enable such quick decision making processes.
However, it should be noted that the current design chart does not

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S. Rathnarajan et al. Cement and Concrete Composites 126 (2022) 104329

• At later ages, due to better pore refinement and consequential

changes in the moisture conditions inside concrete, SCM-based
concretes can exhibit very slow progression of carbonation front,
leading to possible similar long-term carbonation depth in SCM-
based and OPC concretes.
• When SCMs are used, the carbonation coefficients obtained from
accelerated carbonation tests is not linearly related to the coefficients
obtained from natural carbonation tests; material composition has
significant influence on this relationship.
• KCO2, natl can be modeled using KCO2, accl, CCO2, wb, and RL as pre­
dictor variables and the resulting model (named as A-to-N model)
shows reasonable accuracy (MAPE ≈12%). The model is expressed as
follows:

KCO2, natl = 3.7KCO2, accl 9.6

[( )9.7 ]
CCO2, natl
× + KCO2, accl − 9.4
× (w/b × SCM)0.13
CCO2, accl

• For concretes with lower replacement level (≤30% slag/fly ash) and
water-to-binder ratio (≤0.5), an increase in cover depth of ≈5 mm is
sufficient to achieve equivalent service life as that provided by OPC
concretes. This difference reduces as the cover depth is higher and
target service life is longer.
Fig. 13. Cover depth required for achieving 50 years of corrosion-free ser­
vice life.

Declaration of competing interest

Table 6
Calculated mean KCO2, natl of different binders. The authors declare that they have no known competing financial
Binder type Exposure condition KCO2 (mm/year0.5) interests or personal relationships that could have appeared to influence
the work reported in this paper.
Mean COV (%)

OPC Natural-Sheltered 4.4 15

OPC + Sg 5.1 23
Acknowledgements
OPC + Fa 6.1 27
OPC + Sg + Fa 6.0 14 The authors acknowledge the financial support from the Ministry of
Education, Government of India and the Institute of Eminence Research
Initiative grant on Technologies for Low carbon and Lean Construction
consider the effecs of sustained and dynamic loads that could result in
from the Indian Institute of Technology (IIT) Madras, Chennai, India.
cracking, creep and shrinkage in concrete, and the long term changes
The authors also acknowledge the financial support received from
(say, across the decades) in the atmospheric carbon dioxide levels. Also,
Lafarge de Researche, France, and the Swiss Development Agency and
the current study focused on concretes with the water-to-binder ratio
EPFL, Switzerland. The authors are thankful to Dr. Pavan Vaddey, Ms.
between 0.45 and 0.65. However, concretes with SCMs can be made
Anila and Ms. Priya, and other lab technicians in the Department of Civil
with lower water to binder ratios using high-range water-reducing ad­
Engineering at IIT Madras, Chennai, India for their assistance in this
mixtures. With a low w/b ratio (say ≤ 0.4), the concretes with SCMs can
long-term study.
have KCO2, natl less than 4.5 mm/year0.5. Further studies need to be
carried out in concretes with lower water to binder ratio to understand
the true potential of concretes with SCMs against carbonation. References

