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Construction and Building Materials 144 (2017) 406–411

Contents lists available at ScienceDirect

Construction and Building Materials


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

Effects of self-healing cracks in bacterial concrete on the transmission


of chloride during electromigration
Hao Ling ⇑, Chunxiang Qian
College of Materials Science and Engineering, Southeast University, Nanjing 211189, China
Research Institute of Green Construction Materials, Southeast University, Nanjing 211189, China

h i g h l i g h t s

 The effects on transmission of chloride were test through multiple methods.


 The method of electromigration was used to accelerate the transmitting of chloride.
 The microbial self-healing cracks could impede the transmission of chloride.

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

Article history: The microbial self-healing concrete has been a new technology to repair cracks, the former study showed
Received 25 November 2016 that the precipitated CaCO3 could fill the cracks and reduce the permeability coefficient of cracks. On this
Received in revised form 26 February 2017 basis, the impacts on resisting transmission of chloride were studied to evaluate the protective effects of
Accepted 27 February 2017
microbial self-healing cracks, through multiple characterization methods such as electrochemical test,
visual examination of cracks surface, weight-loss ratio of reinforcements and chloride ion content.
Besides the method of electromigration was used to accelerate the transmission of chloride. The results
Keywords:
show that the microbial self-healing cracks can indeed impede the transmission of chloride in cracks and
Concrete
Self-healing
have protective effects for reinforcements in the concrete.
Chloride transmission Ó 2017 Elsevier Ltd. All rights reserved.
Electromigration
Reinforcement

1. Introduction it will affect the normal use of concrete structure, resulting in total
destruction and even collapse.
Concrete materials have the advantages of high compressive The traditional repairing methods are passive in most cases.
strength, better fireproofing and durability, easiness in obtaining They have complex technology, high cost and even some destruc-
materials [1], which have been widely used in many practical tive effects on the environment, which can’t satisfy the require-
projects like water conservancy and hydropower, traffic, industrial ment of modern intelligence and multifunction for concrete
and civil construction. They have become one of the most materials [3]. In 1995, Gollapudi et al. first proposed the method
extensively used civil engineering materials. But during the prepa- of using biology progress to repair cracks and got a bran-new solu-
ration and usage of concrete, the external loads and other factors tion for the problem [4]. Microbial self-healing methods mainly
can result in loosing and spalling on the surface, seriously making utilize the metabolism of bacteria to induce mineral precipitation.
cracks in the concrete [2]. The cracks will reduce the capacities of They have the advantages of simple technology, low cost and free
anti-permeability, anti-chloride-corrosion and anti-carbonization of contamination, which have become the research hotspot [5–9].
greatly, which can make the corrosion of interior reinforcements Bacteria induced mineral precipitation has been proposed as an
much easier and lower the carrying capacity and durability of alternative and environmental technique to improve the capacity
structure. If the repair of concrete cracks isn’t completed in time, of concrete crack-healing in recent years [10–12]. For the self-
healing effects of microbial self-healing methods, Wiktor et al.
applied contrast test to the self-healing specimens and the control.
The results indicated microbial self-healing concrete had more
⇑ Corresponding author at: School of Materials Science and Engineering, South- mineral precipitation and could repair wider cracks (470 lm),
east University, Jiulonghu Campus, Nanjing 211189, China. while only 210 lm width of cracks was in the control [13]. Luo
E-mail address: seulinghao@163.com (H. Ling).

http://dx.doi.org/10.1016/j.conbuildmat.2017.02.160
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
H. Ling, C. Qian / Construction and Building Materials 144 (2017) 406–411 407

et al. prefabricated 0.3 mm cracks in the specimens. They found


that the microorganism repaired plenty of cracks in 5 days and
could fill the surface of cracks completely in 20 days [14]. In their
other researches, the bacterium loaded by pottery sand could
repair maximum width of 1 mm. They also found that maximum
CaCO3 were precipitated in the opening of cracks and mainly con-
centrated on the area of 1.5 mm depth from the surface of cracks
[15]. In addition, the changes of permeability coefficient before
and after the healing of cracks can characterize the remediation
effect. Wang et al. verified that microbial self-healing concrete
was able to reduce the permeability coefficient of cracks, especially Fig. 1. The schematic of making cracks by steel sheets.

