Construction and Building Materials 28 (2012) 571583

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Construction and Building Materials

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Review

A review: Self-healing in cementitious materials and engineered

cementitious composite as a self-healing material
Min Wu a,, Bjrn Johannesson a, Mette Geiker a,b
a
Department of Civil Engineering, Building 118, Technical University of Denmark, 2800 Lyngby, Denmark
b
Department of Structural Engineering, Norwegian University of Science and Technology, Trondheim, Norway

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

Article history: Cementitious materials are the most widely used building materials all over the word. However, deteri-
Received 17 June 2011 oration is inevitable even since the very beginning of the service life, then maintenance and repair work,
Received in revised form 29 August 2011 which are often labor- and capital-intensive, would be followed. Thus, self-healing of the affected cemen-
Accepted 30 August 2011
titious materials is of great importance. Self-healing phenomenon in cementitious materials has been
Available online 14 December 2011
noticed and been studying for a long time. The possible mechanisms for self-healing phenomenon in
cementitious materials, which are summarized based on substantial experimental studies and practical
Keywords:
experience, are reviewed. In order to endow or enhance the self-healing property of cementitious mate-
Self-healing
Cementitious materials
rials, many different and innovative strategies have been proposed and developed during the past dec-
Healing agent ades. Then the different strategies employed for the self-healing of cementitious materials, i.e. the use
Healing strategy of hollow bers, microencapsulation, expansive agents and mineral admixtures, bacteria and shape
ECC memory materials, are reviewed and summarized. A comparison study is conducted subsequently on dif-
Micro-crack ferent strategies to self-healing and on different healing agents used as well. Engineered Cementitious
Crack-width control Composite (ECC) is a new type of cement-based materials, which has unique properties compared with
traditional cementitious materials. Further, a summary about the research status of self-healing on ECC is
given. It shows that ECC bears great potential in realizing effective self-healing due to its unique micro-
crack behavior and tight crack-width control property combined with its relatively high percentage of
cementitious components and low waterbinder ratio.
2011 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 572
2. Self-healing strategies in cementitious materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
2.1. Hollow fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 573
2.2. Microencapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 574
2.3. Expansive agents and mineral admixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 575
2.4. Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
3. Comparison study and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
3.1. Healing agent. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
3.2. Different strategies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
3.2.1. Encapsulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
3.2.2. Expansive agent and mineral admixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
3.2.3. Bacteria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
3.2.4. Shape memory materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 578
4. Self-healing in Engineered Cementitious Composite (ECC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
4.1. Engineered Cementitious Composite (ECC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 579
4.2. Self-healing in ECC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 580
5. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581

Corresponding author.
E-mail address: miwu@byg.dtu.dk (M. Wu).

0950-0618/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2011.08.086
572 M. Wu et al. / Construction and Building Materials 28 (2012) 571583

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 581

1. Introduction been noticed by the French Academy of Science in 1836 already

Many concrete structures including infrastructures suffer from
serious deterioration all over the world. Thus inspection and main-
tenance techniques for concrete structures have therefore become
the focus of increasing attention. However, the implementation of
continuous inspection and maintenance is difcult, especially in
the case of large-scale concrete structures such as infrastructures,
owing to the considerable amount of labor and funds required.
On the other hand, repair may be difcult or impossible to be exe-
cuted because of existing conditions such as the location of the
damage in the affected structure. Many infrastructures such as
highways and tunnels are also in continuous service and in such
cases repair work becomes very difcult. Moreover, even if such re-
pair work were possible in principle, the cost and amount of labor
required for diagnosis and repair work can be prohibitive in the
case of large-scale infrastructures. Under such circumstances,
automatic repair, or rather self-healing, of harmful cracks without
onerous labor and capital requirements of affected structures could
be of great attraction.
Development of articial self-healing materials is inspired by
different materials in our nature. A typical example of self-healing
phenomenon is damaged skins of trees and animals can autono-
mously heal themselves. van Breugel [1] summarized the research
history of self-healing phenomena in cementitious materials: self-
healing or autogenous healing of cracks in fractured concrete has
in water retaining structures, culverts and pipes [2]. The self-heal-
ing phenomenon was studied already by Hyde and Smith [3,4] at
the end of the nineteenth century. A more systematic analysis of
healing phenomena dates back to 1926 and was executed by
Glanville [5]. Already at that time a distinction was made between
self-healing and self-sealing. In the rst case the original strength
of the concrete is completely recovered, whereas in the second
case leaking cracks will be closed but no strength recovery is
obtained. Glanvilles rst studies have been followed by studies
of cracks in bridges [6,7]. Jacobsen and Sellevold [8] observed
self-healing in concrete specimens that had been exposed to
freezethaw cycles. Self-healing of leaking cracks were studied
extensively by Clear [9], Hearn [2,3,10] and Edvardsen [11].
Based on substantial experiment studies and practical experi-
ence, it is believed that self-healing of cracks in cementitious mate-
rials is a combination of complicated chemical and physical
processes. As revealed in most of the literatures studied, several
possible causes can be responsible for the self-healing phenomena
(schematically shown in Fig. 1) [12]:
a. Formation of calcium carbonate or calcium hydroxide.
b. Blocking cracks by impurities in the water and loose con-
crete particles resulting from crack spalling.
c. Further hydration of the unreacted cement or cementitious
materials.

Fig. 1. Possible mechanisms for self-healing in cementitious materials [12].

Fig. 2. Cracks are lled with white residue. (a) White residue lling the cracks after curing clearly observed on the surface of specimen (the width of the specimen is 40 mm)
[15] and (b) crystallized products found in the cracks (the crack width is about 100 lm) [16].
 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
Fig. 3. (a) Hollow glass bers and (b) damage visual enhancement in composite laminate by the bleeding action of a uorescent dye from hollow glass bers [23].
d. Expansion of the hydrated cementitious matrix in the crack
anks (swelling of CSH).
Of all these proposed causes, the primary mechanism is be-
lieved to be attributed to the crystallization of calcium carbonate
[11,1316]. This view is supported by the fact that precipitated cal-
cium carbonate can often be observed at the outside surfaces of the
crack as some white residue, which is shown in Fig. 2a macroscop-
ically and Fig. 2b microscopically. As one of the cement hydration
products dissolved in water, the calcium hydroxide is liberated and
dissipated along the cracking surfaces. Then free calcium ions from
cement hydration react with dissolved carbon dioxide, so self-
healed crystals are formed, growing at both surfaces of the cracks
and nally lling into the gaps. The chemical reaction process
could be described as follows [11]:
H2 O CO2 () H2 CO3 () H HCO3 () 2H CO2
3 1
Ca2 CO2
3 () CaCO3 pHwater > 8
Ca2 HCO3 () CaCO3 H 7:5 < pHwater < 8
According to the early work by Neville [17], self-healing is claimed
to be caused mainly by further hydration of unhydrated cementi-
tious components. However, later it was discovered that this only
applies to very young concrete and it was concluded that the forma-
tion of calcium carbonate is the most likely cause of self-healing at
later ages [18].
Engineered Cementitious Composite (ECC) is a new type of ce-
ment-based engineering material. The special properties of ECC
distinguish itself from the traditional cementitious materials, such
as the high ductility, the micro-cracking behavior and tight crack-
with control property. Moreover, the unique characteristics also
endow ECC with a great potential to realize effective self-healing.
Although the history of ECC is only about two decade, it could be
very promising in engineering application. Thus, a separate section,
Section 4, is devoted to the basics of ECC and the development of
self-healing in ECC materials.
Fig. 4. Schematic diagram of external healing agent supply system, based on the description of [28,29].
573
2. Self-healing strategies in cementitious materials
Damaged skins and tissues can be self-healed, because the host can assimilate
nutrients to produce new substitutes healing the damaged parts. Accordingly, for
the self-healing of cementitious materials, the essence is to provide necessary prod-
ucts which can then ll in the cracks when damage happens. With respect to how to
endow composite materials with self-healing property and improve the self-healing
efciency, many experimental studies and explorations have been conducted and
generated a lot of innovative strategies during the past few decades. Some of their
works are summarized as below.
2.1. Hollow bers
The idea of using hollow bers (sometimes referred to as hollow pipettes or
tubes depending on the diameter) is to store some functional components inside
of the hollow bers which will be embedded into a composite matrix. Thus when
damage or cracking happens, under certain stimulus, the functional components,
or rather healing agents, will ow out and heal the cracks subsequently.
Self-healing using hollow bers embedded within an engineering structure,
similar to the arteries in a natural system, has been investigated at different length
scales in different engineering materials by various authors, for example, in bulk
polymers [19], in polymeric composites [2023]. The suitability of hollow bers
or tubes in allowing the release of healing was in most cases proven. In order to
2 quickly and easily observe the internal damage in composite materials, a damage
visual enhancement method was designed by Pang and Bond [22,23]. In their work,
the bers lled with healing agents which were mixed with uorescent dye to mon-
3 itor the healing process (Fig. 3).
The experimental researches of this self-healing concept to cementitious mate-
rials have been discussed and demonstrated as feasible by several researches.
Dry [2427] adapted the concept of a biological self-healing approach, i.e.
bleeding, for use in a concrete. This idea involved the storage of repair compo-
nents inside brittle vessels distributed within a concrete specimen which after
sustaining damage would break and release a repair medium. Methyl methacry-
late liquid was used inside of hollow porous polypropylene bers within the con-
crete, and released from the bers to reduce concrete permeability. A further
investigation was undertaken into the release of crack adhering adhesive from
hollow glass pipettes into the concrete after exural testing. The adhesive loaded
sample demonstrated an ability to carry about 20% more load under a subsequent
exural test.
Like the active mode described by Dry [25], similar work were conducted by
Mihashi et al. [28] and Joseph et al. [29]. A representative schematic diagram of
the testing set up is shown in Fig. 4. Hollow bers (pipettes) were placed inside
of a cementitious matrix, with one end linked to the supply of healing agent and
the other end sealed. In Mihashis experiment [28], concrete specimens were pre-
pared and glass pipes with outer diameter of 2 mm and inner diameter of 0.8 mm
respectively were placed inside the specimens. Diluted (27%), non-diluted alkali-sil-
ica solution and two-component-blended-low-viscosity epoxy resin were used as
the healing agent. After the preparation, specimens were initially loaded till the
574 M. Wu et al. / Construction and Building Materials 28 (2012) 571583

