Composites Part B 87 (2016) 92e119

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Review

Self-healing materials: A review of advances in materials, evaluation,

characterization and monitoring techniques
D.G. Bekas, K. Tsirka, D. Baltzis, A.S. Paipetis*
Department of Materials Science and Engineering, University of Ioannina, Ioannina 45110, Greece

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

Article history: Self-healing materials are attracting increasing interest of the research community, over the last decades,
Received 1 July 2015 due to their efciency in detecting and autonomically healing damage. Numerous attempts are being
Received in revised form presented every year focusing on the development of different self-healing systems as well as their
3 September 2015
integration to large scale production with the best possible propertyecost relationship. The current work
Accepted 27 September 2015
Available online 31 October 2015
aims to present the most recent breakthroughs in these attempts from many different research groups
published during the last ve years. The current review focuses in polymeric systems and their com-
posites. The reviewed literature is presented in three distinct categories, based on three different scopes
Keywords:
Self-healing materials
of interest. These categories are (i) the materials and systems employed, (ii) the experimental techniques
A. Polymerematrix composites (PMCs) for the evaluation of materials properties and self-healing efciency of the materials/structures and (iii)
B. Mechanical properties the characterization techniques utilized in order to evaluate (off-line) and monitor (on-line) the healing
C. Mechanical testing efciency of the proposed systems. Published works are presented separately in all the different cate-
gories, thus the interested reader is advised to follow the structure of the review and refer to the chapter
of interest.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Self-healing materials are a relatively new class of smart mate-
rials that possess the ability to fully or partially recover a func-
tionality that is mediated by operational use. Local functionality
loss can be dened as the situation when a section of a material or
structure exhibits degraded performance when compared with the
rest of the material/structure. Global functionality loss can be
dened as the situation when the material or structure exhibits
degraded performance when compared to its properties prior to
any exposure to operational loads.
This work focuses on self-healing polymers and their com-
posites. The incorporation of healing agents in polymeric mate-
rials inadvertently leads in a new material with altered
properties when compared to the material that does not possess
the healing functionality. The performance and life-time of the
new composite in conjunction with the efciency of the self-
healing functionality are of primary importance as they are
often competing with each other.
* Corresponding author.
E-mail address: paipetis@cc.uoi.gr (A.S. Paipetis).
The scope of the rst section of this work is to describe the three
primary self-healing approaches (intrinsic, capsule based and
vascular) as well as the critical issues and challenges associated
with each approach. A review of the literature on the materials that
have been used as healing agents over the last ve years is
presented.
The aim of the second section of this review is to present the
most frequently used testing procedures and specimen geometries
found in research publications during the last ve years. Special
consideration is given to the ones that provide, either qualitatively
or quantitatively, insight on the self-healing performance of the
composites. Associated ASTM standards are also presented.
Finally, in order to gain an overall insight into the behavior of
self-healing materials, their structure, performance and self-
healing effectiveness is evaluated via the use of various character-
ization and monitoring techniques. The combination of mechanical
testing and materials characterization techniques can exploit the
actual capabilities as well as restraints associated with these ma-
terials. The ongoing development of the microscopic, spectroscopic
and other characterization methods during the last decades, ren-
ders them invaluable tools, which can provide knowledge about the
structure of materials, their chemical composition, as well as the
way the react. In the last section of the current review, an extensive

http://dx.doi.org/10.1016/j.compositesb.2015.09.057
1359-8368/ 2015 Elsevier Ltd. All rights reserved.
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
overview of the most common monitoring methods is presented.
Typical microscopic methods such as optical and scanning electron
microscopy as well as analytical and spectroscopic methods like
NMR, AFM, FTIR and Raman spectroscopy employed for the eval-
uation and monitoring of self-healing are presented. The present
review covers the literature published during the last ve years,
with more extensive information and paradigms in each different
case.