in the initial 24 h [16]. In the research of Tittelboom et al., it also 3 days. After that, the self-healing specimens were put into the 30 °C water and kept
showed that after using microbial self-healing agent to repair 21 days to ensure that the cracks would be healed effectively in the self-healing
cracks, the anti-permeability and durability of concrete specimens environment and the control specimens were in the same environment for the con-
trast. Those specimens representing the cracks before being healed were put in the
were improved greatly [4]. It demonstrates that microbial self-
standard curing room for 24 days at the same time.
healing technology can make repairing effects on the concrete
cracks to some degree, but how much the real value of repairing 2.4. Electromigration accelerated transmission of chloride
effects and the effect on resisting the transmission of chloride, still
need a further research. The method of using electromigration to accelerate the transmission of chloride
In this study, we mainly used the previous microbial self- is connecting a DC electrical source between the chloride solution and the reinforc-
ing steel bar to produce an electric field among them. The chloride will invade into
healing technology of our research group to test the influence of
the specimen more quickly under the effect of the electric field, achieving the pur-
self-healing cracks on the transmission of chloride, then assessed pose of accelerating the transmission of chloride. We redesigned the electromigra-
the actual contribution for protecting reinforcements. In order to tion device from other study [17]. The working device as shown in Fig. 2.
accelerate the transmission of chloride, we adopt the method of In the device, the reinforced specimens were immersed in the 3.5% NaCl solu-
tion (to simulate the seawater environment). The wires in the reinforced specimens
electromigration. Besides, the reinforcements were imbedded in
were linked with the positive pole of the DC source. The stainless steel mesh with
the specimens to further study the protective performance under 6 mm square hole was placed above the specimens and connected with the nega-
the effects of self-healing cracks. tive pole of DC source by the wire. During the process of electromigration acceler-
ation, the exterior voltage applied in the specimens would make abundant of heat.
The degree of fever depends on the applied voltage and the resistance of cement
2. Materials and methods
materials. Those heat is harmful that can cause the transform of the microstructure
in the cement-based materials and make the specimens damaged in a certain
2.1. Microbial self-healing agent
degree [18]. Therefore, the voltage of DC source used for electromigration acceler-
ation can’t be too high. Considering the problem of voltage and the test time, we
Microbial self-healing agent consisted of two parts: bacteria powder and sub-
chose 15 V as the voltage of DC source in the study. Because the water evaporation
strate. Bacteria power was Paenibacillus mucilaginosus. Cultivation of Paenibacillus
during the test may change the concentration of NaCl solution and lower the liquid
mucilaginosus was conducted in sucrose culture (10 g of sucrose and 3 g of sodium
level, we should always check the amount of solution during the process of
hydrogen phosphate dissolved in deionized water to 1 L, and the pH value was
electromigration. Keep the solution level above the stainless steel mesh to assure
adjusted to about 7.0) at 35 °C for 24 h. Bacteria powder was made from the above
an effective electric circuit between NaCl solution and the steel bar in specimens.
bacteria liquid by freeze drying process. The appropriate temperature of Paenibacil-
lus mucilaginosus growth is 10–40 °C, while the pH value is 7.0–9.0.
2.5. Multiple characterization methods to evaluate the effect on chloride transmission

2.2. Preparation of cement mortar specimens During the process of electromigration accelerating the transmission of chlo-
ride, the chloride reaching the surface of steel bar would induce the corrosion of
There were two kinds of cement mortar specimens, the microbial self-healing reinforcements constantly. Therefore we can monitor the condition of steel bar cor-
and the control. The microbial self-healing specimens were prepared by mixing rosion to assess the degree of chloride transmission. Electrochemical test method is
ordinary Portland cement, sand, self-healing agent and water. The mixing propor-
tion as shown in Table 1. The control specimens had no self-healing agent so with-
out subjection to bio-deposition. The dimensions of specimens were all
50 mm  50 mm  200 mm. There was a 10 mm diameter reinforcing steel bar
with acid dipping treatment imbedded in the middle, the ends of the steel bar
and the location of linking wires were sealed with epoxy resin.

