Cement and Concrete Composites 78 (2017) 84e96

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Cement and Concrete Composites

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

Performance recovery concerning the permeability of concrete by

means of a microcapsule based self-healing system
Biqin Dong, Guohao Fang, Yanshuai Wang, Yuqing Liu, Shuxian Hong, Jianchao Zhang,
Shangmin Lin, Feng Xing*
School of Civil Engineering, Guangdong Province Key Laboratory of Durability for Marine Civil Engineering, The Key Laboratory on Durability of Civil
Engineering in Shenzhen, Shenzhen University, Shenzhen 518060, PR China

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

Article history: This paper presents work toward the development of self-healing materials that hold promise for
Received 4 July 2015 permeability healing of concrete or other cementitious composites. To achieve this innovative system,
Received in revised form Urea-formaldehyde/Epoxy microcapsule was designed and synthesized by an in-situ polymerization
27 October 2016
method, using epoxy resin E-51 as the curing agent and urea-formaldehyde resin as the shell material.
Accepted 7 December 2016
Available online 9 December 2016
The viability of microcapsule and the influence of microcapsules on mechanical properties of specimens
were investigated first. The breakage of microcapsules upon cracking and the crack-healing results were
verified by SEM/EDS. Self-healing capacity was evaluated by crack-healing effect and chloride perme-
Keywords:
Self-healing system
ability. The experimental results shown that the chloride diffusion coefficient decreased from 8.15 to 6.53
Concrete (
1012 m2 s1) after 28-day healing. The healing efficiency of permeability increased to a maximum
Microcapsule level of 19.8%. It was also noticed that several factors such as the amount of microcapsules, particle size,
Microcrack healing age, curing temperature and pre-load level have great influences on the self-healing efficiency.
Permeability © 2016 Published by Elsevier Ltd.

1. Introduction with the help of multitudinous techniques [7e9]. Adding limestone

Concrete deterioration is related to its permeability, especially
in marine and coastal areas [1]. It is well known that a good
designed and manufactured concrete is originally water-tight,
containing discontinuous pores and microcracks. However, once
the concrete is subjected to extreme loading and weathering, it
deteriorates through a variety of physical and chemical process,
which results in cracking. Cracks in concrete generally interconnect
flow paths and increase concrete permeability [2]. The increase of
permeability due to crack propagation allows more water or
aggressive chemical ions (e.g. chloride, sulfate, carbonate) to
penetrate into the concrete, facilitating further deterioration. A
chain reaction of 'deterioration - cracking - more permeable con-
crete - further deterioration' may eventually results in destructive
deterioration of the concrete structure [3e6]. Therefore, it is sig-
nificant to cut off such 'chain' to heal the cracks and decrease the
permeability.
To address these problems, many researches are carried out
* Corresponding author.
E-mail address: xingf@szu.edu.cn (F. Xing).
fines as cement paste replacement would significantly reduce the
early shrinkage of the concrete produced [10,11]. Surface coating
system is another chose as a preventative measure to repair con-
crete and against aggressive chemical ions penetration into con-
crete [12e14]. These enhancements have positive effects on the
initial crack restraining and against harmful ions penetration into
concrete for a certain period. However, they may not be applied to
prevent the lately emerged cracks and further deterioration caused
by freeze-thawing, temperature and mechanical loading, etc.
A new microcapsule-based self-healing system is developed for
solving the long-term cracking problem and preventing further
deterioration [15e20]. In the first step, the healing agent is sealed
in microcapsules. For realizing this step, microcapsule synthesis
technologies are adopted for fabricating ideal microcapsules
[21,22]. In addition, the geometry and texture of microcapsules are
critical during successfully healing process and it is found that
spherical microcapsules could reasonably satisfy this type of re-
quirements in concrete [16,19]. Once microcrack initiates and
propagates, the embedded microcapsule at the crack-tip is broken.
The healing agent inside microcapsule is then released to heal the
crack. The proposed crack-healing concept is proved to be feasible
by several researchers [23,24]. A successful novel attempt is made