2. Materials
The ability of self-healing materials to regain autonomously or
externally assisted, their initial properties is primarily affected by
the selection of the healing agents. Inspired by the biological sys-
tems, intrinsic, capsule-based and vascular methods, are the main
approaches used in order to impart self-healing functionalities to
materials or structures. A variety of self-healing agents have been
extensively studied to meet the requirements of the new highly
demanding applications of smart materials. This section is dedi-
cated to the review of the research on the aforementioned three
approaches as well as the materials that have been proposed as
healing agents over the last ve years.
2.1. Intrinsic self-healing materials
In the recent past, polymer science has reached at a point where
it is possible to synthesize smart polymers that possess the
remarkable, bio-inspired ability of regaining their initial properties
completely, ideally without external input. These polymers
constitute one of the most important categories of self-healing
materials, that of the intrinsic or remendable healing polymers. In
this case, repair is achieved through the inherent reversibility of
bonding in the matrix phase, which acts as a healing agent.
Despite the good healing performance that was achieved in the
rst generation of intrinsic self-healing epoxy systems [1], the
incorporation of dicyclopentadiene (DCPD)/Grubbs' catalyst within
the matrix e an expensive and unstable in the hostile environment
Grubbs' catalyst-limits its applications [2]. Within the aim of the
research community is to maximize the healing efciency and
minimize the cost. Therefore, several other material and techniques
have been developed in order to satisfy these criteria.
Thermally reversible reactions, especially the DielseAlder (DA)
reaction, for cross-linking linear polymers have been extensively
studied by many researchers. Their main advantage is the theo-
retically innite number of repetitions of the healing process
without any further addition of chemical or healing agents [3e6].
Hermosilla et al. [7] presented a novel reversible thermoset poly-
mer based on chemical modication of aliphatic polyketones into
the corresponding derivatives containing furan and/or amine
groups along the backbone. The furan moieties allow for the ther-
mal setting of the polymer by the DielseAlder (DA) and retro-DA
sequence (bis-maleimide), while amine moieties allow for the
tuning of the hydrogen bonding density. This new class of polymer
material showed improved Tg values with respect to the respective
counterparts containing only furan groups. Via this modication,
these materials recover their mechanical properties after three
thermal cycles. In another study, Joost Brancart et al. [8] investi-
gated the ability of furan-maleimide building blocks to create
reversible covenant networks in an epoxy based coating. Furan-
ctionalized precursors were synthesized via reaction of amines
with furfuryl glycidyl ether (FGE). The reversible cross-linking of
the furan-precursors with a bis-maleimide was achieved in a two-
step procedure. Thermal analysis of these composites showed that
modication of the polymer network structure allows for the
tailoring of the temperature for the self-healing process. Jenifer Ax
93
and Gerhard Wenz [9] created a processible, remendable and
highly oriented polymeric material with pending furane sub-
stituents, esterifying hydroxyethylcellulose with both furoyl chlo-
ride and acetic anhydride. In order to achieve crosslinking (DA
reaction), 1,6-bis(N-maleimido)hexane was used. They have shown
that both constituents can be mixed without premature formation
of gels due to the low rate DA reaction under 70
C. Yoshifumi
Amamoto et al. [10] have successfully produced a cross-linked
polymer based on reshufing of thiuram disulde (TDS) units.
Stimulation of the self-healing process occurred under ambient
conditions (visible light, air, room temperature) in the absence of a
solvent. To carry out the self-healing reaction in a bulk material at
room temperature, the reactive TDS units, capable of re-shufing,
were incorporated in the main chain of a low Tg polyurethane. In
a more recent work, Claudio Toncelli and co-workers [11] presented
the successful synthesis and crosslinking of functionalized (varying
amounts of furan groups) polyketones with (methylene-di-p-phe-
nylene)bis-maleimide. In addition, they managed to modify ther-
mal and mechanical properties of the material by controlling the
furan reactions. This self-healable polymer exhibited an almost full
recovery of thermal and mechanical properties for seven consec-
utive self-healing cycles, independently of the furan intake. Gua-
dalupe Rivero et al. [12] managed to produce polyurethane
networks with healing capability, based on PCL and furan-
maleimide chemistry, at mild temperature conditions via one-pot
synthesis. A combination of a quick shape memory effect (contact
of the free furan and maleimide moieties) followed by a progressive
DielseAlder reaction (reformation of the covenant bonds) allows
the remendable process to take place at 50
C, resulting in a com-
plete recovery of the structural integrity without complete melting
of the polymer. A schematic representation of the DielseAlder
based shape memory assisted self-healing process is depicted in
Fig. 1.
