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Cement and Concrete Research 56 (2014) 139–152

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Cement and Concrete Research


journal homepage: http://ees.elsevier.com/CEMCON/default.asp

Self-healing concrete by use of microencapsulated bacterial spores


J.Y. Wang a,b, H. Soens c, W. Verstraete b, N. De Belie a,⁎
a
Magnel Laboratory for Concrete Research, Faculty of Engineering and Architecture, Ghent University, TechnologieparkZwijnaarde 904, B-9052 Ghent, Belgium
b
Laboratory of Microbial Ecology and Technology (LabMET), Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000 Ghent, Belgium
c
Devan Chemicals NV, Klein Frankrijk 18, 9600 Ronse, Belgium

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

Article history: Microcapsules were applied to encapsulate bacterial spores for self-healing concrete. The viability of encapsulated
Received 27 March 2013 spores and the influence of microcapsules on mortar specimens were investigated first. Breakage of the microcap-
Accepted 27 November 2013 sules upon cracking was verified by Scanning Electron Microscopy. Self-healing capacity was evaluated by crack
healing ratio and the water permeability. The results indicated that the healing ratio in the specimens with bio-
Keywords:
microcapsules was higher (48%–80%) than in those without bacteria (18%–50%). The maximum crack width healed
Crack (B)
Water permeability (C)
in the specimens of the bacteria series was 970 μm, about 4 times that of the non-bacteria series (max 250 μm). The
Organic materials (D) (microcapsules) overall water permeability in the bacteria series was about 10 times lower than that in non-bacteria series. Wet–dry
Microbial CaCO3 (D) cycles were found to stimulate self-healing in mortar specimens with encapsulated bacteria. No self-healing was
Self-healing observed in all specimens stored at 95%RH, indicating that the presence of liquid water is an essential component
for self-healing.
© 2013 Elsevier Ltd. All rights reserved.

1. Introduction Due to the harsh environment inside the concrete, encapsulation or


immobilization of bacteria in a protective carrier before adding them to
Self-healing systems with microencapsulated healing agents, have the concrete is preferable [15,16]. A self-healing system by using porous
been developed mainly in polymers and composites [1–4]. The research expanded clay particles for immobilization has been described [17,18].
on the application of microcapsules into concrete to obtain a self-healing Healing superiority in the specimens with bio-agents was observed
capacity was started recently. Yang et al. [5] showed that the addition of after 40 days; the maximum crack width healed reached 0.46 mm,
microencapsulated methylmethacrylate based healing agent into carbon which was almost two times that in the reference specimens. In our ear-
microfiber-reinforced mortar can greatly improve the crack resistance lier work, we developed a system in which glass capillaries were used to
and toughness under fatigue loading. This demonstrated that the con- encapsulate bacteria and filling materials (polyurethane or silica sol gel)
cept of using microcapsules as carriers for self-healing agents in concrete and found that the water permeability in the bacterial series was 2–3
was feasible and very promising. orders of magnitude lower than the non-bacteria series [11]. Addition-
Microbial CaCO3 is regarded as environmentally friendly and eco- ally, diatomaceous earth has also been explored to immobilize bacteria
nomical material which has a promising potential for a wide range of for self-healing. Cracks of a width of 0.17 mm were completely healed
engineering applications, for instance, consolidation and protection of in the specimens in which diatomaceous earth immobilized bacteria
concrete and stone surfaces, repair of defects and flaws (specifically, was incorporated, while no crack healing was observed in the non-
cracks), cementation or consolidation of loose particles (specifically, bacterial series [19]. In these experiments, the cracks were created
soil and sands), etc. [6–13]. The basic principle of applying microbial in the mortar specimens at the age of 14 days, and the healing efficiency
CaCO3 for self-healing concrete is that bacteria and other relevant was analyzed after a healing period of 40 days.
agents are added into the concrete matrix during casting. When cracks In this study, microcapsules were used as bacterial carriers. The mi-
appear, bacteria around the crack surfaces will be activated (by moisture, crocapsules were resistant to the high pH of concrete and humidity sen-
O2, etc.) and precipitate CaCO3 to heal the cracks. In this study, microbial sitive. They are flexible under high humidity (like in water) and become
CaCO3 was precipitated by Bacillus sphaericus through urease catalyzed brittle at low humidity. This means that the capsules can withstand the
urea hydrolysis [14]. mixing process and are easily broken when cracks appear. Upon crack-
ing, microcapsules in crack zone will break. In the presence of water in
the cracks, spores in the broken capsules can germinate and precipitate
CaCO3 to heal the cracks. The aim of this research was to demonstrate
⁎ Corresponding author at: Magnel Laboratory for Concrete Research, Faculty of
Engineering and Architecture, Ghent University, TechnologieparkZwijnaarde 904,
the feasibility of using microencapsulated spores to self-heal cracks in
B-9052 Ghent, Belgium. Tel.: + 32 9 264 59 22; fax: + 32 9 264 58 45. a cementitious matrix. The food of bacterial spores (yeast extract) and
E-mail address: nele.debelie@ugent.be (N. De Belie). the deposition agents including urea and Ca source (Ca-nitrate) were

0008-8846/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.cemconres.2013.11.009
140 J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152