http://dx.doi.org/10.1016/j.cemconcomp.2016.12.005
0958-9465/© 2016 Published by Elsevier Ltd.
 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96
at Shenzhen University by Xing and Dong et al. [25e27] with
promising results using organic microcapsules in concrete. How-
ever, there are two main problems concerning microcapsules based
self-healing cementitious materials, including the limited self-
healing effect and weak boding between microcapsules and
cementitious matrix [28]. As for employing of urea formaldehyde or
epoxy composite as healing agent, although several researches
have been carried on this attempt the comprehensive investigation
of its healing feature concerning impermeability recovery in
cementitious materials has not achieved yet [29,30].
In order to study the performance recovery concerning
permeability of microcapsules based cementitious materials, Urea-
formaldehyde/Epoxy microcapsule was designed and synthesized
by an in-situ polymerization method, using epoxy resin E-51 as the
curing agent and urea-formaldehyde resin as the shell material. The
crack-healing concept based on microcapsules was investigated
with the help of scanning electron microscopy (SEM) and energy
dispersive spectroscopy (EDS). The permeability-healing process
was monitored with the help of mercury intrusion porosimetry
(MIP) and rapid chloride migration (RCM) test. Based on the RCM
results, the changing ratio of chloride permeability over different
healing time were calculated to quantitatively study the healing
efficiency and other influence factors.
2. Materials and methods
2.1. Theoretical background of curing reaction mechanism
Fig. 1 shows the chemical reaction mechanism of healing system
consisting of epoxy resin E-51, BGE (butyl glycidyl ether) and
harden agent (MC 120D), which occurs by a step-growth process. In
the first step, tertiary amine attacks the epoxy functional group to
generate the adduct. In the second step, the newly generated
adduct attacks another epoxy group to produce the clathrate
Fig. 1. Curing reaction mechanism of self-healing system.
85
consisting of positive and negative ions. In the last step, the anion in
clathrate is used as active center to catalyze the copolycondensa-
tion of epoxy group in order to create terpolymer. The terpolymer
made up of epoxy resin, thinner and imidazole has strong con-
nective property. Based on this mechanism, therefore, epoxy resin
E-51 was chosen as core materials of microcapsules (healing agent),
BGE as thinner agent and MC120D as harden agent which were
premixed in cement pastes. Theoretically, once the microcapsules
are triggered upon cracking, the healing agent (epoxy resin E-51)
inside microcapsule release and react with the curing agent (BGE
and MC120D) to form healing products and fill the cracks.
2.2. Microcapsule fabrication
Microcapsules were produced using UF(urea-formaldehyde)/
epoxy resin at a urea/formaldehyde molar ratio of 1:1.5 by means
of in-situ polymerization procedure. Briefly, a mixture of urea and
37% formaldehyde was adjusted to PH 8.0e9.0 with 78% trietha-
nolamine aqueous solution. The UF prepolymer was prepared by
stirring at 70  C until the mixture became transparent. The tem-
perature was then reduced to 40  C. Simultaneously, the oil/water
emulsion was prepared by adding a mixture of 0.5% SDBS (sodium
dodecyl benzene sulfonate) aqueous solution and epoxy resin - BGE
(1-butyl glycidyl ether) mixture (epoxy resin/BGE ¼ 100/17.5). This
oil/water emulsion was added to the UF prepolymer. The reaction
liquid was adjusted to PH 2.0e3.0 with 2% sulfuric acid solution.
The resulting mixture was stirred at 60  C for 2 h, then cooled to
room temperature. After filter and air-dry for 24 h, the resultant
microcapsules were dished with pure water and dried in a vacuum
oven.
2.3. Specimen preparation and pre-processing
The chemical composition of the cement is given in Table 1. The
86 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96
Table 1
Components and mineral composition (%) of cement.
SiO2 Al2O3 Fe2O3 CaO MgO
18.96 6.05 3.42 63.22 1.21
physical and mechanical properties of cement specimens are listed
in Table 2. Thirteen series (from A to M) of specimens were made
and the composition of each series is shown in Table 3. In this
research, PVA fiber was mixed in the specimens in order to control
the crack width. In each series, three types of specimens were made
followed the three type molds as summarized in Table 4, except
series A which was only made in type I. After casting, the molds
were placed in the curing chamber (95 ± 5% RH, 20 ± 2  C). After
24 h, the specimens were demoulded and placed back for a 59-day
extra curing under the same environmental conditions. It should be
noted that 59-day extra curing was applied to minimize the effect
of secondary hydration of the unhydrated cement particles and for
better analyze the healing process of the adopted system.
In addition, in order to study the healing effects, damages
(microcracks) were initiated by applying a compressive load in the
range of 30%e70% of compressive strength (smax) with an incre-
