A study of the degradation of marine concrete

under the coupled effect of wettingdrying

cycles and bending loads
J. Liu*1, J. Deng 2, H. Qin 2, P. Zhang3, C. Pang 3 and W. Sun3
Marine concrete with excellent salt corrosion resistance was cast, followed by ultrasonic testing
technology, chemical analysis of free chloride ion and calculation of the chloride ion diffusion
coefficient to investigate the degradation of the marine concretes subjected to wettingdrying
cycles and bending loads during their exposure to a marine environment. Additionally, an indoor
accelerated corrosion test was conducted. The effects of the water-to-binder ratio, mineral
admixtures, bending loads and other factors on the durability of the marine concrete were
investigated, and initial primary correlation between marine exposure conditions and the indoor
accelerated corrosion test was established based on the diffusion coefficient of chloride ions.
Keywords: Marine concrete, Marine exposure, Indoor accelerated corrosion, Multi-factors coupling, Correlation

Introduction
In practical engineering, the degradation level of concrete
is determined by mechanical, chemical, physical and
other environmental factors. In the marine environment,
the abundant chloride and sulphate salts are responsible
for the chemical corrosion of the concretes. To make it
worse, the damage to concretes in the tidal zone is exacerbated because of the wettingdrying cycles.14 For loaded
concretes, increased internal micro-cracks and propagation of existing cracks were observed, resulting in a
network of micro-cracks that may be potential transmission channels. In this case, penetration of aggressive
media into the concrete is not effectively prevented.57
The coupled effect of the above factors leads to significantly accelerated concrete degradation. To alleviate
this problem, the degradation mechanism of marine concrete under the coupled effects of wettingdrying cycles
and bending loads shall be studied.
Currently, the indoor accelerated corrosion testing is a
method widely applied in the durability studies of concrete.
However, laboratory environment is never a perfect analogue to the field conditions, and the test results obtained
within a short time in the laboratory cannot predict the
long-term exposure tests.810 Studies have shown that
exposure tests can be used to verify the results of the
indoor accelerated tests. For example, previous report11
demonstrated that the exposure test results were in consistent with the results of the indoor electrochemical tests.
1
School of Civil Engineering, Southeast University Nanjing, Nanjing
210096, Peoples Republic of China
2
School of Materials Science and Engineering, Southeast University
Nanjing, Nanjing 211189, Peoples Republic of China
3
Jiangsu Key Laboratory of Civil Engineering Materials, Nanjing 211189,
Peoples Republic of China

*Corresponding author, email dndxljb@126.com

W. S. Maney & Son Ltd 2015

Received 20 October 2014; accepted 18 December 2014
DOI 10.1179/1432891714Z.0000000001236

In this paper, we present a study of the changes in the

dynamic elastic moduli and free chloride distributions in
the concretes exposed to both the marine tidal environment and indoor accelerated corrosion test conditions
to investigate the degradation of these concretes under
multi-factor coupling effects. Ultimately, a primary correlation was established between these two types of tests
based on the chloride ion diffusion coefficient.

Experimental
Materials
In this experiment, the following materials were used:
ASTM Type I ordinary Portland cement, fly ash, blastfurnace slag, river sand with a fineness modulus of 26
and coarse aggregates of crushed limestone with a particle
size of 520 mm and ordinary tap water. The chemical
composition and properties of the cement, fly ash and
slag are shown in Table 1. The super-plasticiser JMPCA (IV) provided by Jiangsu Bote New Material Co.,
Ltd, has a water-reducing rate of 35%.
To improve the ability of concrete to resist the corrosive
salt in seawater, fly ash and slag were added to the concrete
mixture. In addition, three kinds of water-to-binder (W/B)
ratios were designed, to explore if they have influence
on the durability of concrete. The details of mixing proportions are shown in Table 2.
The compressive and flexural strength of concrete were
tested after curing for 90 days in a standard curing room.
The results are given in Table 3.

Methods
Concrete samples were cast in moulds of 70 mm
70 mm 280 mm, with rebar (10) in the centre. The
compressive strength of samples was tested after curing
for 90 days in a standard curing room. Two sides

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Table 1 Property of cement, fly ash and slag

Parameters

Cement

Fly ash

Slag

SiO2 (%)
Al2O3 (%)
Fe2O3 (%)
CaO (%)
MgO (%)
Na2O (%)
SO3 (%)
K2O (%)
Loss
Specific surface (m2 kg1)
Specific gravity (g cm3)