Fig. 5. Self-healing system of internal encapsulation method with hollow glass tubes. (a) Middle section view; (b) side view; (c) epoxy-lled glass tube with aquastick as
sealant [31].

Crack Mouth Opening Displacement (CMOD) was 0.032 mm, followed by removal
of the load. Then the cracked specimens were cured for the second duration for the
development of self-healing capacity. The results showed compared to the refer-
ence sample in which no healing agent was used, specimens with diluted and
non-diluted alkali-silica solution as the healing agent obtained average strength
recovery ratio of 1.1 and 1.5 or so, respectively. While for the specimens with epoxy
resin, the strength recovery ratio showed little improvement. This recovery value
was much lower than that obtained by directly mixing the resin and manually
injecting it into the cracks, which was in the order of three times better recovery.
The author attributed this discrepancy to the insufcient mixing and stirring of
the two components, thus less resin hardened leading to the low recovery ratio.
It is also reasonable to think that some of the epoxy may still remain in the pipes
as one end is sealed. The testing regime of Josephs work [29] was similar despite
of some minor differences. Curved plastic tubes with outer diameter 4 mm and in-
ner diameter 3 mm were used as the healing agent carrier. Ethyl cyanoacrylate was
used as the healing agent. It was concluded that an ethyl cyanoacrylate based heal-
ing agent supplied via an external supply system was capable of achieving a suc-
cessful self-healing. The post-cracked stiffness, peak load and ductility were all
observed to increase post-healing. Observations made during and after testing Fig. 6. Self-healing system for concrete with selective heating around cracks [33].
clearly indicated that, ethyl cyanoacrylate glue was capable of penetrating a signif-
icant area of the crack surfaces under the inuence of capillary suction forces and
gravity.
believed to be responsible for the inadequate release of glue and ink into the crack. The
Different from the external healing agent supply system, internal encapsulation
capillary attractive force of the crack and the gravitational force on the uid mass
of healing adhesives was also studied [3032]. Li et al. [30] explored the feasibility
were insufcient to overcome the capillary resistive force of the glass tube and the
of using this method to embody ECC with self-healing property, which will be dis-
negative pressure force caused by the sealed ends. The small amount of ink ow ob-
cussed in more details in Section 4.2. Thao et al. [31] studied the selection of healing
served on the crack faces was therefore probably attributed to ink released from the
agent, carrier and the connement of a healing agent and the implementation of this
local vicinity of the crack site as the glass tube fractures. Since the crack propagates in
encapsulation method in concrete. In their study, a one part low viscosity epoxy resin
a direction perpendicular to the orientation of the tubes, the amount of adhesive re-
with the viscosity range of 250500 cPa.s was chosen as the healing agent. For the car-
leased locally was minimal compared with the volume remaining in the tubes.
rying tubes, comparison study was conducted between hollow Perspex and glass
Nishiwaki et al. [33] proposed a self-healing system consisting of a self-diagno-
tubes. It showed that glass tubes were more suitable due to the chemical inertness
sis composite, healing agent and a heat-plasticity organic lm pipe. The self-diagno-
to epoxy resin and the brittleness which could be easier to rupture when cracks were
sis composite, which could detect the incidence of cracks, was functionalized as a
initiated, ensuring the leakage of the healing agent contained inside. Dimension study
heating device in a way that the self-diagnosis composite could increase the electric
of the glass tubes showed that the optimal inner and outer diameter were 4 mm and
resistance around cracks and heat the damaged parts selectively through electrify-
6 mm respectively. Then experiment was conducted to prove that the idea could
ing. Then a heat-plasticity organic lm pipe containing a one-component epoxy re-
work. Specimen and testing setup was given as Fig. 5. The control specimens were
sin with super low viscosity embedded in the concrete next to the heating device
loaded to failure to determine the loaddisplacement curve. Specimen with glass
was melted, releasing the healing agent to ll in the cracks (Fig. 6).
tubes were tested beyond the point where an audible pop sound was heard, which
indicated fracturing of the glass tube. The load was held until leakage of the epoxy
was observed on the bottom surface of the specimen. The specimen was then un-
loaded and left unloaded for 4 days before being loaded again using the same dis- 2.2. Microencapsulation
placement rate. The test was terminated soon after more leakage of epoxy healing
agent was observed. The load was then removed and the specimen left to heal for The encapsulation of materials has evolved from examples in nature, ranging
3 days.before being loaded again and tested to failure in the third loading test. The re- from macroscale to nanoscale. The simplest example on a macroscopic scale is a
sults showed that these glass tubes were able to rupture when intersected by cracks in birds egg or a seed, while on a microscopic scale the best example is that of a cell
the concrete and facilitate timely release of epoxy for repair. The owability of this along with its contents [34]. The development of microencapsulation began with
epoxy into cracks through gravity and capillary action and the bonding of crack sur- the preparation of capsules containing dyes; these were incorporated into paper
faces in the host concrete were demonstrated. The specimen recovered part of its for copying purposes and replaced carbon paper [35]. As time passes, many new
strength after 4 days of healing. To minimize the breakage of the glass tubes during technologies have emerged and been developing in many elds. Microencapsula-
casting of the structural members, the embedded glass tubes protected by a tion cannot be dened as a separate product or as a component of a product. Rather,
6.5 mm all-round layer of mortar cured at one-day was recommended. Joseph et al. it is described as a process of enclosing micron-sized particles of solids or droplets
[32] performed a similar experiment. A type of cyanoacrylate with extremely low vis- of liquids or gasses in an inert shell, which in turn isolates and protects them from
cosity of 5 cPa.s was chosen as the healing glue and ink was also contained in the tubes undesirable or unwanted reactions in the external environment [36].
for easier leakage observation. It was concluded that despite some evidence of a small The application of using microencapsulation approach incorporating healing
amount of healing in the tested beams containing a double layer of tubes, the glue had agent to self-healing of materials was demonstrated by White et al. [37]. Fig. 7a
not been drawn into the cracks in sufcient quantity to achieve healing. The negative illustrates this self- healing concept. When the crack ruptures the embedded micro-
pressure forces created by the sealing plugs at either end of the capillary tubes were capsules, the healing agent is released into the crack faces through capillary action.
 M. Wu et al. / Construction and Building Materials 28 (2012) 571583 575

Fig. 7. (a) basic method of the microcapsule approach: (i) cracks form in the matrix; (ii) the crack ruptures the microcapsules, releasing the healing agent into the crack plane
through capillary action; (iii) the healing agent contacts the catalyst, triggering polymerization thus ensuring the closure of the near-by cracks and (b) ESEM image showing a
ruptured microcapsule [37].