ment of 10%. After pre-loading process specimens (typeⅡ and type
Ⅲ)were healed at a temperature of 30  C, 40  C, 50  C and 60  C for
3d, 5d, 7d, 14d and 28d, respectively.
2.4. Proof of crack-healing concept
2.4.1. Physical properties of microcapsule
After microcapsules fabrication, the physical properties of mi-
crocapsules were tested in order to test whether the microcapsule
is suitable for the self-healing system. The morphology of micro-
capsule was evaluated by means of SEM (FEI, Quanta TM 250 FEG,
USA). In order to better understand the morphology of microcap-
sule, the magnification times were set from 500x to 4000x. Besides,
the thermal stability of microcapsules was investigated by means of
thermal gravimetric analyzer (TGA) (TA Instruments, Q50, USA).
TGA curves were obtained under a dynamic atmosphere of syn-
thetic air (flow air of 40 mL min1) and a heating rate of
10  C$min1 from 0 to 500  C with a sample mass of 5.0 mg in a
ceramic pan (50 mL). In addition, biomicroscope (QianKe, XSP-BCC,
China) was applied to visualize the morphology of microcapsules
under different temperatures (with 50  C interval).
2.4.2. Survival of the microcapsules during the mortar mixing
process
Light microscope (CAIKON, XTL-3000C, China) was applied to
visualize the microcapsules before and after mixing with mortar
paste. The magnification range of this equipment was set from 7x to
350x. After the mortar paste (containing 4% microcapsules) was
ready, a glass slide was inserted into the paste and then pulled out.
The glass slide was then subjected to light microscopy to observe
the thin layer of the mortar paste with the remaining
microcapsules.
Table 2
Physical and mechanical properties of cement specimens.
Specific surface area Setting time Compressive Flexural
(m2/kg) (min) strength strength
(MPa) (MPa)
initial Final 3d 28d 3d
362 140 245 38.7 55.8 7.2
Loss on ignition C3S C2S C3A C4AF
3.07 65.35 5.06 10.23 10.40
2.4.3. Breakage of the microcapsule upon cracking
Breakage of the microcapsule upon cracking is the prerequisite
for self-healing behavior caused by healing agent. The fracture
surfaces of the mortar specimens (with 4% microcapsules
embedded) generated during the compressive test were subjected
to SEM analysis to verify the breakage of the microcapsules.
2.4.4. Crack-healing results
After healing, some samples were breached to further study the
crack-healing mechanism and verify the healing results by means
of SEM and EDS (AMETEK EDAX, EDS, USA). Crack filling area was
visualized by SEM and analyzed by EDS in order to clearly identify
the healing products, and indicate whether the crack-healing sys-
tem is feasible.
2.5. Influence of the microcapsules on the initial mechanical
properties of mortar
Mortar specimens (TypeⅠ) with different amounts of microcap-
sules were applied to investigate the influence of microcapsules on
the initial mechanical properties of mortar specimens. The amount
of the microcapsules emulsion added was based on the microcap-
sules dry weight content as 0%, 2%, 4%, 6% and 8% of cement. After
28 days curing, initial compressive strength was measured by
means of pressure testing machine (Jianyi, JYE-2000E, China).
2.6. Self-healing of permeability test procedure
2.6.1. Mercury intrusion porosimetry (MIP) test
Pore properties of the specimens were investigated by MIP
(Micromeritics, Auto pore 9500, USA). The oven-dried mortar
samples (TypeⅡ) were oven-dried under 60  C and added to the
penetrometer (sample container), which was then placed in the
specific position of the MIP instrument 1 (the low pressure vessel).
The pressure applied was from 0 to 29.98 psia. Subsequently, the
dilatometer was transferred into MIP instrument 2 (the high
pressure vessel) and subjected to a high pressure from 36.4 to
29870 psia, flowing again the procedure of mercury intrusion and
extrusion. Thus, porosity and pore size distribution were obtained.
Porosity and pore size distribution were then obtained based on the
previous researches [31,32].
2.6.2. Rapid chloride migration (RCM) test
The rapid chloride permeability test setup (NJ-RAM type) is
shown in Fig. 2. For each series, mortar samples (Type Ⅲ) were put
into the testing-chambers at the certain time. Sodium hydroxide
solution (0.3 mol/L NaOH) and sodium chloride solution (10 wt%
NaCl) were poured in the chambers on the side of concrete sample
separately, where electrode in NaOH chamber becomed an anode
and electrode in NaCl chamber acted as a cathode. During the test, a
voltage of 60 V was continuously applied and the current was
recorded at 30-min intervals using a data logger over a 6-h period.
After the test, mortar samples were cut from the middle portion
of each cylinder. Silver nitrate (AgNO3) was applied to freshly split
samples to determine chloride penetration depth. Silver nitrate
28d
reacts with chloride ions to form white AgCl, as shown in Eq. (1).
Chloride penetration depth was measured as the visible boundary
10.6
of white precipitation of silver chloride (AgCl). 10 points on each
 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96 87