incorporated together with the microcapsules during the mixing 2.4. Microcapsules in mortar specimens —proof of concept 2
process.
2.4.1. Influence of the microcapsules on the mechanical properties of mortar
Mortar specimens (40 mm × 40 mm × 160 mm, n = 3) with
2. Materials and methods different amounts of microcapsules (without bacteria) incorporated,
were cast to investigate the influence of microcapsules on the mechani-
2.1. Bacterial strain cal properties of mortar specimens. The specimens were made with a
water-to-cement ratio of 0.5 and a sand-to-cement ratio of 3 by using
Bacillus sphaericus LMG 22557 (Belgian coordinated collection of mi- Ordinary Portland Cement (CEM I 52.5N), sand (DIN EN 196-1 Standard-
croorganisms, Ghent) was used in this study. B. sphaericus spores were ized sand) and tap water. The amount of the microcapsule emulsion
produced in the liquid minimal basal salts (MBS) medium [20]. The added was based on the microcapsule dry weight content as 0% (R),
MBS medium was autoclaved at 120 °C for 20 min before use. Mature 1%, 2%, 3%, 4% and 5% of cement (by weight). The microcapsule emulsion
spores were transferred as inoculum (1%) into MBS medium. The cultures was first mixed with water. Then the mortar mixture was prepared ac-
were incubated (28 °C, 100 rpm) for 28 days. Subsequently, they were cording to the standard NBN EN 196-1 [23]. After casting, all molds
subjected to pasteurization (80 °C for 20 min, then 5 min in ice-cold were put in an air-conditioned room (20 °C, N95%RH). The specimens
water) to minimize the vegetative cells. Spores were then harvested by were de-molded after 48 h (24 h for R) and were placed in the same
centrifuging the culture (7000 rpm, 4 °C, Eppendorf MiniSpin, Hamburg, air-conditioned room. After 28 days, strength was measured according
Germany) for 7 min. The supernatant was removed and the paste of to the standard NBN EN 196-1 [23].
spores was subjected to vacuum drying for 3 days under room tempera-
ture. Dry paste of the spores was then ground in a cement mill (Aurec S.A, 2.4.2. Survival of the microcapsules during the mortar mixing process
Bruxelles) for 5 s to obtain fine powders for encapsulation. Light microscopy (Leica S8AP0, Switzerland) was used to visualize
the microcapsules before and after they were mixed with mortar
paste. After the mortar paste (containing 1% microcapsules) was ready,
2.2. Microencapsulation of the bacterial spores a glass slide was inserted into the paste and was then pulled out. Imme-
diately, the glass slide was subjected to light microscopy to observe the
Bacterial spores were encapsulated following a patented poly- thin layer of the mortar paste with the remaining microcapsules.
condensation reaction based microencapsulation process [21].
The microcapsule is melamine based, and contains inert substance to 2.4.3. Breakage of the microcapsules upon cracking
protect the spores. The size is about 5 μm. The final product is an emul- Breakage of the microcapsules upon cracking is the prerequisite for
sion consisting of microcapsules and water. The concentration of the self-healing behavior caused by bacteria. The fracture surfaces of the
spores in the microcapsules was around 109 cells/g microcapsules specimens (with 1% microcapsules embedded) generated during the
(dry weight). The dry matter content was 38.9% and 51.7% of the emul- tensile test were subjected to Scanning Electron Microscopy (SEM, FEI
sion containing the microcapsules with and without bacterial spores, QUANTA 200F) analysis to verify the breakage of the microcapsules.
respectively. Dry samples were gold coated by a Baltec SCD030 Sputter Coater before
the SEM examination.

2.3. Viability of the microencapsulated spores —Proof of concept 1 2.4.4. Influence of the microcapsules and nutrients on cement hydration
Except for microcapsules, nutrients that were needed for bio-
The viability of the spores after immobilization into microcapsules precipitation, including the food for bacteria (yeast extract, YE) and depo-
was investigated. In order to investigate whether the spores inside the sition agents (urea and Ca-nitrate) were also incorporated. To investigate
microcapsules were still viable and whether the microcapsules can really the influence of these additives on hydration, hydration heat production
protect the spores from being activated before they were broken, a two- was measured, which can be used as an indicator for hydration degree.
step test (Test 1 and Test 2) was performed. Urea decomposition by Seven kinds of cement paste mixtures of the same water to cement
intact and broken microcapsules (loaded with bacterial spores) was ratio (0.5) were made: a reference cement paste R, and cement pastes
examined. The viability of the spores includes the germination into with urea (4%), YE (0.35%), YE (0.85%), Ca-nitrate (8%), μ-capsules (3%),
vegetative cells (active) and the revival of the ureolytic activity. There- μ-capsules (5%), respectively. The dosage of the additives was versus
fore, the amount of urea decomposed by the spores can be used as an cement weight. The hydration heat production (at 20 °C) was deter-
index to evaluate the viability of the spores. mined by a TAM AIR isothermal heat conduction calorimeter [24].
In a first test (Test 1), 2 mL emulsion with intact microcapsules
(with or without bacterial spores loaded) was added to 100 mL sterile 2.5. Applying microencapsulated spores for self-healing cracks
YU medium (consisting of 20 g/L yeast extract and 20 g/L urea). The
amount of urea decomposed in YU medium was measured. 2.5.1. Preparation of the specimens
In a second test (Test 2), the viability of the spores from broken mi- Six series of specimens were made and the composition of each se-
crocapsules was investigated. The shell of the capsules is impermeable ries is shown in Table 1. Group R are the specimens without any addi-
for spores, which means that spores cannot leak out from the capsules. tions. Group N are the specimens with all nutrients needed for bio-
If the nutrients in the YU medium cannot penetrate through the shell, precipitation. Group C are the specimens with the microcapsules (3%)
spores will not germinate and decompose urea. Microcapsules in emul- without bacterial spores. Group NC are the specimens with nutrients
sion (5 mL) were first dried and then were ground in a mortar to break and microcapsules (3%, no bacterial spores loaded). Group NCS3% and
the capsules. The broken capsules (from 2 to 2.5 mL original emulsion) NCS5% are the specimens with nutrients and microencapsulated bacte-
were added to 100 mL YU medium. The amount of urea decomposed rial spores (3% and 5%, respectively).
was determined. In each series, three types of specimens were made, 5 long rein-
The above-mentioned experiments were performed in duplicate forced prisms, 3 normal prisms and 20 cylinders, as summarized in
(n = 2). The amount of urea decomposed was calculated based on Table 2. After casting, the molds were placed in the air-conditioned
the total ammonium nitrogen (TAN) measured in the medium [22]. room (20 °C, N95%RH). The specimens were de-molded after 48 h
One mole of urea (CO(NH2)2) produces 2 mol of NH+ 4 . The amount of (24 h for R) and were placed in the same air-conditioned room until
NH+ 4 can thus indicate the amount of urea decomposed. the time of testing.
J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152 141