2.3. Creation of artificial cracks and curing condition

In order to simulate the real situation of concrete cracks and reduce the influ-
ence due to the difference of cracks, we used the method of presetting the steel
sheets in the mortar while making the specimens. The width of steel sheets was
40 mm, thickness was 0.2 mm and they must inserted vertically in the mortar with
the depth of 20 mm and separation distance of 40 mm, as shown in Fig. 1. Take off
the steel sheets at the final setting time of mortar, remove the form after one day
and then put the specimens into standard curing room (20 ± 2 °C, RH > 95%) for

Table 1
Composition of self-healing specimens.

Material kg/m3
Ordinary Portland Cement 600
Water 300
Sand 1800
Substrate 12
Bacteria powder 1.2
w/c 0.5
Fig. 2. The device of electromigration accelerated transmission of chloride.
408 H. Ling, C. Qian / Construction and Building Materials 144 (2017) 406–411

nondestructive analysis that can detect the corrosion degree. The final corrosion deposited CaCO3 from microbial mineralization, which hindered
rate can be got by testing the weight-loss ratio of reinforcements that were taken
the chloride from invading into the reinforcement surface through
out from decomposed specimen. Furthermore, observing the condition of corrosion
products spilled from the cracks can also estimate the corrosion degree to some
the cracks and slowed down the process of reinforcement corro-
extent. sion. And the control specimens containing the cement also had
In this experiment, the measurement system used for electrochemical test the ability to heal the crack in the early period, which could reduce
method was three-electrode system, including 10 mm reinforcement for working the corrosion. However, it is not as good as the self-healing
electrode, SCE (saturated calomel electrode) for reference electrode and the stain-
specimens.
less steel sheet for auxiliary electrode. The adoptive measure method was linear
polarization method, derived from the Stern and Geary in 1957 and it’s a simple,
quick and effective non-destructive test methods. The theory is connecting the cor- 3.2. Visual examination of cracks surface
rosion ratio with polarization curve at the point of corrosion potential. When the
overpotential is very little (g < 10 mV), it will have a linear relation with polariza-
During the process of electromigration, it’s easy to find that the
tion current [19].
In the actual data processing, the numerical value of corrosion current Icorr and
corrosion products exceeded form the cracks because of the rein-
self-corrosion potential Ecorr can be obtained from the electrochemical software forcement corrosion. So, it’s a way to evaluate the degree of rein-
VersaStudio by RP fitting. Ecorr is the stable potential that corrosion system can’t forcement corrosion. In Fig. 5, the change of cracks surface
be applied by the additional polarization. The more negative value of Ecorr, the more stained by rust become more and more serious in the control spec-
corrosion tendency. On the contrary, more positive value of Ecorr can make less ten-
imens, so the rust stain are increasing constantly. For the self-
dency of corrosion and better corrosion resistance [20]. Besides, the changes of self-
corrosion potential can reflect the degree of reinforcement corrosion. Some other healing specimens, the degree of cracks surface corrosion is always
studies have pointed that the more corrosion current and negative value of self- slight during the electromigration time. Only after 14 h, we can
corrosion potential indicate the more serious degree of reinforcement corrosion find obvious corrosion exceeding from the cracks. It indicates that
[21]. The single type of data can’t reveal the reinforcement corrosion accurately
the healing of cracks in the self-healing specimens could slow
because the results of electrochemical test always possess some volatility and devi-
ation for the real reinforcement corrosion state. As a result, this study combined
down the transmission of chloride during the process of electromi-
corrosion current data with self-corrosion potential to reflect the corrosion state gration, mainly because the self-healing products filled the cracks,
of reinforcement more accurately. hindered the transmission of chloride in the specimens and pro-
Testing weight-loss ratio can measure corrosion of reinforcements accurately. tected the reinforcement.
The reinforcements should be dealt with acid pickling to wash off the corrosion
products on the surface. During the acid pickling, put two steel bars that have the
same dimension and non-stain to work as calibration of blank value. When acid 3.3. Weight-loss ratio of reinforcement