Table 3
Compositions of the self-healing mortar matrix.

Group Microcapsule fraction Diameter (mm) Harden agent Thinner agent (BGE) Water/cement Sand/cement ratio PVA
(wt.% with binder) (wt.% with microcapsule) (wt.% with microcapsule) ratio (wt.% with binder)
MC120

A 0 e e e 0.67 0.6 1.5

B 2.0 132 20.0 17.5 0.67 0.6 1.5
C 2.0 180 20.0 17.5 0.67 0.6 1.5
D 2.0 230 20.0 17.5 0.67 0.6 1.5
E 4.0 132 20.0 17.5 0.67 0.6 1.5
F 4.0 180 20.0 17.5 0.67 0.6 1.5
G 4.0 230 20.0 17.5 0.67 0.6 1.5
H 6.0 132 20.0 17.5 0.67 0.6 1.5
I 6.0 180 20.0 17.5 0.67 0.6 1.5
J 6.0 230 20.0 17.5 0.67 0.6 1.5
K 8.0 132 20.0 17.5 0.67 0.6 1.5
L 8.0 180 20.0 17.5 0.67 0.6 1.5
M 8.0 230 20.0 17.5 0.67 0.6 1.5

Table 4
Information on the specimens prepared in each series.

Shape Size Number Test performed

TypeⅠ 40
40
160 mm 3 Compressive strength test

Normal prism
TypeⅡ 10
10
30 mm 3 mercury intrusion porosimetry test (MIP)

Cuboid
Type Ⅲ F100
100 mm 54 Rapid chloride migration test
(RCM)
Cylinder

Fig. 2. Schematic illustration of RCM test.

Fig. 3. SEM image of microcapsule.

88 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96

Fig. 4. TGA curve of microcapsule.

Fig. 5. Morphology of microcapsules before and after mixing with mortar.

side were equidistantly selected to calculate the average depth.

Agþ þ Cl /AgCl Yðsilver  whiteÞ (1)

To calculate chloride diffusion coefficient form the RCM test
results for concrete, the chloride content is determined based on
Eq. (2):
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi !
0:0239ð273 þ TÞL ð273 þ TÞLXd
DRCM ¼ XD  0:0238
ðU  2Þt ðU  2Þ
(2)

where DRCM is the diffusion coefficient (
1012 m2/s), U is the

voltage (volt), T is the average value of initial and end temperature
of the cathode solution ( C), L is the thickness of specimen (mm), Xd
the average of chloride penetration depth (mm), and t is the test
time.

2.6.3. Evaluation of the self-healing efficiency

The chloride diffusion coefficient is usually chosen as important
parameter to investigate the permeability of cementitious Fig. 6. SEM image of the microcapsule triggered by micro-crack.
 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96 89

materials [33,34]. In the research, the healing efficiency of the self- 3. Results and analysis
healing system, hRCM, is calculated based on the chloride diffusion
coefficient (Eq (3)). 3.1. Proof of crack-healing concept