Then the healing agent contacts the embedded catalyst, triggering polymerization
and ensuring the closure of the near-by cracks. A typical ruptured microcapsule im-
age is shown in Fig. 7b.
Boh and umiga [38] reviewed the application of microencapsulated additives
in building and construction materials. In order to facilitate the further hydration
of the matrix, different additives are encapsulated into microcapsules which are
then embedded into the matrix. Tomiuchi and Nishihama [39] patented applica-
tions of microencapsulated water in the production of cement-based building
boards with uniform strength. Typical compositions consisted of cement, mixed
with ber (e.g. asbestos, synthetic ber) and microcapsules containing water for
hardening. The building boards with uniform strength were manufactured on a belt
conveyer by compression-molding, resulting in cement hardening. In another
invention [40], high strength cement-based building boards were manufactured
from a mixture of hydraulic material (gypsum), brous material, additives, and gel-
atin microcapsules containing water glass as a setting accelerator. Microencapsulat-
ed or gelled water was used in cartridges of quick-setting cement [41]. A premixed
mortar mixture was patented, consisting of cement and microcapsules containing
water [42]. In a patent by Okamoto et al. [43] on manufacturing concrete and mor-
tar mixes, water was encapsulated in an acrylate superabsorbent polymer. In the
production of concrete or mortar, the water was released from the superabsorbent
to promote hydration of the surrounding cement. They also discussed about some
other application elds of this microencapsulation in building materials, i.e. re-
proong, freeze and freezethaw resistance, expansion and degradation resistance,
reduction of hydration heat release, etc.
In the work conducted by Nishiwaki [44], microcapsules lled with epoxy resin
as one component of the healing agent (the shell material of ureaformaldehyde
formalin with the diameter of 2070 lm) and microcapsules with acrylic resin as
a hardener (the shell material of gelatin with the diameter of 125297 lm) were
used. Both compression and splitting tests were carried out to conrm the problems
of this method for self-healing. The results showed: (1) it was difcult to harden the
two-component healing agent; (2) the quantity of healing agent lled in the micro-
capsules was limited to a very small amount; (3) bond strength between the micro-
capsules and the matrix needed to be stronger than the strength of the
microcapsules. In order to solve these problems: (1) one component healing agent
as the core material might be used; (2) the diameter of the microcapsule should be
big enough; (3) the bond strength between the shell materials and cementitious
matrix should be improved. Finally it was concluded that there were still a lot of
technical problems.
It is also reported that microcapsules incorporating sodium silicate were used
[45]. In the reported research, concrete was rstly loaded to the point of almost
breaking. Then the load was removed and followed by curing for about 1 week.
Measurements showed the specimen with 2% microencapsulated sodium silicate
proceeded to recover 26% of its original strength, while the reference concrete only
recovered 10%. It was believed that the strength recovery ratio could be even higher
by increasing the quantity of the healing agent.
2.3. Expansive agents and mineral admixtures
The formation of cementitious products such as AFt, AFm and CaCO3 in cracks
and calcium hydroxide crystals in air voids in cracked concrete has been observed
[46,47]. It was hypothesized that these hydration products had been leached out
and recrystallized in water that had own through the cracks. Based on this
thought, in an attempt to develop a self-healing method, Kishi and coworkers
[4649] studied the effect of different agents on the self-healing behavior of con-
crete. The investigated agents include expansive agent, geo-materials and chemical
admixtures as well as some combination of them.