2138
471
368
6503
253

053

067
3622
315

5242
3325
553
349
107

145
4000
235

3348
1221
140
3635
1060

066
056
036
4600
282

(70 mm 280 mm) opposite to each other were designated as the exposed surfaces and other sides were passivated with epoxy resin. Then, the samples were placed in
a marine tidal zone for the field exposure test. Meanwhile,
indoor accelerated tests of wettingdrying cycles were
simultaneously conducted, in which the corrosive
medium was a solution of mixed salts whose concentration was five times higher than that in seawater
1
(800 g L1 Cl + 120 g L1 SO2
Mg2+).
4 + 725 g L
The samples were immersed in the solution for 8 h, followed by drying at 60 2C for 38 h and natural
cooling. Each wettingdrying cycle took 48 h.
As shown in Fig. 1, a long-term constant bending load
was applied on the concrete samples by a four-point
bending spring. The bending stress ratio, which is defined
as the ratio of applied stress to the ultimate bending strength,
was 0, 035 and 050 for three groups of samples, respectively; each group consists of three samples. Afterwards,
samples were tested by the NMB-4A non-metallic ultrasonic detector to detect the change in the speed of the ultrasonic wave. The data obtained were then converted into
dynamic elastic moduli to evaluate the degradation level
of concrete (as illustrated in Fig. 2).
The samples were cut along the direction perpendicular
to the exposed surface, followed by removal of the coarse
aggregates, sample grinding using a porcelain mortar and
filtration by a square-hole sieve with 063 mm. The concentrations of chloride ions in the concrete samples were
analysed by a method reported previously.12 Finally, the
specimens were separated into five layers: 03, 69,
1215, 1821 and 2427 mm (only the tension zone was
kept if the samples were under bending load).

Results and discussion

Effects of environmental corrosion factors
Corrosion tests were conducted on the samples of C50B
under the following conditions: the mixed salt solution

Table 3

Concrete compressive and flexural strength after 90

days

Group

Compressive strength (MPa)

Flexural strength (MPa)

C30F
C50B
C50F
C50S
C50FS
C80F

323
590
568
592
576
800

69
93
83
88
87
108

1 Schematic diagram of loading equipment

2 Schematic diagram of ultrasonic testing

(single factor), mixed salt solution + wettingdrying

cycles (dual factors) and mixed salt solution +
wettingdrying cycles + 35% bending load (triple
factors). The variations in relative dynamic elastic
moduli (Ed) with exposure time are presented in Fig. 3
and the concentrations of free chloride ions in the concrete samples after 660 days are provided in Fig. 4.
According to Fig. 3, under the effect of the single
factor, Ed increased continuously in the first 300 days
but decreased afterwards. The initial increase can be
attributed to the improved concrete compactness as a
result of the continuous hydration action inside the concrete in the early stage of erosion. However, as the corrosion continued, an expansion pressure resulting from
the accumulated corrosion products and volume expansion was generated and eventually exceeded the ultimate

Table 2 Mixing proportions of concrete

Mix composition/(kg m3)
Group

Cement

Fly ash

Slag

Water

Fine aggregate

Coarse aggregate

Super-plasticiser

W/B ratio

C30F
C50B
C50F
C50S
C50FS
C80F

253
449
314
225
179
396

109
0
134
0
135
170

0
0
0
225
135
0

188
157
152
158
148
130

724
673
672
676
673
678

1086
1122
1119
1126
1121
1017

043
382
255
279
229
453

052
035
034
035
033
023

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3 Ed of concrete samples versus exposure time

5 Ed of concrete samples versus exposure time

tensile strength of concrete. As a result, micro-cracks were

observed in the concretes, resulting in new channels that
may facilitate ion penetration. Macroscopically, a
decrease in Ed was observed. Additionally, the damage
to the concrete was more severe in the presence of two
or three factors, which showed 488 and 691% decrease
in Ed, respectively, as compared to 152% decrease in
the case of single factor.
As shown in Fig. 4, the concentration of free chloride
ions was maximum on the concrete surface and decreased
with increasing diffusion depth. On the other hand, the
maximum concentration of chloride ions in the concretes
exposed to two factors was higher than that in the concretes exposed to single factor. This can be explained by
the capillary absorption in the wettingdrying cycles,
which is a key factor for the concentration of chloride
on the surface layer as it led to accelerated ion penetration
into the concrete. However, the transport mechanism of
chloride ion in the bulk of concrete is dominated by diffusion. Additionally, no significant difference between the
concentration distribution of the chloride ions in the
samples exposed to three factors and that of samples
exposed to two factors was observed, despite that the
overall quantity of chloride ions was larger in the case
of three factors. For this reason, it is concluded that the
wettingdrying cycles led to both accelerated decrease
of dynamic elasticity modulus and accelerated penetration of chloride ions. The long-term presence of the
bending load did not change the erosion mechanism of
the salt on the concrete. However, the bending load