3.1.1. Suitable microcapsules

D  Dinitial As shown in Fig. 3, the microcapsule has an excellent surface
hRCM ¼ ð1Þ
healed
100% (3) texture (such as the roughness) which will in turn enhance the
Dinitial
adhesion to the cement paste. On the basis of the TGA curves
where hRCM is the repairing rate of the self-healing system (%), (Fig. 4), two thermal events are identified. The first mass loss take
Dhealed is the chloride diffusion coefficient after healing place below 250  C, which is attributed to vaporization of moisture
(
1012 m2/s), Dinitial is the chloride diffusion coefficient after pre- as capsule wall may adsorb water during sample handling. As
loading test (
1012 m2/s). The hRCM is defined as how many shown in Fig. 4(a), the microcapsules keep the integrality of surface
decrease of chloride migration coefficient after healing comparing topography at 100  C. The local deformation of microcapsule occurs
with the data after pre-loading test. at 200  C (see Fig. 4(b)). However, it seems that the microcapsules

Fig. 7. SEM/EDS results of self-healing area.

60
230 μm
3.68%
180 μm
5.59%
5.93% 132 μm

14.96%
16.76% 15.86% 16.69%
18.34%
20.76%
Compressive strength (Mpa)

22.95%
24.90%
27.56%
40

20

0
0 2 4 6 8
Microcapsules content (%) of cement by mass
Fig. 8. Initial compressive strength properties of the specimens with different amount of microcapsules.
90 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96

still keep the integrality. The second event (the second mass loss)
which begins at 250  C ends around 500  C and is strictly related to
the thermal decomposition of microcapsule (see Fig. 4(c)). The re-
sults clearly demonstrate that the microcapsules remain thermal
and mass stable until the temperature of 250  C is reached. The
experimental results reveal that the adopted microcapsules satisfy
the self-healing system due to their basic physical properties.
3.1.2. Survival of the microcapsules during mortar mixing
As shown in Fig. 5 (a), the microcapsule has a regular round
shape. After mixing with other components of mortar, the final
mortar paste is shown in Fig. 5 (b). It is noticed that the
microcapsules keep a complete morphology and connected well
with the cement paste. Comparing the images of the microcapsules
before and after mixing with mortar, it can be deduced that the
microcapsules can survive during the mixing process and has a
good compatibility with cement paste.
3.1.3. Breakage of the microcapsules upon cracking
The microcapsules were broken under cracking with pre-
loading process. As shown in Fig. 6, microcapsule is broken at the
fracture surface. However, the capsule shell still remains in the
matrix, which indicates a good bond strength between microcap-
sules and the mortar matrix. The finding reveals that the desired

Fig. 9. (a) Pore size distribution of mortar samples with and without microcapsules. (b) Porosity fractions of mortar samples with and without microcapsules at different ranges of
pore size.
 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96 91

trigger system actually works upon cracking.
3.1.4. Crack-healing results
As shown in Fig. 7, the SEM results reveal that crack area is filled
by the healing products. With the further element identify by
means of EDS, the high amount of nitrogen and carbon are
observed in the healed area, which are the main elements of
healing agent but normally do not exist in the cementitious ma-
terial. In other words, the self-healing system indeed works on the
crack-healing. In generally, crack width and connectivity are the
main factors affecting the permeability of concrete. Thus, it is no
doubt that crack-healing is the prerequisites for the permeability
healing. In a word, the above-mentioned feasibility studies mani-
fest that the adopted microcapsule based self-healing system is
indeed suitable to fulfill the healing functionality in concrete.
3.2. Influence of the microcapsules on the initial mechanical
properties of mortar
As shown in Fig. 8, the initial compressive strength is decreased

Fig. 10. (a) Pore size distribution of microcapsules based samples before and after healing.
(Microcapsule: content ¼ 6.0 wt.% by cement, diameter ¼ 230 mm).
(Samples: pre-loading level ¼ 60% smax, healing temperature ¼ 50  C).
(b) Porosity fractions of microcapsules based samples before and after healing at different ranges of pore size.
(Microcapsule: content ¼ 6.0 wt.% by cement, diameter ¼ 230 mm).
(Samples: pre-loading level ¼ 60% smax, healing temperature ¼ 50  C).
92 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96