Fig. 8. ESEM image of healing products. (a) Comparison between geopolymeric gel phase from self-healing area and hydrogarnet phase from original area and (b) formation
of hydrogarnet phases, AFt phases and calcite in self-healing zone [49].
576 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
In an comparison experiment conducted between the reference and the sample
in which 10% cement was replaced by expansive agent consisting of C 4 A3 e S, CaSO4
and CaO (lime). The results showed that for concrete beams incorporating expan-
sive agent, a crack with an initial width of 0.22 mm was almost healed after
1 month. Re-hydration products between cracks were observed. However, for the
normal concrete beam, the cracks still remained and were only partly closed after
the same time. Thus recrystallization of expansive agent in air voids for self-healing
was more effective than that of normal concrete [46]. In one following study [48], a
geo-material with a SiO2 content of 71.3% and an Al2O3 content of 15.4% was added
with the expansive agent. It was found that geo-polymers were formed by the poly-
merization of individual aluminate and silicate species, which were dissolved from
their original sources at high pH in the presence of alkali metals. Detailed studies
showed that the geo-polymeric gel size was smaller than 2 lm and that the crack
interface phases of the original cracking zone formed several hydrogarnet phases.
This indicated that hydrogarnet phases or AFt phases, as shown in Fig. 8, were
formed from expansive agent and therefore played an important role in crack-
bridging materials. EDS analysis also revealed that most of the modied geo-poly-
meric gel was structured by dense phases as compared to hydrogarnet phases.
Chemical additives were also studied in this series of investigations [48,49]. It
was concluded that the addition of carbonates such as NaHCO3, Na2CO3 and Li2CO3
to normal concrete contributed to an increase of the cementitious recrystallization
and precipitated particles in concrete. In particular, when utilizing the appropriate
dosages of carbonates and the expansive agent, the self-healing ability in cracks
could be enhanced.
2.4. Bacteria
Some researchers propose the use a biological repair technique by the introduc-
tion of bacteria into concrete [50,51]. This approach dates back to the mid-1990s in
the research of Gollapudi et al. [52], who suggested a method for repairing cracks
with environmentally friendly processes. The idea is to incorporate ureolytic bacte-
ria, which aids in the precipitation of calcium carbonate (CaCO3) in the micro-crack
region. The microbial precipitation of calcium carbonate (CaCO3) is determined by a
number of factors, which include the concentration of dissolved inorganic carbon,
the pH, the concentration of calcium ions, and the presence of nucleation sites
(areas of extremely localized budding or reaction). The rst three of these factors
are provided by the metabolism of the bacteria while the cell walls of the bacteria
acts as the nucleation sites [51].
The bacteria used in the research conducted by Tittelboom and coworkers for
concrete [51] is intended to produce urease, an enzyme that catalyzes urea
2
(CO(NH2)2) into ammonium NH 4 and carbonate CO3 . The chemical process
appears as follows: 1 mol of urea is hydrolyzed intracellular to 1 mol of
Fig. 9. Schematic scenario of crack-healing by concrete-immobilized bacteria. Bacteria on fresh crack surface become activated due to water ingression, start to multiply and
precipitate minerals such as calcite, which eventually seal the crack and protect the steel reinforcement from further external chemical attack [50].
carbamate and 1 mol of ammonia (Eq. (4)); carbamate spontaneously hydrolyses
to form one additional mole of ammonia and carbonic acid (Eq. (5)); these prod-
ucts then form 1 mol of bicarbonate and 2 mol of ammonium and hydroxide ions
(Eqs. (6) and (7)); the last two reactions give rise to a pH increase, shifting the
bicarbonate equilibrium, resulting in the formation of carbonate ions (Eqs. (7)
and (8)) [51].
CONH2 2 H2 O ) NH2 COOH NH3 4
NH2 COOH H2 O ) NH3 H2 CO3 5
H2 CO3 H2 O () HCO3 H 6
2NH3 2H2 O () 2NH4 2OH 7
HCO3 H 2NH4 2OH () CO2
3 2NH4 2H2 O 8
Because the cell wall of the bacteria is negatively charged, the bacteria are able to
draw cations from the environment, including positively charged calcium ions,
which deposit on their cell wall surface. The Ca2+-ions then react with the CO2
3 -ions
leading to the precipitation of calcium carbonate (CaCO3) at the cell surface. This
precipitation serves as the nucleation site (Eqs. (9) and (10)). With this method of
bacterially inducing localized CaCO3 precipitation, the cracked faces could be lled.
The scenario of crack-healing process by concrete-immobilized bacteria is also sche-
matically shown in Fig. 9; ESEM images of precipitated CaCO3 with different shapes
on the surface of cracks are shown in Fig. 10.
2
Ca2 Cell ) Cell-Ca 9
Cell-Ca
2
CO2 ) Cell-CaCO3 # 10
3
2.5. Shape Memory Materials
It is also noted that some researchers [5458] suggested incorporating func-
tional materials, i.e. shaping memory alloy or shaping memory polymers, into
cementitious materials. The basic concept is that when cracks are initiated, the
shape memory materials which have a shorter predened memorized shape than
the current state will contract or shrink in a restrained condition, thus a shrink force
will be generated, which optimally leads to the closure of cracks.
In 1932, Chang and Read observed a reversible phase transformation in
goldcadmium (AuCd), which is the rst experimental record of the shape memory
transformation [59]. Up to date, many types of shape memory alloys (SMAs), have
been discovered. Among them, Nitinol, which was discovered by Buechler and
 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
(a) Plate-like precipitates
Fig. 10. ESEM images showing self-healing activity in bacteria-based concrete specimens. Larger (50500 lm-sized) calcium carbonate-based produced by concrete
incorporated bacteria on the surface of cracks. Scale bars: left picture 100 lm, right picture 50 lm [53].
Fig. 11. Schematic of intelligent reinforced concrete specimen [59].
co-researchers [60], possesses superior thermo-mechanical and thermo-electrical
properties and is the most commonly used SMAs. Nitinol SMAs have two unique
properties: shape memory effect and superelasticity. The shape memory effect re-
fers to the phenomenon that SMAs return back to their predetermined shapes upon
heating. The superelasticity refers to the phenomenon that SMAs can undergo a
large amount of inelastic deformation and recover their shape after unloading.
By utilizing the shape memory effect of SMA wires, Song and Mo [61] proposed
the concept of Intelligent Reinforced Concrete (IRC). The IRC used stranded mar-
tensite SMA wires for post-tensioning (as shown in Fig. 11). By monitoring the elec-
tric resistance change of the shape memory alloy wires, the strain distribution
inside the concrete could be obtained. In the presence of cracks due to explosions
or earthquakes, by electrically heating the SMA wires, the wire strands contracted
and reduced the cracks. This self-rehabilitation could handle macro-sized cracks.
The concrete structure was intelligent in the sense that it was able to detect self-
rehabilitate. Sakai et al. [54] investigated self-restoration of a concrete beam using
super elastic SMA wires. The experimental results revealed that the mortar beam
with SMA wires recovered almost completely after incurring an extremely large
crack.
Similarly, shape memory polymer (SMP) materials were also proposed to be
incorporated into cementitious matrix [57,58]. The basic concept is that: (1) crack-
ing occurs in the cementitious material due to early age shrinkage, thermal effects
and/or mechanical loading; (2) the shrinkage mechanism in the embedded shape
memory polymer tendon (or tendons) is activated by heating, which results in crack
closure and compressive stresses being developed across the closed crack faces. The
closure of cracks can enhance the natural self-healing process and in general such
closure serves to enhance the durability of the structural component. Based on
the experiments, Jefferson et al. [58] concluded that the concept of post-tensioning
mortar beams using oriented shrinkable polymer tendons was viable for crack clo-
sure and low-level pre-stressing. It was also shown in their work that the most
effective shape memory material for the tendons, as judged from a series of screen-
ing tests, was polyethylene terephthalate (PET) Shrinktite. This material has a
shrinkage potential of approximately 34 MPa under restrained conditions when
heated to a temperature of 90 C and allowed to cool. And the effect of heating com-
bined with additional curing helped to increase the strength of the mortar by
approximately 25%.
3. Comparison study and discussion
Of all the proposed self-healing strategies, some of them focus
and dig into the intrinsic self-healing potential of cementitious
materials themselves, such as the unhydrated cementitious
577
(b) Robust-spherical precipitates
components inside and the capability of the matrix to provide cal-
cium ions; while there are also some studies which try to endow
cementitious matrices with self-healing capacity through the intro-
duction of external chemicals or functional materials, like the
embedded healing agent (different kinds of resin) and the shape
memory materials. Combined use of more than one single method
is also found [62]. About the healing agent and all the methods
reviewed in this study, a summary can be discussed as follows.
3.1. Healing agent
An ideal self-healing system is supposed to sense the damage or
cracks which could trigger the release of the healing agent, or in
another word a healing agent should be released upon necessity.
Thus the healing agent is often carried inside of hollow bers (pip-
ettes or tubes) or microcapsules preventing the unexpected release
or contact with the matrix. As discussed by Joseph et al. [32], in
addition to being readily available and cost-effective, a suitable
agent should have the ability to be readily encapsulated within
the agent carriers and be sufciently mobile to allow migration
to the areas of damage following release. Additionally, crack
reopening should be resisted post-healing, and therefore the
