Construction and Building Materials 84 (2015) 320–330

Contents lists available at ScienceDirect

Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Comparative study of white and ordinary concretes with respect of

carbonation and water absorption
Ana Paula Kirchheim a,⇑, Vanessa Rheinheimer b, Denise C.C. Dal Molin a
a
Department of Civil Engineering, Federal University of Rio Grande do Sul, UFRGS, PPGEC-NORIE, 99 Osvaldo Aranha Ave., Porto Alegre 90035-190, Brazil
b
Berkeley Education Alliance for Research in Singapore Limited, Sinberbest, 1 Create Way, 11-01, 138602 Singapore, Singapore

h i g h l i g h t s

 Degree of carbonation and water absorption of concretes are evaluated.

 Concretes with white cement are compared to ordinary Portland cement.
 Results were analyzed statistically.
 Results show that the type of cement plays a major role.
 Water permeability or surface water absorption tests presented a good correlation with carbonation.

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

Article history: This research compares the degree of carbonation and water absorption of concretes with white cement
Received 1 July 2014 versus ordinary Portland cement. For this, four types of white concrete (WPC1–4), ordinary Portland con-
Received in revised form 25 February 2015 crete (OPC) as control, and three water/cement (w/c) levels. Results were analyzed statistically.
Accepted 4 March 2015
Compressive strength was used as control for the durability tests. Results show no carbonation in con-
Available online 25 March 2015
cretes with w/c ratio 0.4. Concretes WPC1, WPC2, and OPC with w/c 0.6 showed the highest carbonation
level. The best performance was with WPC3, demonstrating that the type of cement plays a major role.
Keywords:
Water permeability or surface water absorption tests presented a good correlation with carbonation.
White Portland cement
White concrete
Ó 2015 Elsevier Ltd. All rights reserved.
Durability
Carbonation

1. Introduction to evaluate its performance and durability. The main advantage of

Concrete is one of the most versatile and useful building materi-
als. Nevertheless this material sometimes displays two undesirable
features: poor aesthetic properties, i.e. poor visual appearance and
poor durability in aggressive environments [1]. Different types of
Portland cement are manufactured to attain different physical,
chemical, and mechanical properties in concrete structures,
depending on the type of structure and where it is to be located.
White Portland cement (WPC) is produced following same
specifications as type I or III cements, i.e., ASTM C 150 [2]; however,
its production requires additional care [3]. White cement is differ-
entiated from ordinary Portland cement by its color—which is
obtained using raw materials with low iron and manganese oxide
contents and special care during manufacture, mainly cooling and
milling process. Because this produces a material with different
characteristics compared to OPC, comparative studies are needed
⇑ Corresponding author. Tel.: +55 51 3308 3518.
E-mail address: anapaula.k@ufrgs.br (A.P. Kirchheim).
using WPC instead of OPC is that it can be used either without or with
pigments, thus avoiding the use of dyes. Many architects use WPC
because of its flexibility in terms of color aesthetic.
The ability to prevent the ingression of harmful chemical or gas-
eous species is directly related to the durability of the concrete
applied in structures that last to a long term, the major index for
this capacity is their own permeability. Permeability governs the
permeation of moisture, ionic, and gaseous species into concrete,
and affects durability properties, such as carbonation, sulfate
attack, acid attack, air permeability, freeze-tawn, water absorption,
corrosion of steel rebar and alkali-aggregate reaction [4,5].
Regarding the durability of concretes with WPC, some studies were
done in order to analyse and improve its behavior with respect to
the sulfate resistance [6], the electrical resistivity and conductivity
[7] and also shrinkage, oxygen permeability and the chloride pene-
tration properties [8] with addition of blast-furnace slag activated
by sodium sulfate. Ferraro and Nanni [9] presented a fundamental
investigation on the strength, porosity, corrosion resistance and
thermal conductivity of white concrete blended with an off-white

http://dx.doi.org/10.1016/j.conbuildmat.2015.03.020
0950-0618/Ó 2015 Elsevier Ltd. All rights reserved.
 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330 321

rice husk ash. Also Jang et al. [1] assessed the color expression Table 1
characteristics and physical properties of colored mortar with the Chemical, physical and mechanical characteristics of the cements used.

addition of ground granulated blast-furnace slag and Muynck Chemical composition Content (wt%)
et al. [10] evaluated 12 different products formulations to prevent OPC WPC1 WPC2 WPC3 WPC4
algal fouling in white architecture concrete. Comparing the results
Loss on ignition (LOI) 3.76 9.37 7.01 2.09 2.16
to concretes without mineral admixtures or treatments all the Silicon dioxide (SiO2) 19.53 19.20 20.29 22.27 24.52
analysed properties were greatly improved. Aluminum dioxide (Al2O3) 3.91 3.53 3.66 4.29 2.10
Carbonation resistance of concrete has also been highly con- Iron oxide (Fe2O3) 2.89 0.16 0.17 0.21 0.36
cerned, especially when concrete structures are reinforced with Calcium oxide (CaO) 63.19 62.46 63.86 66.04 67.42
Magnesium oxide (MgO) 1.94 1.53 1.02 1.06 0.53
steel rebar [4]. Steel is maintained passive in the high alkalinity
Sulfur trioxide (SO3) 3.07 2.87 3.16 3.26 2.01
of the concrete pore solution, however this passivity can be dis- Sodium oxide (Na2O) 0.04 0.01 0.01 0.01 0.08
rupted and corrosion takes place. As corrosion is a gradual process Potassium oxide (K2O) 0.61 0.08 0.08 0.18 0.11
it is often difficult to detect its development in the early (initiation) Insoluble residue 0.54 1.80 1.29 0.35 0.26
Carbonic anhydride (CO2) 2.45 8.61 5.27 0.33 0.58
stages [11]. One of the processes behind these anomalies is con-
Free calcium oxide (CaO) 1.27 – – – –
crete carbonation. The natural carbonation of concrete depends C3S 78.37 84.36 80.89 70.42 73.43
simultaneously on the materials’ characteristics and the surround- C2S – – – 10.74 14.92
ing environment [12]. CO2 diffusion in the concrete mass will C3A 5.47 9.09 9.41 11.01 4.96
change its initially strongly alkaline environment to lower pH val- C4AF 8.79 0.49 0.52 0.64 1.10