significantly (at a confidence level of 5%) only for a dosage of mi- addition, as shown in Fig. 11, capillary porosity, continuous pore
crocapsules higher than 2%. The negative effect become more and diameter and pore connectivity are taken account to further
more serious with the increase of microcapsules. The compressive investigate the healing process. It is found that the capillary
strength is dramatically decreased by about 5%e25% with porosity drops from 19.3% to 15.09% after 14 days healing. During
increasing addition of 2%e8% microcapsules. It can be seen that the this healing period, the continuous pore diameter is dramatically
added microcapsules have negative effect on the compressive decreased by 95.37 nme52.37 nm. Finally, the pore connectivity
strength of the specimens, which finding agrees with previous present similar decreasing trend comparing with other two pa-
research [35]. De Belie et al. found that the compressive strength rameters, decreasing from 33.48% to 26.89%. The experimental re-
would dramatically decreased by 15%e34% with increasing addi- sults reveals that this mortar specimens have significant crack-
tion of 1%e5% microcapsules. Comparatively, the adopted micro- healing effects due to healing process, indicating that a more
capsules have less negative effect on compressive strength than dense and lower permeability would be achieved after healing
previous researches. Moreover, it also demonstrated that the [2,40].
negative effect on compressive strength of specimens from adding
microcapsules is inevitable from the point of this self-healing ma-
terials. Besides, the mechanical properties would also be affect by 3.4. Self-healing efficiency
the size of microcapsules. The compressive strength of mortar
specimens with microcapsules of 132 mm diameter slightly The development of self-healing process can be quantitatively
decrease by 3.68% with the content of 2%, which is lower than other analyzed base on the ratio of chloride diffusion coefficient. An
bigger size microcapsules. The similar phenomenon is also found in example is shown in Fig. 12, it can be seen that there is a high
other content level. The finding indicates that both content and size decreasing rate of chloride diffusion coefficient (D) at the first 3
of microcapsules have significant negative impact on the me- days healing, from 8.15 to 7.00 (
1012 m2 s1). After then the
chanical properties especially when the content is more than 4 wt% decreasing rate become slow. And the coefficient D gradually
by cement and the size is bigger than 230 mm. reached a stable value after 28 days healing. In the end, the coef-
In generally, strength is influenced by the composition and the ficient D drop to the lowest level of 6.53 (
1012 m2 s1). Based on
microstructure of the specimen [36e38]. Factors such as water to this ratio of coefficient D, the healing efficiency of permeability was
cement ratio, aggregates grading, age and curing condition can also calculated. As shown in Fig. 12, it can be seen that during 28-
influence strength since they will influence the hydration degree day healing period, the healing ratio hRCM gradually reached a
and microstructure of the specimen. With more hydration, more stable value of 19.8%. The similar developing trends are also found
pore space will be replaced by solid phase, hence less porosity and
higher strength can be reached. Thus, microstructure is the 'root'
factor influencing strength. At the same time, strength is mainly
influenced by the pore structure. Generally, a pore size of <20 nm is
classified as harmless. A pore size smaller than 50 nm is regarded as
less harmful, while 50e200 nm is harmful. A pore size larger than
200 nm is classified as extremely harmful [39]. As shown in
Fig. 9(a), the addition of microcapsules obviously modifies the pore
distribution of mortar samples. The porosity of mortar specimens
increases with the increase of microcapsules (Fig. 9(b)). Although
adding of microcapsules decrease the pore size distributed from
27.19% to 19.66% (with 4% microcapsules) and 12.01% (with 8%
microcapsules) in the range from 50 to 200 nm, they cause larger
pores of >200 nm. This is the reason why the compressive strength
of samples with microcapsules is lower than the control sample.
What's more, in this study, the specimens were made with the
same raw materials, using same w/c ratio and sand to cement ratio
and other composition. The only different is that extra healing
agents were added in some of the mixes, which consisted of curing
agent and microcapsulated healing agent. Therefore, it can be
concluded that the addition of microcapsules would modify the
pore structure of the specimens and finally reduced its compressive
strength.