healed parts should have sufcient mechanical properties after
curing, ideally equal to or greater than that of the cementitious
matrix. In order to improve long-term durability, the agent should
also have sufcient longevity and compatibility with the cementi-
tious matrix over the lifetime of the structure.
Resin was often chosen as the healing agent in the studies. Two
component epoxy resins, which were separately stored adjacent
to one another within a cementitious matrix, were studied by
Mihashi et al. [28]. And it was concluded that insufcient mixing
of the two different released resins resulted in poor polymerization
degree and therefore poor mechanical performance of the adhesive.
One component epoxy resin [31,33] and cyanoacrylates, or rather
578 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
superglue [25,30,32], were also studied respectively. It shows that
one component resin is more suitable than its two-component
counterpart as it involves no mixing after release. Viscosity is an-
other important parameter in choosing the healing agent, because
the viscosity decides the mobility of the healing agent, which affects
the encapsulation process of the agent within the carriers and
migration of the agent after the wall of the carriers are ruptured.
Different from the mechanism of using resins as an external
supplied healing agent, the intrinsic property of cementitious ma-
trix including unhydrated cementitious components and with the
ability to provide calcium ions were explored by incorporating
water [39,4143,62] and alkaline-silica solution [28,40,45] as the
healing agent. The products generated to ll in the cracks from
either further hydration or the reaction between calcium ions
and silica solution are a form of CSH gel, which is a same com-
ponent in the matrix. Thus, a good compatibility is expected. How-
ever, healing efciency under such circumstances becomes more
complicated as the matrix is another important inuencing factor
besides the healing agent itself.
3.2. Different strategies
3.2.1. Encapsulation
Encapsulation is a widely used method to achieve self-healing.
In terms of this methodology, further to what makes an ideal
self-healing system mentioned in Section 3.1, the damage or cracks
must be able to trigger the release of the encapsulated healing
agent, meaning the wall of the capsules should on one hand be able
to prevent the inner agent from undesirable release and on the
other hand be sensitive enough to the pressure generated by the
damage or cracks, which could ensure the rupture of the wall.
Although being discussed in different categories in the above liter-
ature study, using hollow bers (pipettes or tubes) and microen-
capsulated capsules both share the same concept and belong to
the same encapsulation family, of which the only difference is
the healing agent carrying system. However, there are advantages
and disadvantages for each carrying system:
(1) For the external healing agent supply system schematically
shown in Fig. 4, the major advantage is that additional sup-
ply of healing agent is possible, thus a large amount of heal-
ing agent can be handled, which also ensures the
effectiveness of this system under multiple damage events.
Additionally, the mechanical properties can be expected to
be recovered at a high ratio after healing from damage.
While the major disadvantage is that the casting of concrete
becomes difcult. This problem can be solved in a laboratory
with enough carefulness. However, it may become a severe
problem if large amount of concrete needs to be cast on
the construction site [28].
(2) For the internal encapsulation of healing agent in hollow
tubes represented by Fig. 5c, the system is simpler compared
with the external supply system. As long as there is healing
agent reaming in the system, it is possible to work under
repeated damage. Apart from the disadvantage shared with
the external supply system in practice, it was also found that
due to negative pressure generated at each end of the sealed
capillary tubes, a large amount of healing agent remained
inside the tubes following their completely fracture, even
though the viscosity of the healing agent was already very
low (5 cPa.s roughly). And this phenomenon would be even
more serious if the viscosity of the healing agent increases
[32].
(3) In the use of microcapsules, the treatment is easy and they
can respond to fracture at many different locations as the
capsules are dispersed inside of a matrix. However, a
successful manufacture of desirable microcapsules for the
application in cementitious materials is often not that
straightforward. Moreover, the healing agent that can be
handled in this carrying system is smaller than the two sys-
tems mentioned earlier. Besides, the bond between the
microcapsules and the matrix is often a concern. If the
strength of the capsule wall is higher than the bond strength,
the microcapsules would not rupture after the initiation of
the cracks, then no healing agent will be released and no
healing of the cracks will happen.
It should also be noted that the possible negative effect on ma-
trix mechanical properties with the introduction of hollow bers
and capsules, whose dimension and fraction matters.
3.2.2. Expansive agent and mineral admixtures
Due to the expansive characteristic after introduction into
cementitious materials, expansive agents, sometimes combined
with other mineral additions and/or admixtures, could denitely
improve the self-healing capacity, if appropriately used. If an
expansive agent without any protection pre-mixed with cement,
then after the addition of water, the expansive agent will hydrate
simultaneously with the cement, sometimes even quicker than ce-
ment particles to form expansive hydrates depending on the com-
ponents [64,65]. As stated in some researches [6669], unexpected
expansion could happen more than often in cementitious matrices
if the restraint is not appropriately set, which could lead to the
immature failure from the inside of the matrices resulting in low-
ering of strength or even no strength at all. So if the expansive
agents are consumed too early or unnecessary, they on one hand
cannot generate the expansive hydration products to ll in the
cracks when damage happens, and on the other hand could possi-
bly be leading to unexpected damaging disruption of cementitious
matrices. Prudence needs to be taken when expansive agents are to
be used. The above mentioned encapsulation method, i.e. expan-
sive agents encapsulated into (micro) capsules, could be an
alternative.
3.2.3. Bacteria
Adopting bacteria induced carbonate precipitation to ll the
cracks is very innovative and this method, which is a result of bio-
logical activities, is pollution free and natural. As stated in [70], the
microbial precipitation depends on several factors, including: the
concentration of dissolved inorganic carbon, the pH, and the con-
centration of calcium ions and the presence of nucleation sites.
Also, when bacteria are used to work for the healing of cracks in
concrete, the major hindering factor is the high alkaline environ-
ment of concrete, restricting the growth of the bacteria. Therefore,
necessary measures need to be taken to protect bacteria in con-
crete [7174]. So, in order to ensure the effective mineral precipi-
tation which could lead to the healing of cracks, care should be
taken to meet the prerequisites. It is a new and promising method
and currently the research in this aspect focuses more on the dura-
bility side while there is little touch on the mechanic properties
and further researches need to be conducted [50,51].
3.2.4. Shape memory materials
It has been shown that concept of using shape memory materi-
als works. However, since concrete material is often used in huge
amount in practice, it is very cost-sensitive. Thus, the relatively
high cost makes their use unviable for all but the most specialized
of applications. It is also noted that the common activation or trig-
gering of this working mechanism involves heating to certain tem-
perature. So, rstly the way to realize heating in a cementitious
matrix with shape memory materials makes the whole self-healing
system rather complicated and thus it increases the complexity to
 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
Table 1
A summarized comparison between different strategies.
Strategy Advantage
Encapsulation
External supply system 1. Healing agent release on necessity
2. Adjustable large amount of healing agent
3. Effectiveness under multiple damage events
Internal encapsulation 1. Healing agent release on necessity
2. Medium amount of healing agent
3. Possible effectiveness under multiple damage events
Microcapsule 1. Healing agent release on necessity
2. Response to many damage locations at the same time
3. Possible effectiveness under multiple damage events
Expansive agent and mineral 1. Good healing efcacy
admixtures 2. Good compatibility of the generated healing products
with the cement matrix
Bacteria Biological activities and a pollution free and natural way
Shape memory materials 1. Macro-sized cracks can be handled
2. High ratio of mechanical properties recovery
3. Effectiveness under multiple damage events
Fig. 12. Uniaxial tensile stress-deformation relation of concrete, FRC and HPFRCC
[90].
apply this healing system on construction site besides the aggre-
gated non-cost-effectiveness. Secondly, we should also bear in
mind that certain hydration product is not stable in and after ele-
vated temperature treatment, for example, Delayed Ettringite For-
mation (DEF) as mentioned by many authors [7581], which also
would lead to uncertainties of adopting this method. A more expli-
cit comparison about the reviewed different self-healing strategies
is summarized in Table 1.
4. Self-healing in Engineered Cementitious Composite (ECC)
4.1. Engineered Cementitious Composite (ECC)
It is well known that normal concrete is a brittle material, and
the brittleness becomes even more pronounced with the ever-
increasing concrete strength grade. This phenomenon has drawn
increasing attention and the exploration of using bers to address of the densied matrix. The dense matrix allows a strong bond
this concern started very early [82,83] and has been lasting since it
579
Disadvantage
1. Difculty in casting
2. Negative effect on the mechanical properties of the cement matrix if too