ues, which will lower alkalinity of concrete to such an extent that Fineness – residue on 75 lm 0.5 0.4 0.4 0.9 10.3
steel embedded may rust and spall the concrete cover [4]. These sieve – 200%
Density (g/cm3) 3.09 2.99 2.99 3.05 3.07
parameters are key in evaluating the accessibility of aggressive
Specific surface (cm2/g) – Blaine 4190 4500 4380 3490 3950
agents and estimation of corrosion propagation. Water for normal consistency 29.8 33.0 31.4 28.2 31.8
Eventhough there are lots of research regarding carbonation for paste (%)
OPC mixtures in different levels (micro, macro, chemical and Initial set (h:min) 3:05 2:35 2:40 1:20 2:05
physical) and conditions ([12–27], among many others), there is Final set (h:min) 4:25 3:25 3:40 2:10 3:25
Expandability of Le Chatelier – 1.0 1.5 2.5 3.0 0.5
a lack of information in this field for WPC concretes. The differ- cold (mm)
ences in chemical components proportions are critical in compar- Expandability of Le Chatelier – 0.5 0.5 0.5 1.0 10.0
ing WPC with OPC because these differences reflect changes in warm (mm)
performance properties for both fresh and hardened concrete; Compressive strength (MPa)
characterizing these properties is critical. The objective of this 3 days 34.6 23.4 26.0 29.1 22.7
work is to assess the carbonation depth and the water absorption 7 days 40.7 31.3 35.4 36.7 33.1
28 days – 45.4 51.1 47.1 51.0
in WPC concretes and compare OPC samples in the same condition.
The compressive strength for the mixtures was used as control.

Table 2
2. Materials and methods Granulometry of fine and coarse aggregates.

Sieve size # % Retained

2.1. Materials
(mm)
Fine Coarse
Four types of white cement were used for producing concrete specimens, which aggregate aggregate
are identified herein as WPC1–4. A high initial strength OPC was produced as a con-
19.0 0 0
trol sample. It is similar to WPC because of (1) the absence of any additional sup-
12.5 0 61
plementary cementitious materials, and (2) the similar particle size distribution.
9.5 0 89
The OPC sample used as control had a composition similar to ASTM type I cement.
6.3 0 98
The chemical, physical, and mechanical characteristics of all the cements used are
4.80 0 99
described in Table 1. Granulometric distribution of the aggregates (sand and gravel)
2.40 5 100
are described in Table 2. A modified polycarboxylic ester superplasticizer base was
1.20 21 100
used in some mixes to maintain the necessary workability.
0.60 52 100
0.30 92 100
0.15 100 100
2.2. Mix proportions and specimen preparations <0.15 100 100
Maximum characteristic 2.4 mm 19.0 mm
A total of 15 mixtures were tested, with five different types of cement and three dimension
water/cement (w/c) ratio. Each mixture was repeated twice. The mix proportions Fineness module 2.70 6.88
are described in Table 3. The slump was fixed in 70 ± 10 mm. The concrete was pro- Density 2.63 kg/dm3 2.81 kg/dm3
duced and consolidated with mechanical equipment. After the samples were mixed,
they were left in molds for 24 h, removed, and then transferred to a cure chamber
with controlled temperature (23 ± 2 °C) and relative humidity higher than 95%.
After 28 days, the carbonation samples were placed in a homogenization cham- 2.3.2. Water absorption test
ber, while the water absorption samples were cut and dried on stove (60 °C) until Designed by Kelham [32], the water absorption test method consists on
the water loss was stabilized. More details on each test are described in the follow- 10  10  6 cm molded prisms that were cured for 28 days. At that point, the top
ing section. and bottom were cut from the prism to obtain a 2.5-cm-thick core section. This sec-
tion was kept at ambient temperature for one hour and then weighted and placed in
an oven at 110 °C until a steady mass was reached. The lateral surfaces were sealed
2.3. Test methods and procedures with epoxy resin to fix an unidirectional flux of water inside the sample. A plastic
lid was placed on top with a vent to allow air circulation. Samples were immersed
2.3.1. Compressive strength in pure water and the gain of mass was measured at 2, 5, 15 and 30 min and 1, 2, 3,
Samples were tested under compressive strength according to the Brazilian 6, 8, 24, 48, 72, 96 and 120 h intervals. The gain of mass was measured over time up
standard NBR 5739/2007 [28]; this standard correlates to ASTM C 39 [29]. The to the saturation of the sample, at which point the weight was considered stable.
cylindrical 9.5  19.5 cm samples were tested at 3, 14, and 28 days, three samples By graphing the mass gain over the root square of time, it possible to identify
of each type per age. ASTM C192 [30] was followed for making and curing the sam- two different phases during the absorption process. The first is related to capillary
ples, and ASTM C617 [31] for capping the cylindrical samples for compressive tests. water absorption itself, and the second is related to saturation of water. The
322 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330

Table 3 Table 5
Mix proportions. Parameters used for the statistical model.