resulted in expanded internal transport channels, thus

accelerating the degradation of the concrete.13

4 Concentration of free chloride ions in concrete samples

6 Concentration of free chloride ions in concrete samples

Effects of W/B ratio

As indicated in Table 2, the W/B ratios after blending
with fly ash were 052, 034 and 023 for samples C30F,
C50F and C80F, respectively. Corrosion tests were conducted on the three groups of samples subjected to
triple factors afterwards. The variation in Ed with
exposure time is depicted in Fig. 5, and the concentrations
of free chloride ions in the samples after exposure for 660
days are plotted in Fig. 6.
The results given in Fig. 5 showed similar trends of Ed
for different samples, despite that their W/B ratios were
significantly different. This serves as an indicator of a
gradual decrease in the early stage of corrosion. Owing
to a lower W/B ratio, sample C30F showed faster ion
intrusion and larger quantity of the corrosion products
in the pores, which resulted in stronger capability of
filling and compacting in the early stage of hydration.
In addition, Ed of sample C30F increased by 14%
within 50 days. In the later stage of corrosion, the
decrease of Ed was accelerated drastically and the decreasing rates of different samples were as follows: C30F >
C50F > C80F. According to Fig. 6, the diffusion rate of
chloride ions was highest in sample C30F, resulting in
the highest rate of degradation, which is in consistent
with the decrease of Ed. Additionally, in virtue of a

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Degradation of marine concrete subjected to wettingdrying cycles and bending loads

9 Ed of concrete samples versus exposure time

7 Ed of concrete samples versus exposure time

decrease in the W/B ratio, the compactness of samples

was improved and the degradations were alleviated.

Effects of mineral admixtures

To investigate the effects of mineral admixtures, corrosion
tests were conducted on four groups of samples with
different mineral admixtures subjected to three factors.
The variations in Ed with exposure time are presented
in Fig. 7 and the concentrations of free chloride ions in
the concrete samples after exposure for 660 days are
plotted in Fig. 8.
As shown in Fig. 7, the Ed of all samples exhibited a
slight increase in the early stage of corrosion, followed
by a rapid decrease. The most drastic decrease was
observed in sample C50B, where Ed decreased by 692%
within 660 days. On the contrary, Ed of sample C50FS
showed a 415% decrease, which was the minimum
value observed. According to Fig. 8, the concentration
of free chloride ions in the C50FS group was the lowest.
Indeed, it was 38, 163, 318, 364 and 218% lower
than that in the C50B group (maximum) at diffusion
depths of 03, 69, 1215, 1821 and 2427 mm, respectively. The results revealed that the addition of mineral
admixtures, especially the combination of fly ash and
slag, can significantly improve the corrosion (by Cl)
resistance of concrete. Two possible reasons have been
proposed. First, the addition of fly ash and slag led to a
filling effect of micro-aggregates that can decrease the
porosity of the concretes, refine the apertures and retard
the diffusion of harmful media. Second, large-sized

8 Concentration of free chloride ions in concrete samples

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pores were filled by the secondary products produced

by the pozzolanic effect, resulting in inhibited concrete
degradation.14,15
In summary, these studies showed that C50FS concrete
is an ideal candidate for marine concretes in virtue of its
excellent resistance to seawater. In addition, with the
addition of fly ash and slag, the performance of C50FS
concretes was even better.

Effects of bending load

To investigate the effects of bending load, destructive load
testing was performed on sample C50F after exposure to
a marine tidal environment. The variation in Ed with
exposure time is given in Fig. 9 and the concentrations
of free chloride ions in the concrete samples after
exposure for 1050 days are plotted in Fig. 10.
According to Fig. 9, the Ed of the samples bearing 50%
bending loads showed maximum decrease, which was
605% after 1050 days, followed by the samples bearing
35% bending loads (412%). The Ed of the samples
without load showed minimum decrease (293%).
Meanwhile, as shown in Fig. 10, the samples bearing
50% bending loads exhibited the highest concentrations
of free chloride ions at every diffusion depth. For
instance, at the diffusion layer 2427 mm from the
surface, the concentration of free chloride ions in the
samples bearing 50% bending load was 378% higher
than that in the samples without load. These results indicated that in the later stage of corrosion, the degradation
rate of the samples bearing 50% bending load was
maximum, and for the samples without load, the

10 Concentration of free chloride ions in concrete samples

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Degradation of marine concrete subjected to wettingdrying cycles and bending loads

Table 4 Diffusion coefficient of chloride ion after various

exposure times ( 1012 m2 s1)
Exposure time (d)