many hollow bers adopted
1. Difculty in casting
2. Negative effect on the mechanical properties of the cement matrix if too
many hollow bers adopted
3. Possible difculty of healing agent release
1. Difculty in preparing capsules and in casting
2. Limited amount of healing agent
3. The bond between capsules and the matrix is a concern
4. Negative effect on the mechanical properties of the cement matrix if too
many capsules adopted
1. Undesirable expansion if not well treated
2. Healing products generated on necessity is not guaranteed
3. Effectiveness under multiple damage events could be a problem
1. Many prerequisites to be met
2. Measures should be taken to protect bacteria in concrete
3. Mechanical properties recovery and effectiveness under multiple
damage events could be concerns
1. Cost intensive
2. Heating to stimulate the healing process can lead to uncertainties
Fig. 13. Typical tensile stressstrain curve and tight crack width control of ECC [95].
starts. There is a class of materials separate from FRC in that differ-
ent magnitude of tensile ductility is achieved, often accompanied
by a strain hardening response distinct from the tension response
of FRC. Naam and Reinhardt [84] classied such materials as High
Performance Fiber Reinforced Cementitious Composites (HPFRCC).
Fig. 12 shows the comparison of uniaxial tensile stress-deforma-
tion relation of concrete, FRC and HPFRCC. Recently two new clas-
ses of HPFRCC emerge: (1) drastically improved toughness with
improved ductility, represented by Ductal [85], which has a high
tensile strength of 12 MPa and a ductility of 0.020.06%; (2) signif-
icantly increased ductility, represented by Engineered Cementi-
tious Composite (or ECC for short) [8688]. The development
approach for these two different classes of materials is quite differ-
ent. For Ductal, the approach is to employ a tightly packed dense
matrix to increase both tensile and compressive strength of the
material. Fiber is added to counteract the resulting high brittleness
with the ber that results in a high post-cracking strength as long
580 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
as a ber with high strength is utilized. While for ECC, it is to create
synergistic interactions between the ber, matrix, and interface to
maximize the tensile ductility through the development of closely
spaced multiple micro-cracks which help to release the stresses
generated. It is reported that ECC has a typical moderate tensile
strength of 46 MPa and a high ductility of more than 3%, which
is hundreds times that of normal concrete [89,90].
ECC is a class of specially designed, ultra ductile ber reinforced
cementitious composites originally invented in the early 1990s
[91] and continuously evolved over the last two decade [90]. It is
characterized by high ductility in the strain range of 37%, tight
crack width of around 60 lm and relatively low ber content of
2% or less by volume [90,92]. The most fundamental mechanical
property of ECC is its metal-like property, i.e. the ability to carry
higher loads after rst cracking while undergoing further deforma-
tions. Based on micromechanics design, the bers used in ECC are
tailored to work with the matrix for the purpose of constraining
localized brittle fracture and guaranteeing more uniform distribu-
tion of micro-cracks. Due to the slip-hardening behavior of bers,
ECC can take increasing load that generates new cracks at other
locations. A typical tensile stressstrain curve of ECC is shown in
Fig. 13. It can be found that rst cracking in ECC is followed by
increasing stress accompanied by a rise in strain; while for tradi-
tional FRC, tensile load capacity drops as a single crack enlarges
during tension softening (Fig. 12).
The crack width is another important parameter that affects the
durability of a concrete structure. Fig. 13 also shows the tight crack
width control of ECC. As can be observed that after the tensile
deformation increases to around 1% strain, the early micro-cracks
stop widening and remain more or less constant with the crack
width around 60 lm, which is much smaller than the typical crack
width observed in steel reinforced concrete and normal ber rein-
forced concrete. Moreover, the self-control of crack width can be
seen as an intrinsic property of ECC materials, rather than depend-
ing on steel reinforcement ratio and structural dimensions [93,94].
4.2. Self-healing in ECC
Li et al. [30] reviewed the self-healing concept of bleeding
mechanism proposed by Dry [25] as mentioned in Section 2.1,
which is to release chemicals that seal the tensile cracks, followed
by air curing of the released chemicals in the cracks, leading to
regaining of mechanical properties of the uncracked composite.
He argued that the self-healing mechanism described could not
work in normal concrete, cement or even ber reinforced concrete,
because the width of the tensile cracks in such materials could not
be easily tuned. Localized fracture led to continued increases in
crack width under decreasing tensile load, and rapidly exhausted
the amount of chemical available for crack sealing and composite
re-healing. Thus, for the proposed self-healing concept to work, it
was critical that the tensile crack width be controlled, and it must
be limited to within tens of micrometers. Otherwise, very large
hollow glass tubes would be needed, which in turn negatively
modied the mechanical properties of the composite. This is in
good agreement with many other researches conducted in this
eld, which also state the importance of the crack width
[9,11,9599].
Since the tight controlled crack width is one intrinsic property
of ECC, it provides a good basis for implementing this self-healing
concept to ECC. In the research [30], two different levels of exper-
iments were designed to demonstrate the feasibility of the afore-
mentioned bleeding concept. The rst level involved the ECC
material system with a single hollow glass ber without any
healing chemical, with the tests conducted in situ in a loading
stage under an ESEM. The rst-level experiments were designed
for conrming the sensing and actuation mechanisms in ECC
specimens. The second-level tests involved exural specimens of
ECC systems which contain glass bers lled with sealing agent
(ethyl cyanoacrylate). These experiments were conducted under
standard (MTS) load frames and were intended to establish the
rehealing effectiveness of the sealing agent after the material suf-
fered crack damage in load cycles. The sensing and actuation
mechanisms were validated by observation of ESEM and the effect
of recovery was validated by regaining of exural stiffness. Mean-
while, he also mentioned though the feasibility study showed great
potential, there were many remaining issues needed to be further
investigated and addressed before practical applications.
Besides the introduction of external chemical as the healing
glue, Li et al. [88,94,100,101] studied the self-healing phenomena
as an intrinsic property of cementitious matrices, focusing on the
exploration of the matrix itself and its interaction with the exposed
environment. In their experiments, deliberately pre-cracked ECC
specimens were exposed to various commonly encountered envi-
ronments, including water permeation and submersion, wetting
and drying cycles, and chloride ponding. The mechanical and trans-
port properties could be largely recovered, especially for ECC spec-
imens preloaded to below 1% tensile strain. Besides the small crack
width, the low water/binder ratio in addition to the large amount
of y ash in their mixture also helped promote self-healing via con-
tinued hydration and pozzolanic activities.
In an effort to develop ECC materials with locally available
waste material and/or by-products, Zhou et al. [102] have devel-
oped a number of mixtures with blast furnace slag (BFS) powders
and limestone (LP) powders, all characterized with 23% tensile
strain capacity and tight crack width (typically below 60 lm). Qian
et al. [15] noticed that the mixtures proposed in Zhou et al. [102]
were different from that used by Li et al. [88,95,100,101] in the
components (e.g. large amount of BFS and LP instead of y ash)
as well as much higher water/binder ratio (0.450.60 versus
0.23), which suggested that the amount of unhydrated cementi-
tious materials after 28 day curing might be much smaller com-
pared with the samples in Li and coworkers investigations. So
the self-healing behaviors of this type of ECC were studied. It
showed that ECC materials which were made with large amount
of BFS, LP along with relatively high water/binder ratio still perse-
vered the similar self-healing behavior compared with the ECC
materials used in previous studies which were characterized by
high percentage of y ash and low water/binder ratio. The reason
was attributed to the same tight crack width. It was also concluded
that self-healing behavior in ECC heavily depended on the avail-
ability of unhydrated cement and other supplementary cementi-
tious materials, such as BFS. So low water/cementitious material
ratio and high percentage of cementitious material were conducive
to promote self-healing behavior. The importance of crack width
was also emphasized in the study as far as continuous hydration-
based self-healing was concerned, as it required much less healing
products to ll in the cracks and much easier for the healing prod-
ucts to grow from both faces of the crack to get connected.
Further studies were conducted by Qian et al. [103], in which
the curing conditions (air curing, carbon dioxide curing, wet/dry
curing and water curing) and the inuence of the addition of
nano-clay containing water which acted as the internal water sup-
ply for further hydration along the micro-cracks were investigated.
The results showed that the recovery level could be signicantly
higher with the addition of nano-clay and higher cementitious
material content in the mixtures. Finally he also pointed out that
there was no nal crack occurring at the new location for air cured
samples for all mixtures studied, which suggested that the healing
under air curing, even though with internal water supply from
nano-clay, had relatively weak strengthening effect, making it dif-
cult to shift nal fracture sites from preexisting cracks to new
locations. The ineffective healing under air curing condition was
 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