Water/cement Sand Gravel Cement consumption Controllable factors Levels

ratio (kg/m3) (kg/m3) (kg/m3)
Water/cement ratio 0.40; 0.50; 0.60
0.40 699.0 1052 487.3 Age (for compressive strength) 3; 14 and 28 days
0.50 803.2 1052 382.7
0.60 870.5 1052 315.0
After 28 days of curing, the samples were kept in a closed chamber to decrease
and homogenize the internal humidity until weight difference between measure-
ments of two consecutive days were not higher than 1%. Samples had the top and
bottom faces sealed with paraffin and were transferred to a 100% CO2 carbonation
chamber in a room with 70 ± 2% relative humidity and a temperature 25 ± 1 °C. A
similar chamber was used by [25,26,34,35]. Although the CO2 gas concentration
used has been of 100% and it might be claimed that it modifies the carbonation rate,
in terms of comparison, this still valid for the current state of knowledge.
Measurements were made at four different ages, varying for each type of
cement–water/cement ratio, depending on the concrete characteristics. Samples
with 3-cm-thick layers were fractured out and freshly evaluated. The depth of car-
bonation was determined using phenolphthalein, which shows no color for a pH
lower than 9.2 and a violet color at higher pH levels when concrete is not car-
bonated. Measurements of 12 points on the surface were made (Fig. 1) for the depth
of carbonation.
The experimental program was statistically based to improve the reliability of
the test results. In this context, a variance test analysis was run for each property
studied to evaluate its relevance. Both multiple linear regression and nonlinear
regression for statistical analysis of the effects and interactions between the con-
trollable factors were used. Significance of the tests for the five types of cement
was evaluated with the software Statistica 5.0. The software Statgraphics and
SPSS 8.0 were used for linear regression analysis and non-linear regression, respec-
Fig. 1. Scheme of the measurement points in the cross section of the sample.
tively. They provide adjusted equations for each model tested, as well as the
parameters for the variance analysis and the r2 values for each analysis.

intersection of both lines is the nick point or saturation point. The absorption tax, in
g/cm2h1/2, is calculated using the slope ratio of the first line related to the effective 3. Results and discussion
absorption area of each sample. The capillary resistance, in h/m2, is the ratio
between saturation and the square of the sample’s thickness.
3.1. Compressive strength

2.3.3. Concrete carbonation

Carbonation tests were accelerated in laboratory in order to obtain faster
Variance analyses for compressive strength were developed
results. The samples—6  6  18 cm prisms—allowed for fracturing layers of 3 cm considering the different types of cement, the water/cement ratio,
to conduct the carbonation measurements, as recommended by RILEM [33]. and age of test. Results are shown in Table 4.

Table 4
Variance analysis: compressive strength.

Source SQ DF SQR F P value Effect

1 – water/cement 4193.36 2 110 920.38 0.000 Significant
2 – cement 83.28 4 110 18.28 0.000 Significant
3 – age 1223.76 2 110 268.60 0.000 Significant
Iteration 1–2 22.30 8 110 4.89 0.000 Significant
Iteration 1–3 0.36 4 110 0.08 0.989 Not significant
Iteration 2–3 9.51 8 110 2.09 0.043 Significant
Iteration 1–2–3 5.01 16 110 1.10 0.364 Not significant

where SQ, sum of squares; DF, degrees of freedom; SQR, sum of squared error; F: F-test, calculated; p = significance level, associated with the calculated value F.

Fig. 2. Compressive strength evolution: (a) over time, for different types of cement and w/c ratio 0.5. (b) As a function of water/cement ratio and type of cement, for 28 days.
 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330 323