Table 1 surface water. The test was done in an air-conditioned room (20 °C,
Composition of the specimens in each series. 60%RH). The water absorption coefficient k (g.cm−2.h−1/2) was deter-
Group Cement Sand Water Nutrients Microcapsule Dry weight of Bacterial mined by Eq. (1).
(g) (g) (g) (g) emulsion (g) microcapsules spores
pffiffi
(g) Q =S ¼ k t ð1Þ
R 450 1350 225 0 0 0 N
N 450 1350 214 57.8 0 0 N Q is the weight of water absorbed at different time intervals (g); S is the
C 450 1350 212.4 0 26.1 13.5 N
area in contact with water (cm2); k is the slope of a plot of water
NC 450 1350 201.4 57.8 26.1 13.5 N
NCS3% 450 1350 192.8 57.8 34.7 13.5 Y
absorbed per square centimeter in function of the square root of time.
NCS5% 450 1350 178.7 57.8 57.8 22.5 Y A vacuum saturation test was also performed. The specimens were
dried in an oven at 60 °C until the weight changes were less than 0.1%
Nutrients included yeast extract, urea and Ca(NO3)2.4H2O. The addition ratio was 0.85%,
4% and 8% of cement by weight. Ca(NO3)2.4H2O contains 30.5 wt.% water. Therefore the at 24 h intervals. The completely dry specimens were then subjected
amount of the mixing water was reduced by the amount of the water in Ca(NO3)2.4H2O to the vacuum saturation test (NBN B 24-213) [26]. The specimens in
and the amount of the water in the microcapsule emulsion. The last column shows dry state were placed in a container and were subjected to vacuum for
whether bacteria were present (Y) or not (N).
3 h and then de-ionized water was added into the container till the
cylinders were completely immersed. The vacuum was maintained
during water addition and lasted 1 h more at constant water level.
2.5.2. Creation of cracks and incubation conditions After the vacuum was stopped, the specimens were kept submersed
28 days after casting, the long reinforced prisms were subjected to a for another 12 h. The final weight of the water saturated specimens
tensile test to create multiple cracks. A uniaxial tensile load was applied was measured. The saturated water absorption was calculated by
to the specimen at a speed of 0.01 mm/s under stroke control. The loading Eq. (2).
was stopped at the point where the average crack width in the specimen
reached 150 μm. The details about determination of stopping point can be Ws ¼ ðWw −Wd Þ=Wd  100% ð2Þ
seen in the supplementary file.
The cylinders were also subjected to a splitting test (Walter&Bai,
250/50, Switzerland) to make cracks after 28 days. The crack width
was controlled by the value of the crack opening measured by the Ws saturated water absorption ratio
attached LVDT. The final crack width in the cylinders was about 0.20– Wd dry weight of the specimen
0.22 mm. Ww wet weight of the water saturated specimen
The cracked specimens were subjected to five incubation conditions:
1) 20 °C, N95%RH; 2) immersion in water; 3) immersion in the deposi-
tion medium (DM); 4) wet–dry cycles with water; 5) wet–dry cycles 2.5.4. Mercury intrusion porosimetry (MIP) test
with DM. DM was composed of 0.2 M urea and 0.2 M Ca(NO3)2. During Pore properties of the specimens were investigated by MIP (PACAL
one wet–dry cycle, the specimens were immersed in water/DM for 16 h 140+440 Series, Thermo Fisher Scientific). The freeze-dried samples
and were then exposed to air for 8 h. The incubation of 2), 3), 4) and 5) (around 5 g) were added to the dilatometer (sample container),
was performed in an air-conditioned room (20 °C, 60%RH). which was then placed in the specific position of the MIP instrument 1
(PACAL 140 Series). The pressure applied was from 0 to 200 kPa. Subse-
2.5.3. Capillary water absorption and vacuum saturation of the quently, the dilatometer was transferred into MIP instrument 2 (PACAL
mortar specimens 440 Series) and was subjected to a high pressure from 0.1 MPa to
After 3 months, two of the three normal prisms (40 mm × 40 mm × 400 MPa, following again the procedure of mercury intrusion and
160 mm) were subjected to the standard strength test [23] to investi- extrusion. Porosity and pore size distribution were obtained.
gate the later age strength of the specimens with additions. The third
prism was cut into 3 cubes (40 mm × 40 mm × 40 mm) for the water 2.5.5. Evaluation of the self-healing efficiency
absorption test (based on the RILEM 25 PEM (II-6) [25]). The cubes Since the self-healing by the aid of microorganisms is mainly due to
were put in the 40 °C oven until the mass changes were less than 0.1% the microbial precipitation of calcium carbonate, measurement of the
at 24 h intervals The four sides of the cubes adjacent to the cut surface healed part of the crack by the deposition and the subsequent regain
were then wrapped in an aluminum tape to prevent water evaporation of water tightness can directly indicate the healing efficiency.
through the sides during the water absorption test. The cubes were
brought into a water bath with a water level of 10 ± 1 mm and the 2.5.5.1. Crack filling. Crack filling was visualized by light microscope
cut surface facing downwards. At regular time intervals, the cubes (Leica S8 APO, Switzerland). The filling efficiency was evaluated by the
were taken out from the water bath and weighed after removing the healing ratio (r), which was the ratio between healed crack area and

Table 2
Information on the specimens prepared in each series.

Shape Size Number Test performed

Type I 30 mm × 30 mm × 360 mm (Reinforcement inside: 5 Multiple-cracking: monitor crack healing


D = 6 mm, L = 660 mm) by light microscopy

Type II 40 mm × 40 mm × 160 mm 3 Two for strength test;


one for water absorption test

Type III D = 78 mm, h = 22 mm (with two steel fibers inside) 20 Water permeability test
142 J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152

initial crack area. The initial images of the cracks in the specimens were
taken immediately after multiple cracking. During incubation, the spec-
imens were subjected to light microscopy every week in the first month
and at the end of the second month. The values of the initial and final
crack area in the images were determined by a Leica image analysis
program. The morphology of bio-CaCO3 precipitated in the cracks was
studied by SEM analysis.

2.5.5.2. Water permeability test. The cracked cylinders were in different


incubation conditions for 8 weeks and were subjected to the water per-
meability test. The cylinders stored under the condition of 95%RH were
not subjected to the water permeability test because no visual healing
occurred. The detailed description of the test process and the calculation
Fig. 2. Strength properties of the specimens (with different additions of microcap-
of the water permeability coefficient (k) can be seen in the previous
sules, 0% (R), 1%, 2%, 3%, 4% and 5% of cement by mass, respectively) at the age of 28 days.
research [11].