A new approach for the development of self-healing nano-
composites was proposed by Sandra Schafer and Guido Kickelbick
[13]. In their study surface-functionalized silica nanoparticles were
used as cross-linking agents in thermally triggered self-healing
Fig. 1. Schematic depiction of the DielseAlder based shape memory assisted self-
healing process in a polyurethane material based on PCL and furan-maleimide
chemistry [12].
Reprinted with permission from Rivero G, Nguyen L-TT, Hillewaere XKD, Du Prez FE.
One-Pot Thermo-Remendable Shape Memory Polyurethanes. Macromolecules.
47(6):2010e8. Copyright (2014) American Chemical Society.
94 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
nanocomposites based on Diels-Alder (DA) chemistry of poly (butyl
methacrylates) and structurally varied polysiloxanes. It has been
observed that the healing properties of the nanocomposite are
highly affected by the molecular structure of the crosslinker (spacer
length), the length of the polymeric chain but also by the type of the
polymer. DA reaction seemed to be favored by the use of modied
polymers (high mobility) and by the presence of particles that have
long spacer groups along with lower molar amount of coupling
agent.
Apart from the DielseAlder reaction, different healing chemis-
tries have been explored to meet the application requirements of
self-healing polymers in different occasions. Healing functionality
was successfully incorporated in a polyurethane (PU) elastomer by
crosslinking the tri-functional homopolymer of hexamethylene
diisocyanate (tri-HDI) and polyethylene glycol (PEG) with
alkoxyamine-based diol. It has been shown that the design of the
polyurethane molecules can be used to optimize not only the me-
chanical properties but also the healing performance. Moreover,
the healing process is completed only by a single step dynamic
equilibrium of CeON bonding, unlike to self-healing based on
reversible DA bonds, which has to be heated up to a certain tem-
perature for disconnecting the intermonomer linkages and then
cooled down for reconnection [14]. Additional efforts have been
made towards the production of autonomously self-healing mate-
rials using non-covalently bonded systems where the polymeri-
zation and/or the crosslinking occur by intermolecular interactions
of the monomer units and/or the side chains. Compared to chem-
ically cross-linked hydrogels, supramolecular hydrogels demon-
strate better reproducibility of the healing procedure. Takahiro
Kakuta et al. [15] used the hosteguest interaction to produce self-
healing materials that can recover their initial strength even after
being sectioned in the middle. The aforementioned self-healable
supramolecular materials consisted of cyclodextrins (CD) - guest
gel crosslinked between poly(acrylamide) chains with inclusion
complexes. The obtained CDeguest gels exhibit a self-standing
property without chemical crosslinking reagents, indicating that
the newly formed hosteguest interactions between the CD and the
guest units stabilize the conformation of the CDeguest gels. In
another study, [16], a promising non-covalent thermal-switchable
self-healing hydrogel was developed by mixing hydrophobically
modied chitosan (hm-chitosan) with thermal-responsive vesicle
composed of 5-methyl salicylic acid (5 mS) and dodecyl-
trimethylammonium bromide (DTAB). By altering the temperature,
the hydrogel can be switched from sol to gel state (Fig. 2). These
transitions can be reversibly performed for several cycles in a
similar way to a supramolecular gel. The gelation temperature in
particular, can be easily controlled by varying the ratio of DTAB to
5 mS.