Table 6 Tables 6 and 7 present variance analysis (ANOVA) for the model
Variance analysis of the multiple regression for the different concretes. and the calculated parameters for the isolated factors for each type
Parameters Coefficients Standard error t-Test P value of cement.
OPC Constant 1095.84 415.01 264.05 0.0127 It is important to note that in the variance analysis, when the p-
1/wc0.1 267.33 135.27 197.62 0.0568 value is lower than 0.01, the correlation between variables is sta-
a0.1 371.26 141.89 261.65 0.0134 tistically significant at a confidence level of 99%. For each type of
wc0.1/a0.1 424.46 137.71 308.23 0.0042 cement, the following equations were established by adjusting
WPC1 Constant 221.22 192.96 114.64 0.0000 the linear multiple regression results of the compressive strength
1/wc5 0.16 0.03 296.49 0.0060 (Eqs. (1)–(5)):
a0.9 120.64 229.13 526.54 0.0000
wc0.1/a0.1 179.17 165.28 108.41 0.0000
wc0:1 1
WPC2 Constant 330.57 0.78 424.25 0.0000 fcOPC ¼ 1095:8  424:5   267:3  0:1  371:3  a0:1 r2 ¼ 92:6%
a0:1 wc
1/wc0.5 0.38 0.03 126.47 0.0000
1/a2 276.32 0.22 124.60 0.0000 ð1Þ
wc10/a0.1 0.12 0.01 822.16 0.0000
WPC3 Constant 158.25 113.84 139.00 0.0000 1 wc0:1
1/wc0.1 172.05 107.80 159.60 0.0000 fcWPC1 ¼ 221:2  0:16   179:2  0:1  12:1  a0:9 r2 ¼ 95:9%
wc5 a
a1 194.92 353.40 551.556 0.0000
wc4/a0.1 192.15 0.66 292.415 0.0076 ð2Þ
WPC4 Constant 162.24 168.12 965.068 0.0000
1/wc 50.81 134.79 376.982 0.0010 1 wc10 1
a5 0.49 0.20 241.655 0.0240 fcWPC2 ¼ 33:1 þ 0:38  5
 0:12  0:1  2:8  2 r2 ¼ 96:5%
wc0.1/a0.1 137.15 148.36 924.442 0.0000
wc a a
ð3Þ

1 a4
Table 7 fcWPC3 ¼ 158:2 þ 172:1  0:1
þ 19:5  a  1:9  0:1 r 2 ¼ 93:3%
Parameters of the analyzed factors for compressive strength for the different wc wc
concretes. ð4Þ
Source SQ DOF MQ F P value
OPC Model 2019.24 3 673.08 133.99 0.000 wc0:1 1
Residue 160.742 32 502.32 – –
fcWPC4 ¼ 162:2  137:2  þ 5:1   0:49  a5 r 2 ¼ 97:0%
a0:1 wc
Total 2179.98 35 – – –
ð5Þ
WPC1 Model 1879.23 3 625.41 227.29 0.000
Residue 797.979 29 275.17 – – where:
Total 1956.03 32 – – –
wc = water/cement ratio;
WPC2 Model 2889.59 3 963.20 253.46 0.0000
Residue 106.405 28 380.02 – –
a = age.
Total 2996.00 31 – – –
WPC3 Model 2111.90 3 703.97 107.02 0.0000
The high r2 obtained from the modeling of compressive strength
Residue 151.30 23 657.80 – – means that at least 92% of the experimental data fits the model.
Total 2263.20 26 – – – Observed and expected values for compressive strength are
WPC4 Model 2875.72 3 958.57 245.66 0.0000 presented in Fig. 3. Good correlation was observed when the real
Residue 897.47 23 390.21 – – values obtained from testing were compared with the values
Total 2965.47 26 – – – obtained from the model.
The models show a good correlation between the predicted and
observed values. Fig. 4 shows the predicted compressive strength
values for each cement and water/cement ratio.
The isolated factors in order of importance are: water/cement All white concrete studied present lower strength than the OPC
ratio, age, type of cement, and iteration between water/cement used as a control, except for concretes WPC2–4 with w/c 0.4.
ratio and cement type, as well as iteration between type of cement However, the difference in strength was lower than 10% in all
and age; these were statistically significant in the results of the cases, and for this reason it is considered that the white concrete
compressive strength. studied have similar performance to control OPC for the different
Fig. 2 shows the average of compressive strength as function of w/c ratio. A difference in cement composition has to be taken into
the iteration between age and type of cement. Note that the com- account, since white cement has generally more C3A and C3S than
pressive strength of the concretes with different cements increased normal OPC. Besides, white cement is ground finer, with smaller
at different rates: after 3 days the WPC4 had only 66% of its final particles. That means they present higher strength in early ages,
strength at 28 days, while the OPC had 81%. The other cements however with the progress of the reaction to up to 28 days, there
had about 70% of their final strength on day 3. is a tendency that white cement and OPC concretes will present
Fig. 2b shows the values for compressive strength at 28 days for similar strength. These results are consistent with those found by
all types of cement based on the water/cement content of the con- Benitez et al. [36] who, using a water/cement ratio of 0.35, found
crete produced. Note that the influence of the water/cement ratio values 20%, 18%, and 12% higher for WPC than for the control
differs depending on the type of cement. The OPC showed higher OPC used herein for ages of 3, 7, and 28 days, respectively. Katz
compressive strength at 14 days, but at 28 days, the WPC3 cement [37] obtained for WPC concrete values 70% and 22% higher than
demonstrated comparable compressive strength. Cements type those measured for the control sample at 7 and 28 days. Ferraro
WPC4 and WPC2 showed similar behavior. and Nanni [9] obtained 36 MPa in specimens of WPC with 0.44 of
Results obtained for each type of cement were modeled to a lin- w/c ratio, using 471 kg/m3 of cement at 28 days. Lubeck et al. [7]
ear multiple regression. The parameters defined as controllable found similar results in white concretes with similar w/c ratio
factors and used for the statistical analysis are listed in Table 5. and amounts of cement.
324 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330

Fig. 3. Compressive strength for concretes with the different types of cement, observed and expected: (a) OPC. (b) WPC1. (c) WPC2. (d) WPC3. (e) WPC4.