2.6. Statistical analysis


after 3 days, the urea was completely decomposed. According to the
Statistical analysis was done with the software SPSS 19.0. A one-way above results, it can be concluded that the spores were still viable
ANOVA was used to compare the average values. Significant differences after immobilization into the microcapsules. Furthermore, only when
between multiple average values were determined according to a the capsules are broken, the spores can germinate and decompose urea.
Student–Newman–Keuls test. The level of significance was 0.05. In No urea was decomposed in the series of the microcapsules (intact
the following graphs and tables, the average values and the standard and broken) without spores loaded (data not shown).
deviations are shown.
3.1.2. Influence of the microcapsules on the mechanical properties of mortar
3. Results The addition of microcapsules did not significantly affect the volume
density (data not shown) but had a negative effect on the mechanical
3.1. Proof of concept properties of the specimens. As shown in Fig. 2, the tensile strength
was decreased significantly (at a confidence level of 0.05) only for a
3.1.1. Viability of the microencapsulated spores dosage of microcapsules higher than 3%.
The viability of the spores after being immobilized into microcap- The addition of microcapsules had a more negative effect on the
sules was evaluated by using the amount of decomposed urea as an compressive strength of the specimens. As shown in Fig. 2, the compres-
index. A limited amount of urea was decomposed in YU medium with sive strength was dramatically decreased by 15% to 34% with increasing
the addition of intact bio-microcapsules, around 3 g/L after 1 day; no addition of 1% to 5% microcapsules.
obvious increase occurred from 1 day to 3 days (Fig. 1). While in the The mechanical properties of the specimens with both microcap-
series of the broken bio-microcapsules, the urea was completely sules and nutrients were investigated to see the combined effect of the
decomposed after 3 days though only small amount (around 3–4 g/L) bio-healing agents. In this case, the strength at a later age (90 days)
of urea was decomposed in the first day. It should be noted that there was tested. The results are shown in Fig. 3. According to the statistical
was already small amount of urea decomposed (about 1–2 g/L) in the analysis, no significant difference was observed in tensile strength of
medium before the addition of microcapsules. This is due to the heating the specimens in different series. Regarding the compressive strength,
process during sterilization of the medium. In addition, during the en- the minimum decrease was noticed in the series of N, around 9%.
capsulation process, a limited amount of spores were not encapsulated Other series with microcapsules showed distinct decrease, varying
into capsules but stayed in the emulsion. These free spores germinated from 22% (NC) to 47% (NCS5%). It can be seen that the addition of
and decomposed a limited amount of urea in the first day. The spores nutrients had less effect on the long-term strength than the addition
inside the capsules could only start to germinate when the capsules of microcapsules. The decrease of the strength was therefore mainly
were broken and hence they could reach the nutrients. Spores need due to the addition of microcapsules.
time to transform from dormant state to activate state. Therefore, only
3.1.3. Survival of the microcapsules during mortar mixing
The microcapsule emulsion was first mixed with water; the distribu-
tion of the microcapsules in water is shown in Fig. 4(a). It can be seen
25
1d
3d
Urea decomposed (g/L)

20

15

10

0
Bacteria loaded Bacteria loaded
microcapsules (unbroken) microcapsules (broken)

Fig. 1. Urea decomposed in YU medium after the addition of the bio-microcapsules. Fig. 3. Mechanical properties of the specimens at the age of 3 months.
J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152 143

Fig. 4. Microcapsules (without spores) in the emulsion (a) and mixed with mortar paste (b).

that the microcapsules have a regular round shape. The microcapsule Fig. 5. Fracture surface of the mortar specimen with microcapsules (3%) embedded
solution was then mixed with other components of mortar; the image (a: 5000 ×; b: 20,000 ×).
of the final mortar paste is shown in Fig. 4(b). It was noticed that
quite some light round dots adhered to the cement or sand particles 3.2. Influence of the microcapsules on water absorption of the
and distributed all over the mortar paste. Comparing the images of the mortar specimens
microcapsules before and after being mixed in mortar, it can be deduced
that these dots were those unbroken microcapsules. Although the addition of nutrients and microcapsules had a negative
effect on the mechanical properties, they had a positive effect on
3.1.4. Breakage of the microcapsules upon cracking decreasing capillary water absorption of the specimens. Compared
The microcapsules were broken under tensile force. As shown in with the R series, the decrease of water absorption in the specimens
Fig. 5, at the fracture surface, many microcapsules were broken and
capsule shells still remained in the matrix, which indicated a good
bond strength between microcapsules and the mortar matrix. It is also 15 400
seen from Fig. 5 that the size of the microcapsules is in the range of
2–5 μm.
Cumulative heat production (J/g)

12
Heat production rate (J/gh)

300
3.1.5. Influence of the microcapsules and nutrients on cement hydration
The heat production rate and cumulative heat production of each R
9
kind of cement pastes are shown in Fig. 6. It can be seen that the urea(4%)
YE(0.35%)
Ca-nitrate can accelerate cement hydration. 0.35% YE, urea and 3% YE(0.85%)
200
μ-capsules delayed somewhat the appearance of the second hydra- 6 Ca-nitrate(8%)

tion peak. When the dosage of YE reached 0.85% and the dosage of µ-C3%

μ-capsules reached 5%, more delay happened. However, it was found


µ-C5%
100
that the cumulative heat production after 7 days was quite similar for 3
R, urea(4%), YE(0.35%), μ-capsule 3% and μ-capsule 5%: in the range of
355–364 J/g. The YE(0.85%) had somewhat lower heat production of
342 J/g, indicating a lower hydration degree. It was also noticed that 0 0
0 1440 2880 4320 5760 7200 8640 10080
Ca-nitrate not only accelerated hydration but also had a positive effect Time (min)
on the hydration degree. The heat production after 7 days was about
397 J/g, which was about 9% higher than for the R. Fig. 6. Influence of different additives on the isothermal heat production (20 °C).
144 J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152

0.3 series N also had some larger pores around 0.3–0.4 μm. Differently,
the sample in series C had more heterogeneous pore size distribution,
0.25 with a large amount of big pores around 2 μm and small pores (about
0.02 μm). Samples in series NC, NCS3% and NC5% had a similar pore
Water absorbed (g/cm2)