6. Conclusions
5-year long natural carbonation tests and 4-month long accelerated
carbonation tests were conducted on 34 concretes with OPC, fly ash,
slag, and LC3. Based on the data collected, a model to estimate KCO2, natl
using KCO2, accl in concretes exposed to tropical climate was developed
and carbonation depth at 50 years were estimated for the 34 concretes.
Moreover, a design chart to calculate the required cover depth for
concretes with different binders and target service life was developed.
The following are the major conclusions from this study.
• In urban tropical climate, the carbonation resistance of concretes in
Sheltered exposure is 10–20% less than that in Open exposure.
• The incremental increase in carbonation depth (Δxd) at later ages
demonstrated the ability of concretes having SCMs to achieve similar
or even better long-term carbonation resistance compared to OPC
concretes at later-ages (say > 5 years)
[1] M.D.A. Thomas, P.B. Bamforth, Modelling chloride diffusion in concrete: effect of
fly ash and slag, Cement Concr. Res. 29 (1999) 487–495. http://www.sciencedirec
t.com/science/article/pii/S0008884698001926.
[2] L. Jiang, B. Lin, Y. Cai, A model for predicting carbonation of high-volume fly ash
concrete, Cement Concr. Res. 30 (2000) 699–702, https://doi.org/10.1016/S0008-
8846(00)00227-1.
[3] K.K. Sideris, A.E. Savva, J. Papayianni, Sulfate resistance and carbonation of plain
and blended cements, Cement Concr. Compos. 28 (2006) 47–56, https://doi.org/
10.1016/j.cemconcomp.2005.09.001.
[4] K.L. Scrivener, V.M. John, E.M. Gartner, Eco-efficient cements: potential
economically viable solutions for a low-CO2 cement-based materials industry,
Cement Concr. Res. 114 (2018) 2–26, https://doi.org/10.1016/j.
cemconres.2018.03.015.
[5] T. Sakthivel, Compressive strength and elastic modulus of concretes with fly ash
and slag, Journal of Institution. of Engineers, Series. A. 100 (2019) 575–584,
https://doi.org/10.1007/s40030-019-00376-w.
[6] B.S. Dhanya, M. Santhanam, R. Gettu, R.G. Pillai, Performance evaluation of
concretes having different supplementary cementitious material dosages belonging
to different strength ranges, Construct. Build. Mater. 187 (2018) 984–995, https://
doi.org/10.1016/j.conbuildmat.2018.07.185.
[7] Z. Zhang, Q. Wang, H. Chen, Y. Zhou, Influence of the initial moist curing time on
the sulfate attack resistance of concretes with different binders, Construct. Build.
Mater. 144 (2017) 541–551, https://doi.org/10.1016/j.conbuildmat.2017.03.235.
[8] F. Pacheco Torgal, S. Miraldo, J.A. Labrincha, J. De Brito, An overview on concrete
carbonation in the context of eco-efficient construction: evaluation, use of SCMs