3.2. Carbonation Statistical data treatment for carbonation in concrete was made
by a nonlinear multiple regression with software SPSS 8.0. It
Depth of carbonation was analyzed. This method is widely used defined a trend curve through the points and then analyzed the
in research, as it is an easy way to measure the entrance of CO2 in determining factors for each model. The proposed statistical model
concrete. As in concrete, the carbonation faces are not regular; the for carbonation in concrete is shown in Eq. (6):
average of the faces 2 (lateral left) and 4 (right lateral) (Pmf24)
(indicated in Fig. 1) were chosen as parameter because those are Pmf 24 ¼ B0  wcB1  aB2 r2 ¼ 74:7% ð6Þ
the faces that indicate the progress of the carbonation front with
time. Faces 1 and 3 were the top and bottom faces during the where:
molding process and did not present regular results, which was Pmf24 = Average depth of carbonation for faces 2 and 4 (cm);
probably due to bliding. For this reason, these values were not used wc = water/cement ratio;
for the calculation. a = age (days).
 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330 325

mixtures with different contents of limestone (LS) filler, increas-

ing the LS content always led to a significant increase of the car-
bonation depth, mainly because the LS appeared to act only as a
filler material. The authors suggested that the LS content in con-
crete used as a replacement for PC should not exceed 15%;
beyond this limit, a substantial increase in the carbonation depth
(over 80%) was recorded in their experiment. However, decreas-
ing w/c resulted in a significant reduction in the carbonation
depth and the drawback of using this kind of cement can be miti-
gated as can be seen in Fig. 8.
In the same way, values for specific surface (blaine) followed
the same tendency as the carbonation: Sample WPC1 has higher
specific surface (4500 cm2/g), followed by WPC2 and WPC4, and
a lower specific surface is found in the WPC3 (3490 cm2/g).

Fig. 4. Compressive strength for the various concretes at different w/c ratio at
28 days.

Eqs. (7)–(11) define the values for B0, B1, and B2, as well as the
r2, for each type of cement. Values observed and estimated for
depth of carbonation for each type of cement are presented in
Fig. 5:

Pmf 24ðOPCÞ ¼ 2579:5  wc13:8  a0:5 r 2 ¼ 86:0% ð7Þ

Pmf 24ðWPC1Þ ¼ 53  wc6:5  a0:6 r 2 ¼ 75:0% ð8Þ

Pmf 24ðWPC2Þ ¼ 245  wc9:3  a0:5 r2 ¼ 80:0% ð9Þ

Pmf 24ðWPC3Þ ¼ 332  wc12:8  a0:5 r 2 ¼ 75:0% ð10Þ

Pmf 24ðWPC4Þ ¼ 217:3  wc10:33  a0:5 r2 ¼ 77:4% ð11Þ

Carbonation curves representing the predicted values for depth
of carbonation can be used as a reference for predicting and com-
paring the potential for carbonation in all the studied cements
since at least 75% of the variability shown by the observed values
is addressed in adjusting the curves of concrete analyzed. Note that
in all the figures that there is a good correlation between the pre-
dicted curves and the observed values. An increase in the depth of
carbonation with an increase in the w/c ratio is observed in Fig. 6
as expected, since w/c ratio is directly related to porosity.
An analysis of all concretes demonstrates that concrete sample
WPC3—even with a high w/c ratio—reacts better to carbonation
than concrete sample WPC1 with a w/c ratio 0.5. In addition, esti-
mated values for the concrete with a w/c ratio 0.5 nearly equaled
the values found for all cements with a w/c ratio 0.4. This proves
again that, besides the w/c ratio, the type of cement is significant
in terms of carbonation levels. In this case, the better behavior of
the WPC3 and WPC4 can be explained by its physical and chemical
composition (Fig. 7).
For the chemical point of view the white Portland cements
used differ mainly by the CaCO3 content. Table 1 presents the val-
ues of carbonic anhydride (CO2) 2.45; 8.61; 5.27; 12.33 and
12.58, which corresponds approximately to a level of CaCO3
5.5%, 19.6%, 12%, 0.7% and 1.32%, respectively for the OPC and
WPC1–4. The WPC1 cement (19.6% CaCO3) shows the greatest
depth of carbonation, and that the WPC3 cement (0.7% CaCO3)
shows the best performance. This result indicates that the lime-
stone filler used to grind the clinker during WPC production gen- Fig. 5. Estimated and observed values for depth of carbonation for concretes
erated a negative effect on carbonation resistance. In the same produced with different cements: (a) OPC; (b) WPC1; (c) WPC2; (d) WPC3; and (e)
way Meddah et al. [38] found similar behavior analyzing OPC WPC4.
326 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330
Fig. 6. Prediction curves for depth of carbonation according to the water/cement
ratio.
Venquiaruto et al. [39] found higher depths of carbonation for
concretes with addition of fine particles when studying concretes
with different amounts of mineral additions. However, they
explain it as a function of the higher reactivity of the finest addi-
tion, which combines faster with Ca(OH)2 in the mix.
The loss of ignition measures the proper degree of sintering and
the natural aging of the cement (setting of the most volatile anhy-
drous components, water vapor in air causing incipient hydration,
and, as consequence a reduction of mechanical strength).
Carbonation of concrete with WPC followed the same trend as
the loss of ignition, i.e., the higher the loss of ignition, the higher
the carbonation. Values for loss of ignition are between 2.09 and
9.37, which are within the limit of the Brazilian standard NBR
12989 [40], however exceed the limit of the ASTM C150 [2], which
is of 3%.
Fig. 8 presents the expected values for depth of carbonation at
28 days of each type of cement for the three w/c ratios analyzed.
Fig. 7. Results from the characterization of each type of cement compared to depth of carbonation.
3.2.1. Correlation between compressive strength and carbonation
The compressive strength was correlated with depth of car-
bonation (Fig. 9); Since CO2 enters the concrete as it matures, there
is a corresponding increase in strength. Eqs. (1)–(5) were used to
estimate the compressive strength, and Eqs. (7)–(11) to determine
the depth of carbonation.
Observing the different concrete together, a reasonable sta-
tistical correlation was found for the depth of carbonation
(r2 = 80.5%, Fig. 12b). This factor increases when analyzing every
type of concrete separately due to the influence of the different
chemical composition of cements on the carbonation; see Fig. 10.
Values found for each relationship were the same for all types of
concrete. However, there is a difference among the curves: con-
crete carbonation has a good correlation with compressive
strength when evaluating for every type of cement, as values for
r2 are at least 98.5%, and higher than 99% for the majority of the
cases.
In general, the depth of carbonation decrease with an increase
in compressive strength, similar behavior were found by
[12,15,16,21,23], and others, for OPC samples. However for a w/c
ratio 0.6, the OPC presented higher values for carbonation parame-
ters even with a higher compressive strength when compared to
the WPC samples. This proves that the total porosity that governs
the compressive strength is not the only factor influencing the con-
crete carbonation: the pore structures and the cement chemistry
play an important role as well.
3.3. Capillary water absorption
The obtained values for the absorption rate were used to calcu-
late the curve for predicting capillary resistance, while the
obtained values for capillary resistance were used to predict the
absorption rate curve. After a trial adjustment, Eq. (12) was
developed:
1
Ar ¼ 29:05 ð12Þ
M0:6
where:
Ar = Absorption rate (g/cm2 h1/2);
M = Capillary resistance (h/m2);
 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330
Fig. 8. Average depth of carbonation for faces 2 and 4 for the five types of concrete after 28 days of accelerated carbonation tests.
Fig. 9. Relationship with compressive strength for all the cements after 28 days of
testing for depth of carbonation for faces 2 and 4.
Fig. 11 presents values for absorption rate as a function of the
iteration between types of cement and w/c ratio. For an assessment
of type of cement and w/c ratio and their iterations, an initial
analysis of all types of cement studied was developed using the
software Statistica, showing the significancy of each iteration,
which results are presented in Table 8.
The statistical treatment for absorption rate for concretes was
developed using multiple regression nonlinear analysis by defining
a trend curve and assigning trial values. The proposed model is
presented in Eq. (13):
B1
Ar ¼ B 0 
wcn
Values for B0, B1, and n, for each type of cement are presented in
Table 9. The model for absorption rate is presented in Fig. 13,
which represents the behavior expected for each concrete.
327
Fig. 10. Relationship between compressive strength for each type of cement after
28 days of testing with depth of carbonation.
As shown in the model curves (Fig. 12) and in the iteration
curves (Fig. 11), the better performance of WPC2 samples is
obvious when compared to the other samples. As expected for all
samples, the higher the w/c ratio, the higher the water absorption.
Fig. 13 presents the correlation between capillary absorption
rate and compressive strength for all concrete studied at 28 days.
A good correlation between the absorption rate for each type of
concrete and the compressive strength is observed, as noted that
WPC2 has, for w/c ratio 0.4, compressive strength 3.61% higher
than for OPC samples, while its absorption rate was 42.17% lower.
However, compressive strength cannot be alone taken into account
ð13Þ
as the property governing water absorption rate in concrete. OPC
presented a compressive strength 10.23% higher for water/cement
ratio 0.6 when compared to WPC2, while the absorption rate was
13.48% lower.
328 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330

Fig. 13. Water absorption rate versus compressive strength for all types of cement
at 28 days.

Fig. 11. Absorption rate for all types of cement.

Table 8
Variance analysis of the influence of cement and w/c on the water absorption.

Source SQ DOF SQR P value Effect

1 – cement 0.735 8 144 0.004 Significative
2 – w/c ratio 0.686 4 144 0.000 Significative
Iteration 1–2 0.689 16 144 0.031 Significative

Table 9
Values for B0, B1, and n for each type of cement.

OPC WPC1 WPC2 WPC3 WPC4

B0 0.110 0.1105 0.092 0.110 0.125
B1 0.0001 0.0016 0.00015 0.0003 0.0055
n 5.80 3.18 6.0 4.80 2.50
r2 60.0% 90.0% 93.0% 91.0% 89.0%