size distribution: most of the pores were in the range of 0.04–0.05 μm.
0.2
There was also a small peak at the position of pore size 1–2 μm, which
indicated that there were some large pores (1–2 μm) in these samples,
0.15 similarly with the ones in series C. Furthermore, nano-pores with a size
around 4–5 nm were found in NC and NCS5%.
0.1 In summary, there are two main categories of pores in the samples
R NC with microcapsules, i.e., large pores (around 1–2 μm) and small pores
(0.02–0.05 μm). The samples in R and N had a more homogeneous
0.05 N NCS3%
pore size distribution: the pore size was mainly in the range of
C NCS5% 0.1–0.3 μm.
0
0 12 24 36 48 60 72 84
Time (h) 3.4. Self-healing efficiency
Fig. 7. Water absorption of the specimens with or without microcapsules.
3.4.1. Quantification of self-healing efficiency by microscopy
The development of the crack healing process can be seen from the
with only nutrients (series N), with nutrients and pure microcapsules microscopic images of cracks taken at certain time intervals (0 day,
(series C and NC), with nutrients and bacteria loaded microcapsules 1 week, 2 weeks, etc). An example is shown in Fig. 10. It was clearly
was around 14%, 42% and 48%, respectively, after 72 h (Fig. 7). The series observed that the crack area gradually decreased as time went on. By
with microcapsules, which were loaded with or without bacteria, all 3 weeks, the crack was almost completely healed.
showed a large decrease in the amount of water absorption (more The cumulative healed crack area in each specimen after 8 weeks
than 40%) and in the water absorption rate. The specimens with bio- can be calculated based on its total initial and total final crack area,
microcapsules (with encapsulated spores) showed slightly lower water which is shown in Fig. 11. Although the same methodology was applied
absorption than the ones with pure microcapsules. No significant differ- to create cracks, the cracking behavior was different due to different
ence was observed between series C and NC, and between NCS3% and mechanical properties of the specimens. Crack numbers varied on the
NCS5%. specimens and the crack widths varied from 0.05 mm to 1 mm,
The result of saturated water absorption is summarized in Table 3. resulting in different initial crack area.
The R series had the highest water absorption and the specimens with As shown in Fig. 11, the crack area was decreased after 8 weeks in all
nutrients and microencapsulated bacteria showed the lowest water specimens except those incubated in the air-conditioned room with 95%
absorption. No significant difference was noticed between the series C RH (20 °C), in which no obvious healing was visualized under light mi-
and NC, and between series NCS3% and NCS5%. Series N had a slightly croscopy. It was also noticed that the crack area in all specimens was not
lower water absorption than Series R. Water absorption after vacuum completely healed. The minimum value of the unhealed crack area was
saturation by the specimens with bio-microcapsules was also decreased around 20 mm2, in the specimen of series NCS3%, which was subjected
in the range of 20% to 30%. to wet–dry cycles. Crack healing ratio gave an overall estimation of the
healing efficiency in the specimens (Fig. 12).
Crack healing was observed in all specimens except the ones stored
3.3. Pore properties of the specimens with and without microcapsules at 95% RH. Without the presence of liquid water, the healing ratio in all
specimens was zero. The specimens subjected to full submersion or
Fig. 8 shows the cumulated mercury intrusion into the samples as a wet–dry cycles, all showed certain amount of crack healing. The speci-
function of the pressure applied. It is shown that graphs of R and N have mens without microencapsulated bacteria (series R, N, C and NC) had
a similar steep part and the graphs of NC, NCS3% and NCS5% are quite a healing ratio of 18% to 50%. No significant difference in the overall
close to each other. The ultimate amount of intruded mercury was healing ratio among different series (R, N, C and NC). Yet, the specific
almost the same in these series, except for NCS5%, in which an extra healing ratio of each specimen in the same series varied when subjected
abrupt increase of mercury intrusion occurred at the pressure around to different incubation conditions. In the R series, higher healing ratios
350 MPa, resulting in a higher amount of mercury intrusion. The sample were observed in the specimens which were subjected to the conditions
of series C had much more mercury intruded than the samples in other with the deposition medium. In the series N, C and NC, higher healing
series and the intrusion curve was quite different. The ultimate mercury ratios were obtained when water was used for submersion. When
intruded per unit mass directly relates with the porosity of the matrix. using water as the solution, the healing ratios were higher in the speci-
Therefore, it can be concluded that the specimens in series C had higher mens (except series C) under full immersion than in wet–dry cycles,
porosity than the ones in other series, which had almost the same while using the deposition medium as the solution, the opposite result
porosity. was observed. The healing ratio of the specimens subjected to the con-
The specimens with microcapsules incorporated (with and without ditions using water as the solution was higher than those using medium
bacteria) had different pore size diameter distribution compared to as the solution.
the ones without microcapsules. In series R and N, most of the pores The specimens with microencapsulated bacteria had a much higher
were around 0.1 μm (the peaks in Fig. 9(a) and (b)). The sample in healing ratio, which ranged from 48% to 80%. In view of the overall

Table 3
Saturated water absorption of the specimens in different series.

R N C NC NCS3% NCS5%

Saturated water absorption Ww (%) 5.54 ± 0.14 5.32 ± 0.19 5.22 ± 0.17 5.19 ± 0.21 4.29 ± 0.25 3.85 ± 0.15
J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152 145

0,07

0,06

0,05

Cumulated mercury
volume (ml/g)
R
0,04
N
C
0,03
NC

0,02 NCS3%
NCS5%

0,01

0
0,001 0,01 0,1 1 10 100 1000
Pressure (MPa)

Fig. 8. Mercury intrusion into different samples.

healing ratios, there was no significant difference between the series of the solution. It was noticed that the largest amount of healed crack
NCS3% and NCS5%. The highest value (80%) was obtained in the speci- area (about 80 mm2) was also obtained in the same specimen. The
men of NCS3%, which was subjected to wet–dry cycles with water as healing ratios, in the specimens subjected to the conditions of wet–

a) R b) N
200 200
180 180
160 160
140 140
dV/dlogD

dV/dlogD

120 120
100 100
80 80
60 60
40 40
20 20
0 0
1000 100 10 1 0.1 0.01 0.001 1000 100 10 1 0.1 0.01 0.001
Pore size (um) Pore size (um)

c) C d) NC
200 200
180 180
160 160
140 140
dV/dlogD
dV/dlogD

120 120
100 100
80 80
60 60
40 40
20 20
0 0
1000 100 10 1 0.1 0.01 0.001 1000 100 10 1 0.1 0.01 0.001
Pore size (um) Pore size (um)

e) NCS3% f) NCS5%
200 200
180 180
160 160
140 140
dV/dlogD

dV/dlogD

120 120
100 100
80 80
60 60
40 40
20 20
0 0
1000 100 10 1 0.1 0.01 0.001 1000 100 10 1 0.1 0.01 0.001
Pore size (um) Pore size (um)

Fig. 9. Pore size distribution in the samples from different series of specimens.
146 J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152

0d 1 week

2 weeks 3 weeks

Fig. 10. An example of a crack healing process (specimen in series NCS5% in ‘wd + water’).

dry cycles with water, were higher than those stored at other incubation permeability than those in the conditions with water. In series N, the
conditions. The specimens that were kept immersed in the deposition cylinders in ‘wd + water’ had a lower water permeability than the
medium had lower healing ratios compared with those in water. ones in ‘wd + medium’ and the one in ‘in water’. In the series C, the
It can be seen that the overall healing ratios of the specimens in lowest water permeability was observed in the specimens in the condi-
bacterial series were about 30% higher than those non-bacterial series. tion of ‘in medium’. Compared with the series R, N and C, the series NC
This improved healing efficiency was most probably due to the bacterially had a generally lower water permeability. In the series NCS3%, speci-
induced carbonate precipitation. mens had a large variation of k-values. The lowest water permeability
Table 4 summarizes the values of the maximum crack widths healed was observed in the specimens in the condition of ‘wd + water’. Com-
in different specimens. The specific microscopy images showing the pared with the series NCS3%, specimens in NCS5% had less variation in
maximum healed crack widths can be seen in the supplementary file. k-values within the replicates. As shown in Fig. 14, most of the
It can be seen that the specimens of bacterial series had much wider k-values were in the zone of 10− 6 and 10 − 7 m/s. Therefore, the
cracks healed than for the reference ones. overall final water permeability of the specimens in series NCS5%
Some CaCO3 precipitation (verified by EDS) in the cracks was found was relatively lower compared with the ones in other series. As in
with bacterial indents on the surface (Fig. 13(a)). Some remains of the series NC and NCS3%, the lowest k-values were observed in the
bacteria were also found in between the particles (indicated by the specimens subjected to wet–dry cycles with water, in the range of
white arrow in Fig. 13(b)). 6.4*10− 8 m/s to 1.6*10− 7 m/s.