12
S. Rathnarajan et al.
and/or RAC, Construction and, Building Materials 36 (2012) 141–150, https://doi.
org/10.1016/j.conbuildmat.2012.04.066.
[9] A. Leemann, F. Moro, Carbonation of concrete: the role of CO2 concentration,
relative humidity and CO2 buffer capacity, Mater. Struct. 50 (2017) 2–14, https://
doi.org/10.1617/s11527-016-0917-2.
[10] H. Shi, B. Xu, X. Zhou, Influence of mineral admixtures on compressive strength,
gas permeability and carbonation of high performance concrete, Construct. Build.
Mater. 23 (2009) 1980–1985, https://doi.org/10.1016/j.
conbuildmat.2008.08.021.
[11] P. Chindaprasirt, S. Rukzon, Pore structure changes of blended cement pastes
containing fly ash, rice husk ash, and palm oil fuel ash caused by carbonation,
Journal of Materials in Civil Engineers 21 (N) (2009) 666–671, https://doi.org/
10.1061/(ASCE)0899-1561(2009)21:11(666).
[12] C.-Q. Lye, R.K. Dhir, G.S. Ghataora, Carbonation resistance of fly ash concrete,
Mag. Concr. Res. 67 (2015) 1150–1178, https://doi.org/10.1680/macr.15.00204.
[13] C.-Q. Lye, R.K. Dhir, G.S. Ghataora, Carbonation resistance of GGBS concrete,
magazine of concrete, Research 68 (2016) 936–969, https://doi.org/10.1680/
jmacr.15.00449.
[14] D.O. McPolin, P.A. Basheer, A.E. Long, K.T. Grattan, T. Sun, New test method to
obtain pH profiles due to carbonation of concretes containing supplementary
cementitious materials, J. Mater. Civ. Eng. 19 (2007) 936–946, https://doi.org/
10.1061/(ASCE)0899-1561(2007)19:11(936).
[15] Z. Shi, B. Lothenbach, M.R. Geiker, J. Kaufmann, A. Leemann, S. Ferreiro,
J. Skibsted, Experimental studies and thermodynamic modeling of the carbonation
of Portland cement, metakaolin and limestone mortars, Cement Concr. Res. 88
(2016) 60–72, https://doi.org/10.1016/j.cemconres.2016.06.006.
[16] A. Leemann, P. Nygaard, J. Kaufmann, R. Loser, Relation between carbonation
resistance, mix design and exposure of mortar and concrete, Cement Concr.
Compos. 62 (2015) 33–43, https://doi.org/10.1016/j.cemconcomp.2015.04.020.
[17] C. Tassos, K. Sideris, A. Chatzopoulos, N. Pistofidis, E. Chaniotakis, Influence of
cement type on carbonation of concrete mixtures, MATEC Web Conferences 163
(2018), 05005, https://doi.org/10.1051/matecconf/201816305005.
[18] A. Leemann, H. Pahlke, R. Loser, F. Winnefeld, Carbonation resistance of mortar
produced with alternative cements, Mater. Struct. 51 (2018) 1–12, https://doi.org/
10.1617/s11527-018-1239-3.
[19] C.D. Atis, Accelerated carbonation and testing of concrete made with fly ash,
Construct. Build. Mater. 17 (2003) 1–5, https://doi.org/10.1007/s13398-014-
0173-7.2.
[20] P.H.R. Borges, J.O. Costa, N.B. Milestone, C.J. Lynsdale, R.E. Streatfield,
Carbonation of CH and C-S-H in composite cement pastes containing high amounts
of BFS, Cement Concr. Res. 40 (2010) 284–292, https://doi.org/10.1016/j.
cemconres.2009.10.020.
[21] M. Otieno, J. Ikotun, Y. Ballim, Experimental investigations on the effect of
concrete quality, exposure conditions and duration of initial moist curing on
carbonation rate in concretes exposed to urban, inland environment, Construct.
Build. Mater. 246 (2020) 118443, https://doi.org/10.1016/j.
conbuildmat.2020.118443.
[22] B. Aruhan, Y. Jia, P. Yan, Natural and accelerated carbonation of concrete
containing fly ash and GGBS after different initial curing period, Mag. Concr. Res.
64 (2012) 143–150, https://doi.org/10.1680/macr.10.00134.
[23] M.F. Montemor, M.P. Cunha, M.G. Ferreira, A.M. Simoes, Corrosion behaviour of
rebars in fly ash mortar exposed to carbon dioxide and chlorides, Cement Concr.
Compos. 24 (2002) 45–53, https://doi.org/10.1016/S0958-9465(01)00025-7.
[24] Y.F. Houst, F.H. Wittmann, Influence of porosity and water content on the
diffusivity of CO2 and O2 through hydrated cement paste, Cement Concr. Res. 24
(1994) 1165–1176, https://doi.org/10.1016/0008-8846(94)90040-X.
[25] V.G. Papadakis, M.N. Fardis, C.G. Vayenas, Effect of composition, environmental
factors and cement-lime mortar coating on concrete carbonation, Mater. Struct. 25
(1992) 293–304, https://doi.org/10.1007/BF02472670.
[26] L.J. Parrott, Carbonation, moisture and empty pores, Adv. Cement Res. 4 (1992)
111–118, https://doi.org/10.1680/adcr.1992.4.15.111.
[27] Q. Huy Vu, G. Pham, A. Chonier, E. Brouard, S. Rathnarajan, R. Pillai, R. Gettu,
M. Santhanam, F. Aguayo, K.J. Folliard, M.D. Thomas, T. Moffat, C. Shi, A. Sarnot,