3.3. Pore properties of the specimens before and after healing

Since the volume of pore is almost constant during the healing

process (for the adopted Portland cement), this calculated results of
total porosity could be applied to study the crack-healing effects. As
shown in Fig. 10(a), the porosity and pore size distribution in the
range from 300 nm to 1000 nm and from 50000 to 300000 nm
decrease dramatically due to the healing of micro cracks. More
specifically, as shown in Fig. 10(b), after 3 days and 5 days healing
the fractions of pore size of >200 nm decrease dramatically from
13.85% to 5.72% and 5.35% respectively. However, the other range of
pore size (<20 nm, 20e50 nm and 50e200 nm) of pre-damaged
samples show slight difference before and after healing. In Fig. 11. Pore structure of specimens at different healing time.
 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96 93

in other series specimens (Fig. 13). The chloride permeability is
decreased (i.e. healing efficient increase) after healing in all speci-
mens, but the healing extent is different between them. The min-
imum value of the healing effect is 12%, in the specimen with
132 mm microcapsules. The specimens with the largest size mi-
crocapsules (230 mm) has a highest healing ratio, reaching 19.8%.
The experimental results manifest that the self-healing system has
an obvious healing effect on permeability performance. This is
mainly because of the crack-filling which help to achieve a denser
microstructure and finally increase the impermeability as well as
mechanical performance [41].
3.5. Influence factors
Factors such as microcapsules content, particle size, healing age,
curing temperature and pre-load level have great influences on the
self-healing efficiency. Microcapsules are the essential element for
autogenous healing. Its content (wt.% by cement) and particle size
are the based factors affecting the healing ratio. As shown in Fig. 14,
the healing ratio increases with the increase of microcapsules. The
specimens with bigger microcapsules show better healing effect
than the small one. This phenomenon can be explained by the
probability of microcapsule rupture, which is directly depends on
the particle size and the amount of microcapsules to some extent.

Fig. 12. Change ratio of chloride diffusion coefficient of specimens at different healing time.

Fig. 13. Healing efficiency of impermeability of specimens with different size microcapsule under the same condition (content ¼ 6.0 wt% by cement, pre-loading level ¼ 60% smax,
healing temperature ¼ 50  C) at different healing time.
94 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96

Fig. 14. Healing efficiency of impermeability of specimens with different amount of microcapsules.

However, the negative impact on mechanical properties from high
amount and big size of microcapsules should not be ignored. The
healing age, of course, is another important factor due to the
healing process. The development of healing efficiency can be
seemed form Fig. 15. It is clearly observed that the healing ratio
increases as time goes on. By 28 days, the ratio is almost stable for
all series. What more, curing temperature is also need to be
considered due to the healing mechanism. Fig. 16 clearly shows that
the improve of temperature has positive impact on healing effect. In
generally, a better curing reaction can be achieved under higher
temperature since the healing agent chosen in this research belong
to temperature based type. Finally, Pre-loading level also has strong
impact on healing efficiency (Fig. 17). The healing efficiency has
positive relationship with pre-loading strength on specimens.
Higher loading strength would create more initial damage
(microcracks), thus on the other hand more microcapsules could be
triggered and the cracks would be filled.
4. Conclusion
In this paper, a new family of self-healing materials that promise
for permeability healing of concrete (cementitious materials) is

Fig. 15. Healing efficiency of impermeability of specimens after different healing times.
 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96 95

Fig. 16. Healing efficiency of impermeability of specimens with different self-healing temperatures.

presented. The major conclusions are as follows:
1. The urea-formaldehyde/epoxy resin microcapsule is success-
fully synthesis for the self-healing system, which exhibits an
excellent surface texture, suitable size and remarkable thermal
stability. It demonstrates that the adopted microcapsule is
feasible to be employed in the self-healing cementitious
material.
2. The healing concept of microcapsules based self-healing system
is demonstrated to be feasible. More specifically, the micro-
capsules can survive during the mixing process and has a good
compatibility with cement paste. The microcapsules can be
actually beaked upon cracking and after healing the cracks are
cured by healing products.
3. The inner pore structure dramatically changes with the increase
of healing time. The fractions of larger pore (size of >200 nm),
capillary porosity, continuous pore diameter and pore connec-
tivity decreased dramatically due to the crack-healing process.
Based on chloride diffusion coefficient, the healing efficiency of
permeability increases to a maximum level of 19.8%, indicating
that the system actually works on decreasing permeability. It is
also noticed that several factors such as microcapsules content,

Fig. 17. Healing efficiency of impermeability of specimens with different degrees of pre-loading.
96 B. Dong et al. / Cement and Concrete Composites 78 (2017) 84e96
particle size, healing age, curing temperature and pre-load level
have great influences on the self-healing efficiency.
Acknowledgements
The authors would like to acknowledge financial support pro-
vided by National Natural Science Foundation of China (No.
51538007/U1301241/51478270).
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