3.4.2. Water permeability 4. Discussion


The water permeability of the cracked cylinders after the incubation
under different conditions for 8 weeks is shown in Fig. 14. It can be seen 4.1. Influence of the addition of microcapsules on the properties of
that during the 30 day testing period, the water permeability coefficient mortar specimens
k gradually reached a stable value. There was only a slight difference
between the values at 0 day and 30 days in most cylinders, which indi- To engineer the self-healing capacity inside the mortar specimens by
cated that no additional healing occurred during the testing period. In the aid of bacteria, nutrients needed to be incorporated inside the speci-
the series of R, N and C, the k values at 0 day were all in the range of mens. The best option would be to immobilize spores and the relevant
10−6 to 10− 5 m/s. The series NC had slightly lower initial k values, nutrients in one capsule, which could greatly facilitate spores germina-
around 10−6 to 4.7*10−6 m/s. In the series NCS3% and NCS5%, the initial tion under suitable conditions (water/high humidity, O2) since they are
k values varied from 2.2*10 − 7 to 4.8*10 − 6 m/s, and 2.0*10 − 7 to easily reachable for spores. However, due to the technical difficulties of
2.0*10− 6 m/s, respectively. The specimens subjected to wet–dry cycles encapsulating water soluble agents into microcapsules, this option was
with water had the lowest water permeability (the blue dash-dotted not feasible for the moment. Therefore, the nutrients were added to the
curves in chart NCS3% and NCS5%). It was found that the k values after matrix by mixing together with the mortar paste. The TAM air test results
15 days were almost stable. In this study, the final water permeability show that Ca-nitrate has a positive effect on cement hydration while
of the specimens was represented by the average k-value from days 15 yeast extract delays hydration and decreases hydration degree if the
to 30 (Fig. 15). dosage is higher than 0.85%. Similar results were also reported by
In the series R, the cylinders which were subjected to the incubation Bolobova and Kondrashchenko [27]. Small dosages of carbohydrates or
with DM, both full immersion and wet–dry cycles, had lower water amino acids can enhance the plasticizing effect and accelerate hardening
J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152 147

a) R b) N
160 Initial crack area 160 Initial crack area
Final crack area Final crack area
140 140

Crack area (mm2)

Crack area (mm2)


120 120
100 100
80 80
60 60
40 40
20 20
0 0
95% RH in water in medium wd+water wd+medium 95% RH in water in medium wd+water wd+medium

c) C d) NC
160 Initial crack area 160 Initial crack area
Final crack area Final crack area
140 140
Crack area (mm2)

Crack area (mm2)


120 120
100 100
80 80
60 60
40 40
20 20
0 0
95% RH in water in medium wd+water wd+medium 95% RH in water in medium wd+water wd+medium

e) NCS3% f) NCS5%
Initial crack area Initial crack area
160 160
Final crack area Final crack area
140 140
Crack area (mm2)

Crack area (mm2)

120 120
100 100
80 80
60 60
40 40
20 20
0 0
95% RH in water in medium wd+water wd+medium 95% RH in water in medium wd+water wd+medium

Fig. 11. Initial and final (after 8 weeks) crack area in the specimens of different series (a–f) under different incubation conditions.

simultaneously. However, if the dosage is larger than 0.5%, inhibition of On the other hand, the addition of microcapsules decreased the water
cement hydration will happen. The inhibition effect from organic com- absorption. Strength is influenced by the composition and the micro-
pounds is mainly because they are easily be absorbed on the surface of structure of the specimen. Factors such as water to cement ratio, aggre-
mineral particles, thereby screening the contact of cement with water, gates grading, age and curing condition, admixtures, can influence
and hence decrease cement hydration. Therefore, the dosage of yeast strength because they will influence the hydration degree and micro-
extract used in this research is 0.85% of cement by mass. The limited neg- structure of the specimen. The more hydration, the more pore space
ative effect on the hydration degree from YE can be compensated by the will be taken by solid phase, hence less porosity and higher strength
positive effect from Ca-nitrate. will result. Therefore, microstructure is the ‘root’ factor influencing
The addition of microcapsules had dual effects on the mortar matrix. strength. In this study, the specimens were made with the same cement,
On the one hand, it had a negative effect on the compressive strength. sand and water, using the same w/c ratio and sand to cement ratio. The
only difference was that extra healing agents were added in some of the
100% mixes, which consisted of nutrients and microencapsulated bacteria.
The strength decreased after the specimens were incorporated with
these agents, which means the microstructure was changed. The changes
80%
in microstructure could be due to a different hydration degree, or due to
different arrangement (or distribution) of the components, or both. Ac-
Healing ratio

95% RH
60% cording to the TAM air test results, it can be deduced that the hydration
in water
in medium
40%
wd+water
Table 4
wd+medium
20% Maximum crack widths healed in the specimens of series R and NCS5%.

In water (μm) In medium (μm) wd + water wd + medium


0% (μm) (μm)
R N C NC NCS3% NCS5%
R 240–250 170 75 220–230
NCS5% 850–970 330–400 540–600 280–290
Fig. 12. Healing ratio in each specimen under different incubation conditions.
148 J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152

be extremely harmful [28]. This is another reason why the specimens


a with microcapsules had a lower strength than the reference ones.
In conclusion, the addition of microcapsules had no obvious effect on
hydration degree but mainly modified the pore structure of the speci-
mens. They decreased the total pore space resulting in decreased water
absorption. Yet they were weak points (much lower strength compared
with cementitious materials) in the matrix and created more large pores
resulting in a decreased strength. Therefore, the mechanical properties,
especially the compressive strength, were greatly decreased if the addi-
tion amount was higher than 3%.
It is important to investigate the combined effect of the microcap-
sules and nutrients on the mechanical properties of the specimens.
The experimental results showed that more decrease (around 33% to
47%) in the compressive strength occurred with the addition of both
nutrients and microcapsules. Such a drastic decrease of the compressive
strength is not acceptable in practical cases for economic and safety
reasons. Therefore, it is suggested to restrict the addition of bio-
microcapsules to 3% maximum. The compressive strength of NCS3%
of about 55 N/mm 2 is acceptable for many practical applications.
b Furthermore, some functional additives such as water reducing admix-
tures can be used to increase the mechanical strength of the concrete in
practical situations.