water absorbed after 4 h of wetting. This implies that short-term

Fig. 12. Expected values for absorption rate for all types of cement.
While compressive strength is governed by the total porosity,
the absorption rate depends not only in the total porosity but
mainly in the pore structure: intercomunicability, distribution,
diameter, etc. In this case, when the type of cement is altered,
the direct relation between absorption rate and compressive
strength is changed due to the chemical and granulometric differ-
ences that affect the formation of concrete microstructure.
In addition to the correlation with compressive strength,
expected values for absorption rate and depth of carbonation were
correlated, as presented in Fig. 14.
A good correlation between absorption rate and depth of car-
bonation had already been predicted by [5]: tests for water
permeability or surface absorption of water had good correlation
with experimental carbonation in their research since the same
type of binder is used. Rabehi et al. [23] found that carbonation
depth increases with the initial absorption of concretes. Also
Parrot [41] showed that after 1.5 years of exposure, the depth of
carbonation in site and laboratory samples can be related to the
absorption gives an indirect information on the continuity of the
pore system in the near surface zone, which in turn is vulnerable
to carbonation if very permeable [5]. They observed that these
tests could be a good indicator of the concrete behavior with
respect to carbonation. The authors believe that this highlights
the role played by the open porosity of the cover concrete on its
carbonation, but good estimation of the carbonation depth can
only be determined by tracking the initial absorption of concrete
in the first hour of exposure.
However Kulakowski et al. [16] and Bai et al. [42] argue that this
behavior is only valid when concrete has no supplementary
cementitious materials (SCMs), as increasing SCMs content (in
their studies silica fume and metakaolin) reduces the absorption
rate in concrete, but increases carbonation. Also Shi et al. [4] stud-
ied high strength concrete using fly ash and blast-furnace slag, the
results showed that the relationship between compressive
strength and gas permeability strongly depends on water/binder
(w/b) ratios and mineral admixture types. The authors confirmed
a closer relationship between gas permeability and carbonation
of OPC and attributed to the reason that, although compressive
strength, gas permeability and carbonation rate are all related to
pore structure of concrete matrix, they greatly depend on different
specific pore structure parameters.
 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330
Fig. 14. Relationship between water absorption rate and depth of carbonation for
faces 2 and 4 for all the concretes at 28 days.
4. Final remarks
Results observed in this research show that, regarding concrete
carbonation, the type of cement plays a major role, as does the w/c
ratio. Physical and chemical analyses of the cements show that the
higher the loss on ignition, the insoluble residue, the carbon diox-
ide, and the specific surface of the cement, the larger the carbona-
tion. There is a clear influence of the manufacturing process and/or
chemical composition in the durability of the cement.
At the same time, when the compressive strength increased,
values for depth of carbonation were significantly reduced.
However, compressive strength is not a suitable parameter for
estimating the durability of concrete due to the carbonation front.
Porosity, which governs the compressive strength, is not the only
factor influencing the carbonation of concrete, and the pore struc-
ture and chemistry of the cement are also relevant aspects.
The capillary water absorption pattern confirm that white
Portland cement shows satisfactory performance despite the
increased rate of water absorption by capillarity action, while
water permeability or surface water absorption tests present a
good correlation with carbonation for the same type of cement,
as this will directly influence the formation of the internal struc-
ture and chemistry of the concrete pore water.
Acknowledgments
The authors acknowledge the financial support of CAPES
(Coordenação de Aperfeiçoamento de Pessoal de Nível Superior –
Ministério da Educação – Brazil) and CNPq (Conselho Nacional de
Desenvolvimento Científico e Tecnológico – Ministério da Ciência
e Tecnologia – Brazil).
References
[1] Jang H, Kang H, So S. Color expression characteristics and physical properties of
colored mortar using ground granulated blast furnace slag and white Portland
cement. KSCE J. Civ. Eng. 2014;18:1125–32.
[2] ASTM, STM C150/C150M – 12 standard specification for Portland cement.
ASTM Int.; 2012.
329
[3] Hamad BS. Investigations of chemical and physical properties of white cement
concrete. Adv Cem Based Mater 1995;2(95):161–7.
[4] Shi H, Xu B, Zhou X. Influence of mineral admixtures on compressive strength,
gas permeability and carbonation of high performance concrete. Constr Build
Mater 2009;23:1980–5.
[5] Basheer L, Kropp J, Cleland DJ. Assessment of the durability of concrete from its
permeation properties: a review. Constr Build Mater 2001;15:93–103.
[6] Veiga KK, Gastaldini ALG. Sulfate attack on a white Portland cement with
activated slag. Constr Build Mater 2012;34:494–503.
[7] Lübeck A, Gastaldini ALG, Barin DS, Siqueira HC. Compressive strength and
electrical properties of concrete with white Portland cement and blast-furnace
slag. Cem Concr Compos 2012;34:392–9.