also found in the study conducted by Hua [63], in which the self-
healing behavior of ECC was studied by using Super Absorbent
Polymer (SAP) capsules containing water as the internal reservoir
for further hydration. Although some healing products were de-
tected along the cracked faces, no apparent healed cracks were ob-
served. Thus, it was concluded that the cracks were likely
undergoing the self-healing process, but it was not very effective.
The studies mentioned above indicate the importance of sufcient
water or moisture availability, which on one hand acts as the reac-
tant for further hydration and the medium for ions transport on the
other hand.
Generally, the micro-crack behavior of ECC, with which the rup-
ture possibility of the (micro) encapsulated capsules is greatly im-
proved thus leading to the release of healing agent contained,
ensures the effectiveness of the sensing and actuation mecha-
nisms. The tight crack width in ECC is also very important as it re-
quires much less healing products to ll the cracks and much
easier for the healing products to grow from both faces of cracks
to get connected. Apart from these, in terms of the material itself,
ECC has relative higher percentage of cementitious components
and lower waterbinder ratio compared with traditional cementi-
tious materials. Due to its unique properties, ECC shows great po-
tential in realizing effective self-healing.
5. Concluding remarks
Cementitious materials are widely used all over the world due
to their cost-effectiveness and availability. However, degradation
initiates at a very early stage and thus maintenance and repair
are a huge concern to our society. Smart cementitious materials
with self-healing property, which have the built-in capability to re-
pair structural damage autonomously or with the minimal help of
an external stimulus, are very promising in the eld of application.
(1) Self-healing of cracks in cementitious materials is a combi-
nation of complicated chemical and physical processes. The
possible mechanisms could be: formation of calcium carbon-
ate or calcium hydroxide; blocking cracks by impurities in
the water and loose concrete particles resulting from crack
spalling; further hydration of the unreacted cement or
cementitious materials; expansion of the hydrated cementi-
tious matrix in the crack anks (swelling of CSH). It is also
practical to believe that more than one above mentioned
cause may account for a self-healing phenomenon.
(2) Several innovative strategies to self-healing for cementitious
materials have been proposed and developed. The typical
approaches include using hollow bers, microencapsulation,
expansive agents and mineral admixtures, bacteria and
shape memory materials. It could be concluded that some
of these methods focus and dig into the intrinsic self-healing
potential of cementitious materials themselves, such as the
unhydrated cementitious components inside and the capa-
bility of cementitious matrices to provide calcium ions;
while there are also some studies which try to endow
cementitious matrices with self-healing capacity through
the introduction of external chemicals or functional
materials.
(3) Comparison studies show that there are advantages and lim-
itations about different healing agents and strategies. In
order to realize effective and reliable self-healing, care
should be taken in choosing a healing agent and a suitable
strategy for a specic application.
(4) Engineered Cementitious Composite (ECC) is a new type of
ductile cement-based materials with a promising application
potential. The unique micro-crack behavior and tight
581
crack-width control property combined with its higher per-
centage of cementitious components and lower waterbin-
der ratio compared with traditional cementitious materials
endow ECC with high potential of realizing self-healing. More
efforts should be put into this eld to make smart ECC mate-
rials with effective and reliable self-healing property.
Acknowledgements
Parts of this review work are based on the research conducted
by the rst author studying in Delft University of Technology. Dr.
G. Ye and Prof. K. van Breugel from the faculty of Civil Engineering
and Geosciences are greatly acknowledged.
References
[1] van Breugel K. Is There a market for self-healing cement-based materials. In:
Proceedings of the rst international conference on self-healing materials,
Noordwijk aan zee, the Netherlands; April 2007.
[2] Hearn N, Morley CT. Self-healing property of concrete experimental
evidence. Mater Struct 1997;30:40411.
[3] Hearn N, Morley CT. Self-healing, autogenous healing and continued
hydration: what is the difference? Mater Struct 1998;31:5637.
[4] Hyde GW, Smith WJ. Results of experiments made to determine the
permeability of cements and cement mortars. J Franklin Inst Phila
1889:199207.
[5] Glanville WH. The permeability of portland cement concrete. Building
Research. Technical Paper 3; 1931. p. 161.
[6] Soroker VJ, Denson AJ. Autogenous healing of concrete. Zement 1926;25:30.
[7] Brandeis F. Autogenous healing of concrete. Beton und Eisen 1937;36:12.
[8] Jacobsen S, Sellevold EJ. Self-healing of high strength concrete after
deterioration by freeze/thaw. Cem Concr Res 1996;26(1):5562.
[9] Clear CA. The effects of autogenous healing upon the leakage of water through
cracks in concrete. Cem Concr Assoc Tech Rep 1985;559:31.
[10] Hearn N. Effect of shrinkage and load-induced cracking on water permeability
of concrete. ACI Mater J 1999;96(2):23441.
[11] Edvardsen C. Water permeability and autogenous healing of cracks in
concrete. ACI Mater J 1999;96:44854.
[12] Schlangen E. Fracture mechanics. CT5146 Lecture Notes. In: Hua X. Self-
healing of Engineered Cementitious Composites (ECC) in concrete repair
system. Master thesis, Delft University of Technology; 2010.
[13] Van der Zwaag S, editor. Self-healing materials: an alternative approach to 20
centuries of material science; 2007.
[14] Yang YZ, Lepech MD, Yang EH, Li VC. Autogenous healing of engineered
cementitious composites under wetdry cycles. Cem Concr Res
2007;39:38290.
[15] Qian S, Zhou J, de Rooij MR, et al. Self-healing behavior of strain hardening
cementitious composites incorporating local waste materials. Cem Concr
Compos 2009;31:61321.
[16] Homma D, Mihashi H, Nishiwaki T. Self-healing capability of bre reinforced
cementitious composites. J Adv Concr Technol 2009;7(2):21728.
[17] A.M. Neville. Properties of concrete; 1995.
[18] Neville AM. Autogenous healing a concrete miracle. Concr Int
2002;November:7682.
[19] Dry C. Procedure developed for self-repair of polymer matrix composite
materials. Compos Struct 1996;35(3):2639.
[20] Motuku M, Vaidya UK, Janowski GM. Parametric studies on self-repairing
approaches for resin infused composites subjected to low velocity impact.
Smart Mater Struct 1999;8:62338.
[21] Bleay SM, Loader CB, Hawyes VJ, et al. A smart repair system for polymer
matrix composites. Composites A 2001;32:176776.
[22] Pang JWC, Bond IP. Bleeding composites damage detection and self-repair
using a biomimetic approach. Composites Part A 2005;36:1838.
[23] Pang JWC, Bond IP. A hollow bre reinforced polymer composite
encompassing self-healing and enhanced damage visibility. Compos Sci
Technol 2005;65:17919.
[24] Dry C. Alteration of matrix permeability, pore and crack structure by the time
release of internal chemicals. In: Proceedings of advance in cementitious
materials. American Ceramic Society: Gaithersbury, Maryland; 1990. p. 729
68.
[25] Dry C. Matrix cracking repair and lling using active and passive modes for
smart timed release of chemicals from bers into cement matrices. Smart
Mater Struct 1994;3(2):11823.
[26] Dry C, McMillan W. Three-part methylmethacrylate adhesive system as an
internal delivery system for smart responsive concrete. Smart Mater Struct
1996;5(3):297300.
[27] Dry C. Three design for the internal release of sealants, adhesives and
waterproong chemical into concrete to release. Cem Concr Res
2000;30:196977.
582 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
[28] Mihashi H, Kaneko Y, Nishiwaki T, Otsuka K. Fundamental study on
development of intelligent concrete characterized by self-healing capability
for strength. Trans Jpn Concr Inst 2000;22(2):44150.
[29] Joseph C, Jefferson AD, Cantoni MB. Issues relating to the autonomic healing
of cementitious materials. In: Proceedings of rst international conference on
self-healing materials, Noordwijk aan Zee, Netherlands. Paper 61. Springer
CDROM; 2007.
[30] Li VC, Lim YM, Chan YW. Feasibility of a passive smart self-healing
cementitious composite. Composites B 1998;29B:81927.
[31] Thao TDP, Johnson TJS, Tong QS, Dai PS. Implementation of self-healing in
concrete proof of concept. The IES J Part A: Civil Struct Eng
2009;2(2):11625.
[32] Joseph C, Jefferson AD, Isaacs B, Lark R, Gardner D. Experimental investigation
of adhesive-based self-healing of cementitious materials. Mag Concr Res
2010;62(11):83143.
[33] Nishiwaki T, Mihashi H, Jang BK, Miura K. Development of self-healing system
for concrete with selective heating around crack. J Adv Concr Technol
2006;4(2):26775.
[34] Hemsley AR, Grifths PC. Architecture in the microcosm: biocolloids, self-
assembly and pattern formation. Philos Trans Roy Soc London
2000;358:54764.
[35] Schleicher L, Green BK. Manifold record material. US patent 2730456; 1956.
[36] Ghosh SK, editor. Functional coatings and microencapsulation: a general
perspective. Functional Coatings; 2006.
[37] White SR, Sottos NR, Geubelle PH, Moore JS, Kessler MR, Sriram SR, et al.
Autonomic healing of polymer composites. Nature 2001;409(6822):794.
[38] Boh B, umiga B. Microencapsulation technology and its applications in
building construction materials. Mater Geoenviron 2008;55(3):32944.
[39] Tomiuchi S, Nishihama Y. Inorganic building boards with uniform strength. JP
patent 61031338. Matsushita Electric Works, Ltd.; 1986.
[40] Noda Plywood Mfg. Co., Ltd. Fabrication of hydraulic building boards. JP
patent 60028776. Noda Plywood Mfg. Co., Ltd.; 1985.
[41] Heinen J, Babcock DS. Cartridges of quick-setting cement and gelled water. US
patent 4772326. Construction Products Research Inc.; 1988.
[42] Origasa W, Yoshida A, Kawamoto K. Premixed mortar. JP patent 63260877.
Nippon Sogo Maintenance Co., Ltd., Nichie Yoshida KK; 1988.
[43] Okamoto T, Sato T, Kanbayashi T, Kato C. Preparation of ne grain ice and dry