4.2. Self-healing properties in mortar specimens

4.2.1. Autogeneous healing in the control series


The crack healing ratio in the specimens without microencapsulated
spores was in the range of 18% to 50% in the specimens after 8 weeks
(56 days) under different incubation conditions. The healing that oc-
curred was due to autogenic sources. Cementitious materials have a cer-
tain capacity of autogenous healing depending on the composition of
the matrix and the environment they are exposed to [29,30]. In general,
two main mechanisms are responsible for the autogenous healing:
secondary hydration of the unhydrated cement particles and precipita-
tion of calcium carbonate. Besides that, the swelling of the hydration
products also contributes to the decrease of the crack area.
Fig. 13. Precipitation in the cracks of the specimen NCS5% under the condition of In early age concrete and high strength concrete, there are still many
‘wd + water’ (a: CaCO3 precipitation with bacterial traces on the surface; b: bacterial unhydrated cement particles in the matrix. Therefore, when there is
remains in between).
water available in the cracks, the unhydrated cement along the crack
wall would start hydration again. The formed products could heal the
cracks. The healing efficiency from this source is greatly dependent on
degree after 28 days in the specimens was similar. Therefore, the micro- the age of the concrete, the water to cement ratio (w/c) and the avail-
structure was modified mainly due to the presence of microcapsules. able water in the cracks. Autogeneous healing from the precipitation
In view of the water absorption results, it can be concluded that the of calcium carbonate could happen in any type of concrete. The CO2
open porosity was decreased after the addition of microcapsules. How- from atmosphere dissolves in water and generates CO2− 3 in the alkaline
ever, based on the cumulative mercury intrusion (Fig. 8), this is not the environment (the pH of concrete is around 12.5–13). The free dissolved
case. The specimens with microcapsules had similar or even a bit higher Ca2 + (from the crack surface) reacts with CO23 − and CaCO3 can be
amount mercury intruded, which indicated a similar or a bit higher formed.
porosity. These conflicting results were due to the breakage of the The specimens in this study had a w/c of 0.5 and were cracked at the
microcapsules under high pressure during mercury intrusion. After age of 28 days. Theoretically, complete hydration could be obtained if
the microcapsules broke, more space was released (that is the reason the w/c is larger than 0.42 (1 g cement binds about 0.23 g water and
why more small pores (b 0.05 μm) appeared), therefore MIP results physically absorbs 0.19 g water) in a sealed environment. However, in
exhibited a higher porosity compared with results obtained from satu- practical cases, full hydration of OPC is not possible due to the non-
rated water absorption (original porosity). In addition, the space which uniformly distributed water and limited available space for the develop-
is taken by a microcapsule can still be regarded as a pore or weak point ment of hydration products [24]. It has been reported that the hydration
during strength testing, since it cannot withstand the load from com- degree of OPC at the w/c of 0.5 is about 74% after 28 months [31]. There-
pression (while during the process of water absorption and water fore, in our test, the specimens still had unhydrated cement inside the
saturation, the microcapsules will stay intact and block the pores). This matrix (at least 26% of the initial amount of cement) at the cracking
is one reason why the lower porosity did not contribute to a higher age (28 days).
strength in the specimens with microcapsules. The healing was also due to the precipitation of calcium carbonate.
Strength is not only influenced by porosity, but also by pore size The amount of CaCO3 precipitation depends on the amount of CO23 −
distribution, and pore geometry (connectivity, tortuosity). Although formed and Ca2 + dissolved, which relates with the concentration of
microcapsules took up some pore space, they also caused large pores CO2, the pH in the surroundings and the composition of the matrix.
of 1–2 μm (see Fig. 9). In general, a pore size of b20 nm is classified as Ca2 + can be available from Ca(NO3)2, from Ca(OH)2, or from un-
harmless, while 20–50 nm is thought to be less harmful and 50– hydrated cement particles. The specimens with the addition of nutrients
200 nm is harmful. A pore size larger than 200 nm (0.2 μm) is said to had more crack healing under the conditions of ‘in water’ (47%) and
J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152 149

0 5 10 15 20 25 30 0 5 10 15 20 25 30
1.00E-05 1.00E-05

1.00E-06 1.00E-06

1.00E-07 1.00E-07

R N
1.00E-08 1.00E-08

0 5 10 15 20 25 30 0 5 10 15 20 25 30
1.00E-05 1.00E-05

1.00E-06 1.00E-06

1.00E-07 1.00E-07

C NC
1.00E-08 1.00E-08

0 5 10 15 20 25 30 0 5 10 15 20 25 30
1.00E-05 1.00E-05

1.00E-06
1.00E-06

1.00E-07

1.00E-07
1.00E-08

1.00E-09
NCS3% 1.00E-08
NCS5%

In water: ; In medium: ; wd+water: ; wd+medium:


Y-axis: k-value (m/s); X-axis: Time (d)

Fig. 14. Water permeability of the specimens during the test periods.

‘wd + water’ (38%), because of more released Ca2+ (due to Ca(NO3)2) times (‘in water’) and 2.7–3.1 times (‘wd + water’) of those in the R
compared with the R series (30% and 18%, respectively). However, series. The opposite result was obtained under the condition of
under the conditions of ‘in medium’ and ‘wd + medium’, the speci- ‘wd + medium’. Theoretically, microcapsules occupied some space in
mens in the series R had more crack area healed (34% and 46%, respec- the crack wall which would decrease the area of the exposed cementi-
tively) than that in the series N (25% and 38%, respectively). Similarly, tious matrix, and hence, less Ca2+ could be released. However, on the
series C had higher healing ratios than NC. This is attributed to the fact other hand, the large pores in the matrix due to the addition of microcap-
that although DM can provide extra Ca2 +, the pH of the medium sules (based on MIP results) might facilitate the solubilization of Ca2+
(pH = 5.5–6) was lower than for plain water (pH = 6.8–7.2). A higher and the penetration of CO2−
3 . However, for the specimens with multiple
pH is more beneficial for the dissolution of CO2 and the subsequent cracks of the widths from 0.05 mm to 1 mm, cracks, instead of matrix
transformation of CO2 to CO2− 3 , and hence CaCO3 formation. The addi- permeability, became the main issue for water penetration. Since all
tion of microcapsules had an ambiguous effect on autogeneous healing. specimens showed multiple cracks, with similar crack width ranges
Under the conditions of ‘in water’ and ‘wd + water’, the healing effi- and crack numbers, the permeability in these cracked specimens should
ciency in the microcapsule series was higher than that of the series R. be of the same magnitude. Therefore, the release of Ca2+ mainly depends
The healed crack area in the microcapsule series was around 1.6–2.1 on the Ca source and storage condition (with sufficient water or not).
150 J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152