pickling was accomplished, dry and weigh the reinforcement.
Otherwise the chloride transmission degree can be characterized by measuring After electromigration was finished, the corrosion situation at
the chloride content in the specimens. When drilling hole to get powder used for the ends of reinforcement was very serious. It may because protec-
measuring the chloride content, the location of those drilling hole were the middle
of the specimens surface and the distance from the right side were 60 mm, 100 mm
tive effect of the ends was the weakest. The corrosion products
and 140 mm respectively, which could avoid the chloride immersing from the both heaped up instantly during the test and destroyed the protective
ends exerting an influence on the test results. And the depths of drilling hole are layer of the ends, so the erosion of chloride became easy and fast.
5 mm, 10 mm and 15 mm respectively, as shown in Fig. 3. The powder in the three The corrosion of the ends had nothing to do with the cracks, so we
drilling holes should be put together to assure the quantity of powder in each depth
should avoid the corrosion affecting on the reinforcement weight-
were enough.
loss ratio. In this study, we took out the reinforcement in the spec-
imens and cut out the middle 120 mm section for the weight-loss
3. Results and discussion
ratio test, as shown in Fig. 6. It can exclude the effect of the corro-
sion at the ends and the effect of no corrosion because of the epoxy
3.1. Electrochemical test results
resin protective layer at the touch point of the wire. The chosen
120 mm sections of reinforcement were mainly focus on the area
During the process of electromigration accelerating transmis-
of cracks. It could reflect the influence of healed cracks on the pro-
sion of chloride, the changes of reinforcement corrosion current
tective effect of reinforcement.
and self-corrosion potential, along with the differences of before
Although the initial quality of reinforcement in the chosen sec-
and after cracks healing are shown in Fig. 4. We can find that the
tion is unknown, we can get that by calculational methods, mainly
corrosion current of the self-healing specimens and the control
depending on two parameters of length and linear density. The lin-
specimens are both lower when the cracks were healed. Especially,
ear density can be calculated by the three standard reinforcements.
the self-healing specimens has a lower level than the control. From
The final results and other parameters as shown in Table 2. The
the changes of self-corrosion potential, there are more obvious
average linear density is 5.72 g/cm.
results. During the whole electromigration process, the negative
Take out the reinforcement in the specimen when the electro-
value of self-corrosion potential in the control specimens is higher
migration was finished and choose the middle section. The final
than that of the self-healing specimens, although both of them are
results of average corrosion ratio of reinforcements are shown in
lower than those results of cracks without being healed. In the sit-
Fig. 7. It can be found that in the state of reinforcement corrosion
uation of BH (before healing), there aren’t too much differences.
after 18 h of electromigration, the average weight-loss ratios of
Those results indicate that the corrosion current and the self-
self-healing specimens and the control are both lower than that
corrosion potential can be reduced after the cracks were healed.
of before healing. The self-healing is lower than the control speci-
The cracks in the self-healing specimens may be blocked by the
mens by 0.55(%). This result is consistent with the former results of
corrosion current and self-corrosion potential in the electrochem-
ical test and visual examination of cracks surface. It indicates the
cracks healed by the microbial self-healing agent can better hinder
the transmission of chloride in the state of electromigration, slow
down the corrosion of inner reinforcement and have preventive
effects. We can also find that the weight loss of reinforcements
in the self-healing specimens is lower than that of the control
before the healing. The reason may be that the self-healing speci-
mens also made the healing in the curing room to some degree
Fig. 3. The drilling holes in the specimen. and it’s difficult to avoid it.
H. Ling, C. Qian / Construction and Building Materials 144 (2017) 406–411 409

Fig. 4. The changes of corrosion current and self-corrosion potential with electromigration time (BH: before healing; AH: after healing).

Fig. 5. Visual examination of cracks surface during the electromigration time.

Fig. 6. The chosen section of reinforcement in the weight-loss ratio test.