clathrate water for manufacture of concrete and mortar, and manufacture of
concrete and mortar. EP patent 338739. Mitsui Construction Co., Ltd., Shiiai
Kemutekku KK, Osaka Yuki Kagaku Kogyo Co., Ltd.; 1989.
[44] Nishiwaki T. Fundamental study on development of intelligent concrete with
self-healing capability. Masters thesis, Department of Architecture and
Building Science, Graduate School of Engineering, Tohoku University; 1997.
[45] E. Rattner. Cost-effective self-healing concrete. <http://thefutureofthings.
com/news/10104/cost-effective-self-healing-concrete.html>. (accessed
January, 2011).
[46] Kishi T, Ahn TH, Hosoda A, Takaoka H. Self-healing behavior by cementitious
recrystallization of cracked concrete incorporating expansive agent. In:
Proceedings of the rst international conference on self-healing materials,
Noordwijk aan zee, the Netherlands; April 1820, 2007.
[47] Ahn TH. Development of self-healing concrete incorporating geo-materials: a
study on its mechanism and behavior in cracked concrete. PhD dissertation,
Department of Civil Engineering, The University of Tokyo, Japan; 2008.
[48] Ahn TH, Kishi T. The effect of geomaterials on the autogenous healing
behavior of cracked concrete. In: Proceeding of 2nd ICCRRR, Cape Town,
South Africa; 2008. p. 23540.
[49] Ahn TH, Kishi T. Crack self-healing behavior of cementitious composites
incorporating various miner admixtures. J Adv Concr Technol
2010;8(2):17186.
[50] Jonkers HM, Thijssen A, Muyzer G, Copuroglu O, Schlangen E. Application of
Bacteria As Self-Healing Agent for the Development of Sustainable Concrete.
In: Proceedings of the 1st international conference on biogeocivil
engineering, Delft, The Netherlands; June 2325, 2008.
[51] Tittelboom KV, Belie ND, Muynck WD, Verstraete W. Use of bacteria to repair
cracks in concrete. Cem Concr Res 2010;40:15766.
[52] Gollapudi UK, Knutson CL, Bang SS, Islam MR. A new method for controlling
leaching through permeable channels. Chemosphere 1995;30:695705.
[53] van der Zwaag S. Routes and mechanisms towards self-healing behavior in
engineering materials. Bull Polish Acad Sci 2010;58(2):22736.
[54] Sakai Y, Fukuta T. Experimental study on enhancement of self-restoration of
concrete beams using SMA wire. In: Proceedings of smart structures and
materials 2003: smart system and nondestructive evaluation for civil
infrastructures, San Diego, CA, USA; 2003.
[55] Tawil SE, Rosales JO. Prestressing concrete using shape memory alloy
tendons. ACI Struct J 2004(NovemberDecember):84651.
[56] Saiidi MS, Sadrossadat M, Ayoub C, Itani A. Pilot study of behavior of beams
reinforced with memory alloys. J Mater Civil Eng ASCE 2007;6:154358.
[57] Simon D. Self-healing concrete a sustainable future.
<www.swieet2007.org.uk/les/SelfHealingConcrete.pdf> (accessed on
December, 2010); 2007.
[58] Jefferson A, Joseph C, Lark R, et al. A new system for crack closure of
cementitious materials using shrinkable polymers. Cem Concr Res
2010;40:795801.
[59] Song G, Ma N, Li HN. Application of shape memory alloys in civil structures.
Eng Struct 2006;28:126674.
[60] Duerig TW, Melton KN, Stockel D, Waymanb CM. Engineering aspects of
shape memory alloys. London: Butterworth-Heinemann; 1990.
[61] Song G, Mo YL. Increasing concrete structural survivability using smart
materials. A proposal submitted to Grants to Enhance and Advance Research
(GEAR), University of Houston; January 2003.
[62] Kuang YC, Ou JP. Self-repairing performance of concrete beams strengthened
using superelastic SMA wires in combination with adhesives released from
hollow bers. Smart Mater Struct 2008;17(2):205.
[63] Hua X. Self-healing of Engineered Cementitious Composites (ECC) in concrete
repair system. Master thesis, Delft University of Technology; 2010.
[64] Yamazaki Y, Kamiaka H, Kobayashi S, Hirose T. Expansion mechanism and
hydration of expansive cement. CAJ Rev 34th Gen Meet 1980;34:5961.
[65] Nagataki S, Gomi H. Expansive admixtures (mainly ettringite). Cem Concr
Compos 1998;20(2):16370.
[66] Mehta PK. Mechanism of expansion associated with ettringite formation.
Cem Concr Res 1973;3:16.
[67] Ish-Shalom M, Bentur A. Properties of type K expansive cement of pure
components II. Proposed mechanism of ettringite formation and expansion
in unrestrained paste of pure expansive component. Cem Concr Res
1974;4:70921.
[68] Ish-Shalom M, Bentur A. Properties of type K expansive cement of pure
components III. Hydration of pure expansive component under varying
restraining condition. Cem Concr Res 1975;5:13952.
[69] Cohen MD. Modeling of expansive cements. Cem Concr Res 1983;13:51928.
[70] Hammes F, Verstraete W. Key roles of pH and calcium metabolism in
microbial carbonate precipitation. Rev Environ Sci Biotechnol
2002;1(1):37.
[71] Day JL, Ramakrishnan V, Bang SS. Microbiologically induced sealant for
concrete crack remediation. In: Proceedings of 16th engineering mechanics
conference, Seattle, Washington; 2003.
[72] Bang SS, Galinat JK, Ramakrishnan V. Calcite precipitation induced by
polyurethane-immobilized bacillus pasteurii. Enzyme Microb Technol
2001;28(4):4049.
[73] Ramakrishnan V, Panchalan RK, Bang SS. Improvement of concrete durability
by bacterial mineral precipitation. In: Proceedings of 11th international
conference on fracture, Turin, Italy; 2005.
[74] Bachmeier KL, Williams AE, Warmington JR, Bang SS. Urease activity in
microbiologically-induced calcite precipitation. J Biotechnol
2002;93(2):17181.
[75] Scrivener KL, Damidot D, Famy C. Possible mechanisms of expansion of
concrete exposed to elevated temperatures during curing (also known as
DEF) and implications for avoidance of eld problems. Cem Concr Aggr
1999;21:93101.
[76] Collepardi M. Damage by delayed ettringite formation a holistic approach
and new hypothesis. Concr Int 1999;21(1):6974.
[77] Mehta PK. Sulfate attack on concrete a critical review. materials science of
concrete III. The American Ceramic Society; 1993. p. 10530.
[78] Taylor HFW. Cement chemistry. second ed. London: Thomas Telford
Publishing; 1997.
[79] Heinz D, Ludwig U. Mechanism of secondary ettringite formation in mortars
and concretes subjected to heat treatment. In: Seanlon JM, editor. Concr
durability. Katharine and Bryant Mather Int Conf, SP 100, vol.
2. Detroit: American Concrete Institute; 1987. p. 205971.
[80] Brown PW, Bothe JV. The stability of ettringite. Adv Cem Res
1993;5(18):4763.
[81] Taylor HFW, Famy C, Scrivener KL. Delayed ettringite formation. Cem Concr
Res 2001;31(5):68393.
[82] Romualdi NP, Batson GB. Mechanics of crack arrest in concrete. Proc ASCE Eng
Mech J 1963;89(3EM):14768.
[83] Romualdi JP, Mandel JA. Tensile strength of concrete affected by uniformly
distributed closely spaced short lengths of wire reinforcement. Proc ACI J
1964;61(6):65771.
[84] Naaman AE, Reinhardt HW. Setting the stage: toward performance-based
classication of FRC composites. In: High Performance Fiber Reinforced
Cement Composites (HPFRCC-4). Proceedings of the 4th intl RILEM
workshop. Naaman AE, Reinhardt HW, editors. Published by RILEM S.A.R.L.
2003. p. 14.
[85] Chanvillard G, Rigaud S. Complete characterization of tensile properties of
ductal UHPFRC according to the French recommendations. In: Proceedings of
the fourth international RILEM Workshop on High-Performance Fiber-
Reinforced Cement Composites (HPFRCC 4), Naaman AE, Reinhardt HW,
editors. RILEM, Paris; 2003. p. 2134.
[86] Reinhardt HW, Krger M, Groe CU. Concrete prestressed with textile fabric. J
Adv Concr Technol 2003;1(3):2319.
[87] Mobasher B, Peled A, Pahilajani J. Distributed cracking and stiffness
degradation in fabriccement composites. Mater Struct 2006;39:31731.
[88] Li VC, Yang E. Self-healing in concrete materials. In: van der Zwaag S, editor.
Self-healing materials. Dordrecht: Springer; 2007. p. 16193.
[89] Fischer G, Wang S, Li VC. Design of engineered cementitious composites for
processing and workability requirements. In: Proceedings of the seventh
international symposium on brittle matrix composites, Warsaw, Poland;
2003. p. 2936.
[90] Li VC. Engineered Cementitious Composites (ECC) material, structural and
durability performance. In: Nawy E, editor. Concrete Construction
Engineering Handbook. Boca Raton: CRC Press; 2009 [Chapter 24].
 M. Wu et al. / Construction and Building Materials 28 (2012) 571583
[91] Li VC. From micromechanics to structural engineering the design of
cementitious composites for civil engineering applications. JSCE J Struct Mech
Earthquake Eng 1993;10(2):3748.
[92] Zhou J, Qian S, Ye G, Breugel KV, Li VC. Development of engineered
cementitious composites with limestone powder and blast furnace slag.
Mater Struct 2010;43(6):80314.
[93] Weimann MB, Li VC. Hygral behavior of Engineered Cementitious Composite
(ECC). Int J Restor Build Monuments 2003;9(5):51334.
[94] Yang Y, Michael DL, Yang E, Li VC. Autogenous Healing of Engineered
Cementitious Composites under Wet-Dry Cycles. Cem Concr Res
2009;39:38290.
[95] LiM. Multi-scale design for durable repair of concrete structures. PhD thesis,
The University of Michigan, USA; 2009.
[96] Reinhardt H, Joos M. Permeability and self-healing of cracked concrete as a
function of temperature and crack width. J Cem Concr Res 2003;33:9815.
[97] Jacobsen S, Marchand J, Homain H. SEM observations of the microstructure of
frost deteriorated and self-healed concrete. J Cem Concr Res
1995;25:178190.
583
[98] Ismail M, Toumi A, Francois R, Gagne R. Effect of crack opening on local
diffusion of chloride inert materials. J Cem Concr Res 2004;34:7116.
[99] Aldea C, Song W, Popovics JS, Shah SP. Extent of healing of cracked normal
strength concrete. J Mater Civil Eng 2000;12:926.
[100] Yang Y, Lepech M, Li VC. Self-healing of ECC under cyclic wetting and drying.
In: Proceedings of international workshop on durability of reinforced
concrete under combined mechanical and climatic loads, Qingdao, China;
2005. p. 23142.
[101] Sahmaran M, Li M, Li VC. Transport properties of engineered cementitious
composites under chloride exposure. ACI Mater J 2007;104(6):60411.
[102] Zhou J, Qian S, Sierra Beltran MG, et al. Developing engineered cementitious
composite with local materials. In: International conference on
microstructure related durability of cementitious composites, Nanjing,
China; 2008.
[103] Qian SZ, Zhou J, Schlangen E. Inuence of curing condition and precracking
time on the self-healing behavior of engineered cementitious composites.
Cem Concr Compos 2010;32:68693.