4.2.2. Self-healing efficiency by microencapsulated bacteria the healing efficiency was not increased proportionally. This is probably
The viability test results demonstrated that the spores, after encap- due to the inert substance that is encapsulated together with the bacteria,
sulation into microcapsules, can still germinate and revive the ureolytic which may give a water-proofing effect to the crack surfaces after release.
activity to decompose urea. The prerequisite is that the microcapsules This water-proofing effect could slow down the penetration of water into
need to be broken. Then the spores inside can start to work because the matrix around the crack zone to dissolve the nutrients, and the trans-
the impermeable capsule shell is no longer intact. In the unbroken cap- port of dissolved nutrients to the spores. Hence, with large amount of
sules, the spores stay dormant since no activators (water, nutrients and broken microcapsules, the increased water-repellent effect may make it
oxygen) are reachable. The cracking triggered the breakage of the difficult for the spores to reach enough nutrients to germinate and revive
microcapsules and the increased self-healing efficiency was then con- the ureolytic activity. For future optimization of the dosage of the micro-
tributed by the microencapsulated bacteria. When there was water capsules used, except for mechanical properties, the barrier effect on the
available in the surroundings, the nutrients embedded in the crack diffusion of water and nutrients due to the inert substance on the crack
zone were released and became available for the spores in the broken surface should also be considered.
capsules. The spores then started to germinate and revive the ureolytic
activity. Urea, released from the crack zone or dissolved in the deposi-
tion medium (if present), was decomposed into CO2− 3 and NH3/NH+ 4 4.2.3. Influence of incubation conditions
by the germinated bacteria (catalyzed by bacterial urease) under alkaline The incubation condition has great influence on the self-healing effi-
pH. When CO2− 3 ions met with Ca2+ ions in the surroundings, CaCO3 ciency, both on the autogenous healing in non-bacteria series, and on
2+
formed. The Ca source was derived from the matrix itself, the added the engineered self-healing in bacteria series.
Ca(NO3)2 and the DM (if present). During the incubation period, it was Water is the essential element for autogenous healing. It participates
noticed that the white precipitation existed not only in the cracks, but in all relevant reaction processes, like secondary hydration of unhydrated
also on the surface of the specimens, in the surface pores of the specimens cement, precipitation of CaCO3 and swelling of hydration products. With-
and on the wall of the incubation containers. But most of the precipitation out water, all these reactions would not happen, and hence, healing
was concentrated in the cracks would not occur. Therefore, the specimens, stored in the conditions of
No significant difference in healing efficiency was observed between 95%RH in which no free water is present in the surroundings, had no
NCS3% and NCS5%. Specimens in series NCS3% had slightly higher crack crack area healed, including the ones with microencapsulated bacteria.
healing ratios while the ones in NCS5% had an overall lower water per- This is because bacterial spores also need water to revive and the nutri-
meability. With an increased addition of microencapsulated bacteria, ents in the matrix need to dissolve in water to become available for

in water in medium wd + water wd + medium in water in medium wd + water wd + medium


1.00E-05 1.00E-05

1.00E-06 1.00E-06

1.00E-07 1.00E-07

1.00E-08 1.00E-08

R N
1.00E-09 1.00E-09

in water in medium wd + water wd + medium in water in medium wd + water wd + medium


1.00E-05 1.00E-05

1.00E-06 1.00E-06

1.00E-07 1.00E-07

1.00E-08 1.00E-08

C NC
1.00E-09 1.00E-09

in water in medium wd + water wd + medium in water in medium wd + water wd + medium


1.00E-05 1.00E-05

1.00E-06 1.00E-06

1.00E-07 1.00E-07

1.00E-08 1.00E-08

NCS3% NCS5%
1.00E-09 1.00E-09

Fig. 15. Final water permeability coefficients (k-values) of the specimens in each series (three black dots represent three replicates for each condition).
J.Y. Wang et al. / Cement and Concrete Research 56 (2014) 139–152 151

bacteria. Thus, bio-CaCO3 cannot precipitate if no water is present in the of the dosage of the microcapsules, the composition and pH of the incu-
crack zone. bation solution and the time interval between wet and dry stage is
Theoretically, the DM containing 0.2 M urea and 0.2 M Ca(NO3)2 can needed to improve the healing efficiency. Although it will often not be
provide extra Ca2+ for CaCO3 precipitation and more urea can be avail- possible to change the latter two parameters in a practical situation,
able for bacteria, hence should result in an increased healing efficiency. extra supplementary techniques could be applied, such as surface cover-
However, no significant obvious beneficial effect was obtained when age by moisture retaining materials, to prolong the wet stage beneficial
the specimens were subjected to the conditions with the DM. During for self-healing.
the incubation stage, Ca2+ releases during the dissolution of Ca(OH)2
(CH) in the matrix. CH has very low solubility (1.7 g/L (0.02 M) at Acknowledgments
20 °C). The dissolution of CH follows the equilibrium which is shown
in Eq. (3). The financial support from the Research Foundation Flanders (FWO-
2þ Vlaanderen, grant no. G.0157.08) and Ghent University (a BOF grant) is
CaðOHÞ2 ↔Ca þ 2OH ð3Þ
gratefully acknowledged.

The reaction will shift to the left side if the concentration of Ca2+ is
higher than 0.02 M in the solution. When the reaction shifts to the left Appendix A. Supplementary data
side, the amount of OH− will be decreased, and hence, the pH decreases.
For the sequestration of CO2, transformation from CO2 to CO23 −, and Supplementary data to this article can be found online at http://dx.
CaCO3 precipitation, an alkaline environment is preferable. If the speci- doi.org/10.1016/j.cemconres.2013.11.009.
mens were kept fully immersed in the DM, although more Ca2+ would
be available, the pH condition will restrict the increase of the CaCO3 References
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