[8] Dellinghausen LM, Gastaldini ALG, Vanzin FJ, Veiga KK. Total shrinkage, oxygen
permeability, and chloride ion penetration in concrete made with white
Portland cement and blast-furnace slag. Constr Build Mater 2012;37:652–9.
[9] Ferraro RM, Nanni A. Effect of off-white rice husk ash on strength, porosity,
conductivity and corrosion resistance of white concrete. Constr Build Mater
2012;31:220–5.
[10] De Muynck W, Ramirez AM, De Belie N, Verstraete W. Evaluation of strategies
to prevent algal fouling on white architectural and cellular concrete. Int
Biodeterior Biodegrad 2009;63(6):679–89.
[11] Andrade C, Buják R. Effects of some mineral additions to Portland cement on
reinforcement corrosion. Cem Concr Res 2013;53:59–67.
[12] Monteiro I, Branco FA, De Brito J, Neves R. Statistical analysis of the
carbonation coefficient in open air concrete structures. Constr Build Mater
2012;29:263–9.
[13] Neves R, Branco F, De Brito J. Field assessment of the relationship between
natural and accelerated concrete carbonation resistance. Cem Concr Compos
2013;41:9–15.
[14] Saetta AV, Schrefler BA, Vitaliani RV. Moisture, heat and carbon dioxide flow,
vol. 23; 1993, pp. 761–72.
[15] Ho DWS, Lewis RK. Carbonation of concrete and its prediction, Cem Concr Res
1987; 17(c): 1005–8.
[16] Kulakowski MP, Pereira FM, Dal Molin DCC. Carbonation-induced
reinforcement corrosion in silica fume concrete. Constr Build Mater
2009;23:1189–95.
[17] Morandeau A, Thiéry M, Dangla P. Investigation of the carbonation mechanism
of CH and C–S–H in terms of kinetics, microstructure changes and moisture
properties. Cem Concr Res 2014;56:153–70.
[18] Thiery M, Villain G, Dangla P, Platret G. Investigation of the carbonation front
shape on cementitious materials: effects of the chemical kinetics. Cem Concr
Res 2007;37:1047–58.
[19] Turcry P, Oksri-Nelfia L, Younsi A, Aït-Mokhtar A. Analysis of an accelerated
carbonation test with severe preconditioning. Cem Concr Res 2014;57:70–8.
[20] Visser JHM. Influence of the carbon dioxide concentration on the resistance to
carbonation of concrete. Constr Build Mater 2013;67:8–13.
[21] Marques PF, Chastre C, Nunes Â. Carbonation service life modelling of RC
structures for concrete with Portland and blended cements. Cem Concr
Compos 2013;37:171–84.
[22] Duprat F, Vu NT, Sellier A. Accelerated carbonation tests for the probabilistic
prediction of the durability of concrete structures. Constr Build Mater
2014;66:597–605.
[23] Rabehi M, Mezghiche B, Guettala S. Correlation between initial absorption of
the cover concrete, the compressive strength and carbonation depth. Constr
Build Mater 2013;45:123–9.
[24] Chang CF, Chen JW. The experimental investigation of concrete carbonation
depth. Cem Concr Res 2006;36:1760–7.
[25] Castellote M, Andrade C, Turrillas X, Campo J, Cuello GJ. Accelerated
carbonation of cement pastes in situ monitored by neutron diffraction. Cem
Concr Res 2008;38:1365–73.
[26] Galan I, Andrade C, Castellote M. Natural and accelerated CO2 binding kinetics
in cement paste at different relative humidities. Cem Concr Res 2013;
49:21–8.
[27] Pihlajavaara SE. Some results of the effect of carbonation on the porosity and
pore size distribution of cement paste. Materiaux Constr 1968;1:521–7.
[28] Associação Brasileira de Normas Técnicas ABNT. NBR 5739 – Concreto: ensaio
de compressão de corpos-de-prova cilíndricos; 1994.
[29] ASTM:C39/C39M-12a. Standard Test Method for Compressive Strength of
Cylindrical Concrete Specimens. ASTM Int.; 2012, pp. 1–7.
[30] ASTM:C192/C192M-13. Standard practice for making and curing concrete test
specimens in the laboratory. ASTM Int.; 2013, pp. 1–8.
[31] ASTM:C617/C617M-12. Standard practice for capping cylindrical concrete
specimens. ASTM Int.; 2012, pp. 1–6.
[32] Kelham S. A water absorption test for concrete. Mag Concr Res
1988;40(143):106–10.
[33] RILEM. Measurement of hardened concrete carbonation depth: Rilem
Recommendation CPC-18. Mater Struct 1984; 02: 435–40.
[34] Mohammed MK, Dawson AR, Thom NH. Carbonation of filler typed self-
compacting concrete and its impact on the microstructure by utilization of
100% CO2 accelerating techniques. Constr Build Mater 2014;50:508–16.
[35] Castellote M, Andrade C. Modelling of the carbonation of concrete (UR-CORE)
from fractional conversion data obtained through in situ monitored neutron
diffraction experiment. Rev Ing Constr 2009;24:245–58.
[36] M.E. Benitez A, Balzamo H. Estudio de hormigones convencionales elaborados
con cemento gris y cemento blanco utilizando un aditivo de doble efecto. In
4th Jornadas de desarrollo e innovación; 2002.
330 A.P. Kirchheim et al. / Construction and Building Materials 84 (2015) 320–330
[37] Katz A. Properties of concrete made with recycled aggregate from partially
hydrated old concrete. Cem Concr Res 2003;33:703–11.
[38] Meddah MS, Lmbachiya MC, Dhir RK. Potential use of binary and composite
limestone cements in concrete production. Constr Build Mater
2014;58:193–205.
[39] Venquiaruto SD, Isaia GC. A influência do teor e da quantidade de adições
minerais na carbonatação do concreto. In Congresso Brasileiro do Cimento,
43°, Foz do Iguaçu, 2001. Anais... São Paulo: Instituto Brasileiro do Concreto,
2001.
[40] Associação Brasileira de Normas Técnicas (ABNT). NBR 12989 – Cimento
Portland branco; 1993.
[41] Parrot LJ. Water absorption of cover concrete. Mater Struct
1992;49(25):284–92.
[42] Bai J, Wild S, Sabir BB. Sorptivity and strength of air-cured and water-cured PC-
PFA-MK concrete and the influence of binder composition on carbonation
depth. Cem Concr Res 2002;32:1813–21.