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h i g h l i g h t s
" The colorimetric method can be an easy and practical alternative means to estimate the penetration depth of chloride ion.
" To use a silver nitrate concentration exceeding 0.05 N is recommended if the penetration depth of chloride ion is measured.
" The measurement of penetration depth by the colorimetric method is not practical if the pH of concrete is below 10.
a r t i c l e i n f o a b s t r a c t
Article history: The purpose of the present study are to properly estimate diffusion coefficient and determine the concen-
Received 12 June 2012 tration of sprayed silver nitrate (AgNO3) that corresponds with the critical chloride amount. We also pro-
Received in revised form 14 November 2012 pose a suitable guide for application of the colorimetric method through indoor and field tests.
Accepted 16 November 2012
According to the results, the colorimetric method using AgNO3 showed distinguished change to white
Available online 10 January 2013
reaction (AgCl) from brown reaction (AgOH). Any concentration (more than 0.05 N) of AgNO3 is useful in
evaluation of the diffusion coefficient and is available regardless of age. The model equation for the rela-
Keywords:
tionship between Da (the concentration profile according to distance from the surface) and Dc (the pen-
Colorimetric method
AgNO3
etration depth of the colorimetric method) is also proposed. When AgNO3 of 0.1 N is sprayed, free
Critical chloride content chloride amount (0.045%/1.08 kg/m3) of the color-change border is similar to the critical chloride content
Diffusion coefficient where corrosion is observed. Measurement of penetration depth by the colorimetric method is not appro-
priate when the pH of concrete is below 11.
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction electrical field is artificially used and the applied high voltage leads
to an increase in temperature. Namely, this method cannot be
The chloride diffusion coefficient in concrete is important in applied to real structures. Recently, a new method has been intro-
estimating limits on the life time of structures due to corrosion duced to determine the depth of chloride penetration wherein
as well as for expressing the penetration velocity of chloride. 0.1 N silver nitrate (AgNO3) aqueous solution is sprayed on a
Accordingly, numerous estimation methods have been introduced cross-section of split concrete [5]. This test method is often called
to obtain the chloride diffusion coefficient of concrete [1–9]. The the colorimetric method, because the spraying of 0.1 N AgNO3 solu-
representative method is estimation of the diffusion coefficient tion on a cross-section of split concrete subjected to penetration of
using a general solution of Fick’s second law [2]. This method is chloride leads to the formation of white and brown regions with
completed by measuring the chloride ion amount according to well-distinguished boundaries [5,10]. The colorimetric method is
the distance from the concrete surface. This method, however, en- used extensively in many areas such as RCPT and CMT. Because test
tails a complicated procedure and prolonged test time for measur- process is simple and quick, this method has been used to widely
ing chloride. evaluate the penetration characteristics of chloride (Da).
To mitigate these problems, acceleration tests (rapid chloride However, the colorimetric method has been used without
penetration test (RCPT), chloride migration test (CMT)) have been sufficient investigation into the reaction mechanism and use scope
proposed and revised [3,4]. However, these acceleration followed in condition of corresponding structures. Namely, W/C,
approaches cannot address real diffusion problems, because the age, concentration of AgNO3, and the chloride amount of the col-
or-change border and so on also should be defined [10]. These fac-
⇑ Corresponding author. tors can be regarded as restrictions to the application of the
E-mail address: eiyang@gwnu.ac.kr (E.-I. Yang). colorimetric method under various environmental conditions.
0950-0618/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2012.11.084
240 M.-Y. Kim et al. / Construction and Building Materials 41 (2013) 239–245
The objectives of this research are to properly estimate the dif- Table 1
fusion coefficient and determine the concentration of sprayed Physical properties of aggregates.
AgNO3 that corresponds with the critical chloride amount. In this Item Specific gravity Absorption (%) FM
study, through indoor and field tests, a guideline is proposed for Type
application of the colorimetric method. Studies on the reaction Sand 2.59 1.01 2.65
principle and the factors affecting the colorimetric method, as well Gravel 2.78 0.62 6.80
as on the characteristics of the color-change border by carbonation
and concrete properties are conducted. In order to ensure the reli-
ability of the colorimetric method, the chloride diffusion coeffi-
Table 2
cient (Da) by the colorimetric method is compared with that (Dc) Mixture proportions of concrete.
by Fick’s law [2]. On the basis of an indoor experiment, a field test
was executed to estimate the field applicability of the colorimetric W/C (%) S/a (%) Unit weight (kg/m3)
method. W C S G
40 43 170 425 721 1022
2. Mechanism of colorimetric method 50 45 172.5 345 782 1021
60 46 175 292 816 1024
d½AgOH
In this test, the cylindrical concrete specimens of 100 mm diameter and v2 ¼ ¼ k2 ½Agþ ½OH ð2Þ
100 mm height were used to examine the diffusion coefficient and concentration dt
of the color-change border with mixture proportions of the concrete. Mixture pro-
K
portions of concrete are given in Table 2. After removal of the mold, specimens were ½Cl 0 ½AgCl ½OH 0 ½AgOH
¼ ) Y ¼ XK ð3Þ
stored for 7 days in saturated limewater at a temperature of 20 ± 3 °C. ½Cl 0 ½OH 0
Considering the maximum solubility of Cl, OH, and Ag, the mole ratio given in
3.3. Test variables
Table 4 was used to obtain the factors affecting color-change.