Table 2
Linear density and other parameters of standard reinforcement.

Number ① ② ③
Length (cm) 11.88 11.92 11.80
Quality (g) 67.945 67.938 67.781
Linear density (g/cm) 5.72 5.70 5.74
Fig. 7. The average corrosion ratio of reinforcements.
410 H. Ling, C. Qian / Construction and Building Materials 144 (2017) 406–411

3.4. The test of chloride content

The test results of average chloride content in different depths


at the end of 18 h electromigration are shown in Fig. 8. It can be
found that all the specimens after healing have lower chloride con-
tent than those without healing. Chloride content in the self-
healing specimens is also lower than the control before healing.
For the situation that cracks had been healed, in the depth of
5 mm, the average chloride content of self–healing specimens is
a little higher than that of the control, which may result from the
self-healing agent added into the matrix changing the compact-
ness. But with the depth increasing, the chloride contents of
10 mm and 15 mm are both lower in the self-healing specimens.
The changes may relate to the healing of cracks, but still need fur-
ther analyses. So in this study, we simply simulated the chloride
transmission before and after the healing of cracks.
For the chloride transmission, we mainly considered one- Fig. 9. The simulation of chloride transmission in the crack: (a) self-healing
specimens; (b) control specimens.
dimensional oriented transmission from exterior to interior in
the cracks when simulating, the method was finite element simu-
lation by ANSYS and the other major parameters were set as fol-
4. Conclusions
lows. The initial concentration of chloride C0 = 0, exterior
concentration Ce = 35 kg/m3 (means the chloride solution of 3.5%
During the process of electromigration accelerating transmis-
mass fraction that simulated the seawater environment). The diffu-
sion of chloride, the results of corrosion current and self-
sion coefficient of chloride in the concrete D0 = 5.5  10 12 m2/s
corrosion potential by electrochemical test show that the corrosion
was got from the RCM test. In the research of Ismail et al.,
degree of reinforcements is lower when the cracks were healed by
0.2 mm crack was not a limiting factor controlling the diffusion
self-healing agent.
process perpendicular to the crack wall and had no influence on
The visual examination shows less corrosion products overflow-
the chloride transmission [22]. So the diffusion coefficient of chlo-
ing from the cracks and the lower weight-loss ratio of reinforce-
ride in the cracks Dcr = DS = 2.58  10 9 m2/s, that was the same as
ments that were took out from the self-healing specimens by
the diffusion coefficient in solution. For the area of healed cracks,
destructive test method. The mainly reason is the healed cracks
the compactness of healing substance was lower than the concrete,
can hinder the chloride form invading into the inner of specimens
so the diffusion coefficient of chloride was higher, set as
by the cracks, thus slow down the process of reinforcements
Dh = 5.5  10 11 m2/s. The healing depth of cracks could reach
corrosion.
about 1.5 mm in the previous study [15]. Total simulation time
In addition, the test results of chloride content in different
was 10 days and the final results as shown in Fig. 9.
depths verify that chloride content in the self-healing specimens
In Fig. 9, the chloride mainly diffuses from the crack and has a
is lower after the cracks were healed. It can indicate the lower
peak distribution. When the crack was healed in the self-healing
transmission degree of chloride accurately.
specimens, the diffusion depth is shallower than that of the control
Through those multiple kinds of characterization methods, we
and the chloride concentration is lower in the area of crack. So, we
can get that the microbial self-healing applied on the concrete
can conclude that the lower results of chloride concentration of
cracks can impede the transmission of chloride in the cracks, which
self-healing specimens in 10 mm and 15 mm as shown in Fig. 8
has a directly protective effect on reinforcements. This study also
is related to the healing of cracks. The healing cracks could hinder
shows good application values of microbial self-healing technique
the chloride transmission in the cracks, thus decreasing the inner
used in the practical construction and provides a new approach to
chloride concentration in the specimens.
reinforce the durability of structure.

Acknowledgments

Authors would like to appreciate the financial support from


National Nature Science Foundation of China (Grant No.
51178104) and Scientific Research Foundation of Graduate School
of Southeast University.

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