50

160

260

360

460

560

Indoor accelerated
testing
Marine tidal
exposure

4930

2041

986

644

448

314

2120

1012

788

485

305

253

degradation rate was minimum. This may be explained by

the accelerated formation of micro-cracks in the concretes
in the presence of a bending load, as these cracks are
channels of salt penetration. As the expansion pressure
produced by the accumulated corrosion products
increased and exceeded the ultimate tensile strength of
the concrete, cracks will be generated; thus increasing
the permeability of the concrete and accelerating the
erosion caused by corrosive salts such as chloride and sulphate. As a result, the concretes were suffering from accelerated degradation. It was also observed that larger
bending loads resulted in higher degradation level of
concretes.16,17

11 The fitted curve of the diffusion coefficient over time for

the indoor corrosion test

Correlation between field test and indoor

corrosion test
The mechanism of concrete degradation in seawater and
mixed salt solution is complicated as it is a combination
of various factors, including corrosion caused by chloride, sulphate, magnesium, etc. Based on the chloride diffusion coefficient, we presented a study on the correlation
between the field test in marine tidal environment and the
indoor test accelerated by wettingdrying cycles. The diffusion of chloride ion in concrete follows Ficks second
law,18,19 and its diffusion coefficient can be calculated
using the following equation20

ct = cts

x
1 erf



2 D



where ct is the concentration of free chloride ions (mass

ratio), cts is the concentration of chloride ion on the
surface (mass% of sample), t is time (s), x is distance
(m) and D is the diffusion coefficient determined by the
long-term corrosion test.
On the basis of concentrations of free chloride ions in
the C50FS sample bearing 35% bending load after
various exposure times, the diffusion coefficient was calculated and the results are listed in Table 4.
As the exposure continued, the cementitious material
became further hydrated and the diffusion coefficient of
chloride ions decreased. In the early stage of corrosion,
the hydration of cement and mineral admixtures in the
concrete was incomplete and the micro-filling and volcanic ash effects by fly ash and slag were not fully developed
yet. As the exposure continued, the materials became
further hydrated, resulting in improved pore structure
and interfaces in the concrete and reduced porosity.
As a result, the resistance of concretes to the chloride
ion permeation was enhanced.21
The diffusion coefficients of chloride ion measured in
the two situations were fitted as a function of the exposure
time and the results are shown in Figs. 11 and 12,
respectively.

12 The fitted curve of the diffusion coefficient over time for

field test in marine environment

The correlation between the diffusion coefficient of

chloride ions and the exposure time can be represented
by the following power-law function
D = AD50 tm
where A and m represent the diffusion factor and time
factor, respectively; D50 is the chloride diffusion coefficient after exposure for 50 days and t is the exposure
time in days. For the accelerated corrosion test, A =
4119, m = 0948 and R 2 = 0981; for the field test, A =
1751, m = 0728 and R 2 = 0970.
The results demonstrated a good consistency between
the accelerated corrosion test and the field test.
Therefore, it is possible to establish a relation between
them based on the diffusion coefficient of chloride ions,
thus predicting the result of field test based on that of
accelerated corrosion test. Fig. 13 shows the function
used to fit the relation between the two groups of chloride
ion diffusion coefficients for the C50FS samples.
Indeed, the two groups of diffusion coefficients obey
the following logarithmic function
DField exposure = K ln DIndoor corrosion + B
where K and B represent the environmental factor and the
diffusion constant, respectively; K = 6554, B = 670

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References

13 The fitted curve relating the chloride ion diffusion

coefficients measured in the two tests

and R 2 = 0908. With this formula, the diffusion coefficient of chloride ions measured in an accelerated corrosion test can be used to predict the results of field
exposure.

Conclusion
(1) Marine concrete is a composite material whose
resistance to the seawater can be improved by
decreased water-to-binder ratio. Addition of fly ash
and furnace slag can significantly alleviate the degradation of concretes, and larger bending loads
applied resulted in accelerated damage in the
concrete.
(2) The wettingdrying cycles led to capillary on the
concrete surface, facilitating the migration of
chloride and sulphate salts into the concrete.
Under bending loads, concrete samples showed
significantly accelerated propagation of microcracks.
(3) The results of the marine concrete corrosion tests
under multi-factor environmental effects revealed a
power-law relation between the diffusion coefficient
of chloride ions and the exposure time. Moreover,
the chloride ion diffusion coefficients measured
in the field test and the accelerated indoor test can
be correlated to each other by a logarithmic
function.

Acknowledgements
This work was supported by the National Basic Research
Program of China (the 973 Program) (2009CB623200)
and the National Natural Science Foundation of China
(51108077 and 51308112).

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