Test variables are given in Table 3. The objectives of this study are to review the
mechanism of the colorimetric method, investigate the influencing factors, and con- 3.4.2. Chloride penetration test and estimation of diffusion coefficient
firm the applicability in situ. For influencing factors, reaction velocity, Cl:OH ratio, Penetration of chloride was performed by an immersion test using NordTest
and carbonation in the color-change border were investigated. Also, it was neces- method of NT Build 443 [12]. Seawater was used in the immersion solution. The dif-
sary to determine the most suitable sprayed concentration of silver nitrate and fusion coefficient was calculated each from the immersed specimen by measuring
Table 3
Test variables.
both the concentration profile according to distance from the surface (Dc) and the
penetration depth of the colorimetric method (Da). Equation to calculate the diffu-
sion coefficient is as follows:
Cðx; tÞ x
¼ 1 erf pffiffiffiffiffiffi ð4Þ
C0 4 Dt
!2
xd
Da ¼ pffiffiffiffiffi ð5Þ
yd 4t
1 Cd Ci
yd ¼ erfc ð6Þ
C0 Ci
0.10
Concentration of AgNO 3 Color-change of concrete
0.08
Reaction velocity of AgCl
0.03N
0.06
0.04
0.02 0.04N
0.00
8 0.1N AgNO3
2
Table 6
-12
0
0.35 0.40 0.45 0.50 0.55 0.60 0.65
W/C
10 0.10
W/C=0.4 free chloride
Diffusion coefficient (10 m /s)
W/C=0.5
8 W/C=0.6 0.08
-12
6 0.06
4 0.04
2 0.02
0
0.00
8 12 16 20 24 28 32 36
0.03N 0.04N 0.05N 0.1N
Immersion age (weeks) AgNO3 concentration
Fig. 6. Diffusion coefficient (Da) with age.
Fig. 8. Chloride concentration with AgNO3 concentration at the color-change
coefficient (Da) evaluated for spraying AgNO3 of 0.1 N is less than border.
Da
Dc ¼ ð9Þ
1:4 ðW=CÞ1:5
Chloride concentration (%)
0.08
Table 7
Field test results in marine structures.
Table 8
Field test results in pavement structures.
(b) pH-11 However, the chloride depth and carbonation depth were almost
identical in the case of WY and KJ. The carbonation depth was dee-
per than the chloride depth in GOS. In these cases (WY, KJ, and
GOS), it is not reliable to estimate the depth of the color-change
border. This means that, when carbonation depth is deeper than
that of chloride depth, we cannot recognize the true chloride depth
and, accordingly, it is impossible to apply the colorimetric method
related to the depth.
Therefore, when RC structures receive salt damage and carbon-
ation at the same time, measurement of carbonation depth is very
important before application of the colorimetric method. Accord-
ing to the concentration at the color-change border, the chloride
concentration (1.05 kg/m3) examined in the field was almost sim-
ilar to the free chloride concentration (1.08 kg/m3) determined via
a laboratory test.
(c) pH-12
4.5.2. Pavement structures exposed to deicing salt
Deicing salt is widely used to reduce traffic accidents due to
snowfall or icy conditions in winter. The use of deicing salt, how-
ever, can cause corrosion of bridge structures. This research exam-
ined salt damage using the colorimetric method. Four national
roads situated in the northern region of South Korea were selected
for the study (Table 8).
According to the results, while carbonation depth was mea-
sured to be less, chloride penetration due to the use of deicing salts
was measured as roughly 26 mm on the national roads. As carbon-
ation depth was less than the chloride penetration depth, estima-
tion of the penetration depth and diffusion coefficient is easily
accomplished using the colorimetric method. Concentration at
the color-change border was an average of 1.27 kg/m3 and was
(d) pH-13
similar to the results from lab experiments and marine structure
Fig. 10. Color-change with concentration of AgNO3 and chloride. evaluations.
5. Conclusions
4.5.1. Marine structures exposed to coastal environment
In the case of marine structures, the service life was 5–40 years, The goals of this study are to properly estimate diffusion coeffi-
and they are located at splash (2), coast (2), and air zones (3). Field cient and determine the concentration of sprayed silver nitrate
test results are shown in Table 7. According to the results, the (AgNO3) that corresponds with the critical chloride amount. We
chloride in the splash zone penetrated deeper into the concrete. also proposed a suitable guide for application of the colorimetric
M.-Y. Kim et al. / Construction and Building Materials 41 (2013) 239–245 245
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