Impact of different climates on the resistance of concrete to natural carbonation,
13
Cement and Concrete Composites 126 (2022) 104329
Construct. Build. Mater. 216 (2019) 450–467, https://doi.org/10.1016/j.
conbuildmat.2019.04.263.
[28] Fib Bulletin No. 34, Model Code for Service Life Design, 2006.
[29] S.K. Roy, P.K. Beng, D.O. Northwood, The carbonation of concrete structures in the
tropical environment of Singapore and a comparison with published data for
temperate climates, Mag. Concr. Res. 48 (1996) 293–300, https://doi.org/
10.1680/macr.1996.48.177.293.
[30] J. Khunthongkeaw, S. Tangtermsirikul, T. Leelawat, A study on carbonation depth
prediction for fly ash concrete, Construct. Build. Mater. 20 (2006) 744–753,
https://doi.org/10.1016/j.conbuildmat.2005.01.052.
[31] C. Andrade, M.A. Sanjuán, M. Cheyrezy, Concrete carbonation tests in natural and
accelerated conditions, Adv. Cement Res. 15 (2003) 171–180, https://doi.org/
10.1680/adcr.2003.15.4.171.
[32] A. Durán-Herrera, J.M. Mendoza-Rangel, E.U. De-Los-Santos, F. Vázquez,
P. Valdez, D.P. Bentz, Accelerated and natural carbonation of concretes with
internal curing and shrinkage/viscosity modifiers, Mater. Struct. 48 (2015)
1207–1214, https://doi.org/10.1617/s11527-013-0226-y.
[33] K. Sisomphon, L. Franke, Carbonation rates of concretes containing high volume of
pozzolanic materials, Cement Concr. Res. 37 (2007) 1647–1653, https://doi.org/
10.1016/j.cemconres.2007.08.014.
[34] D.W.S. Ho, R.K. Lewis, Carbonation of concrete and its prediction, Cement Concr.
Res. 17 (1987) 489–504, https://doi.org/10.1016/0008-8846(87)90012-3.
[35] S. Kandasami, T.A. Harrison, M.R. Jones, G. Khanna, Benchmarking UK concretes
using an accelerated carbonation test, Mag. Concr. Res. 64 (2012) 697–706,
https://doi.org/10.1680/macr.11.00138.
[36] F.G. da Silva, P. Helene, P. Castro-Borges, J.B. Liborio, Sources of variations when
comparing concrete carbonation results, J. Mater. Civ. Eng. 21 (2009) 333–342,
https://doi.org/10.1061/(ASCE)0899-1561(2009)21:7(333).
[37] M. Castellote, L. Fernandez, C. Andrade, C. Alonso, Chemical changes and phase
analysis of OPC pastes carbonated at different CO2 concentrations, Mater. Struct.
42 (2009) 515–525, https://doi.org/10.1617/s11527-008-9399-1.
[38] J.H.M. Visser, Influence of the carbon dioxide concentration on the resistance to
carbonation of concrete, Construct. Build. Mater. 67 (2013) 8–13, https://doi.org/
10.1016/j.conbuildmat.2013.11.005.
[39] I. Galan, F.P. Glasser, D. Baza, C. Andrade, Assessment of the protective effect of
carbonation on portlandite crystals, Cement Concr. Res. 74 (2015) 68–77, https://
doi.org/10.1016/j.cemconres.2015.04.001.
[40] IS 265, Ordinary Portland Cement – Specifications, Bureau of Indian standards,
2015, pp. 1–13.
[41] ASTM, C150/C150M-21, Standard Specification for Portland Cement, ASTM
International, 2021, pp. 1–9.
[42] Y. Dhandapani, T. Sakthivel, M. Santhanam, R. Gettu, R.G. Pillai, Mechanical
properties and durability performance of concretes with limestone calcined clay
cement (LC3), Cement Concr. Res. 107 (2018) 136–151, https://doi.org/10.1016/
j.cemconres.2018.02.005.
[43] EN 206 Concrete. Specification, Performance, Production, and Conformity, 2008.
[44] RILEM CPC – 18, Measurement of hardened concrete carbonation depth, RILEM
recommendation, Mater. Struct. 21 (1988) 453–455.
[45] K. Tuutti, Service Life of Structures with Regard to Corrosion of Embedded Steel,
Aci-Sp65-13, 65, 1980, pp. 223–236, https://doi.org/10.14359/6355.
[46] C. Andrade, Evaluation of the degree of carbonation of concretes in three
environments, Construct. Build. Mater. 230 (2020) 116804, https://doi.org/
10.1016/j.conbuildmat.2019.116804.
[47] V. Shah, S. Bishnoi, Carbonation resistance of cements containing supplementary
cementitious materials and its relation to various parameters of concrete,
Construct. Build. Mater. 178 (2018) 219–232, https://doi.org/10.1016/j.
conbuildmat.2018.05.162.
[48] E. Nakamura, Y. Kurihara, H. Koga, Outdoor exposure test of concrete containing
supplementary cementitious materials, Key Eng. Mater. 711 (2016) 1076–1083.
https://doi.org/10.4028/www.scientific.net/KEM.711.1076.
[49] R. Gettu, R.G. Pillai, M. Santhanam, A. Basavaraja, S. Rathanarajan, B.S. Dhanya,
Sustainability-based decision support framework for choosing concrete mixture
proportions, Mater. Struct. 51 (2018) 165, https://doi.org/10.1617/s11527-018-
1291-z.