In a more recent work, Lafont and his team [17], created a
multifunctional self-healing composite capable of multiple healing
by mixing an uncured thermoset rubber with reversible disulphide
bonds, loading it with inert, thermally conductive graphite and
hexagonal boron nitride (hBN) as llers. They proved that higher
the healing temperature the better was the cohesion recovery even
for highly loaded composites. A very promising concept that com-
bines reversible covalent linkages through imine bond formation
with non-covalent interactions through hydrogen bonds between
urea-type groups inside the same polymer structure was presented
by Nabarun Roy and his team [18]. Through polycondensation re-
action between siloxane-based dialdehyde and carbohydrazide
they managed to address reversibility to carbinol (hydroxyl) e
terminated polydimethylsiloxane (PDMS) via the formation of bis-
iminourea type subunits. Acylhydrazone units and lateral hydrogen
bonding interactions impart to the polymer structure reversible
covalent and non-covalent linkages respectively, resulting to a soft
dynamic polymer lm capable of autonomous healing. In addition,
alterations to mechanical properties of the polymer can be ach-
ieved by modifying the length of the siloxane spacer units. In
another study, So Young An et al. [19] reported a novel dual sul-
deedisulde crosslinked networks which exhibited a rapid
(30 se30 min) and effective self-healing ability at room tempera-
ture without external stimuli. The method that has been used for
the synthesis of dual-suldeedisulde crosslinked network, pro-
duced a sufcient density of disulde crosslinkages which was
necessary for the completion of the self-healing process at room
temperature.
2.2. Capsule-based self-healing materials
An alternative approach to achieve self-repair polymeric mate-
rials is the incorporation of capsules within the polymer. Inside
these microcapsules lies the healing agent which will be delivered
to the damaged area upon rupture of the capsule. The rst capsule-
based self-healing concept was proposed by White et al. [2]. They
embedded microcapsules containing healing agent and catalyst
particles into a matrix material achieving a very promising self-
healing efciency. Since then, microcapsules were extensively
studied by many researchers due to their ease of applicability and
their potential for mass production. Several epoxy monomers have
been easily encapsulated using various methods [20e25]. However,
the encapsulation of suitable hardeners remains an issue. Recently,
Li Yuan et al. [26] demonstrated the self-healing ability of a cyanate
ester (CE) resin by the addition of microcapsules within the volume
of the material. The capsules consisted of a poly(urea-
formaldehyde) shell lled with an bisphenol A epoxy (EP) as
curing agent. Diaminodiphenylsulfone (DDS) catalyst was also used
in the CE formulation to decrease the polymerization reaction
temperature. Specimens exhibited an 85% self-healing efciency
proving the effectiveness of the microcapsule approach for the
development of self-healing polymer materials, as well as for ber-
reinforced CE composites. Henghua Jin et al. demonstrated a self-
healing epoxy adhesive suitable for bonding steel substrates us-
ing DCPD lled microcapsules and Grubbs' rst generation catalyst
[27]. It was noteworthy that the addition of both components to the
neat resin epoxy (EPON 828) increased the virgin fracture tough-
ness by 26% and a recovery of 56% of fracture toughness was
reported.
Capsule-based self-healing coatings have been studied by many
researchers over the last three years to due to the increased
importance of maintaining the potential of protection of the un-
derlying substrate [28e33]. In detail, Xiuxiu Liu et al. [33] prepared
a smart self-healing coating consisted of an epoxy resin (diglycidyl
ether of bisphenol A) as matrix and microcapsules lled with the
same polymer as curing agent. Capsules were synthesized by
interfacial polymerization of epoxy droplets with ethylenediamine
(EDA). These microcapsules exhibited high shell strength while
they could rupture under external force, releasing the healing agent
to the damaged area. It should be noted that the complete absence
of catalyst along with the high level of healing efciency, make
epoxy-capsule loaded polymers excellent candidates for the
development of self-healing lms. In another study, Erica Manfredi
and co-workers [34] produced glass ber reinforced polymer
(CFRP) containing a solvent (ethyl phenylacetate e EPA) capsule-
based healing system using vacuum assisted resin infusion mold-
ing technique. Capsules were manually dispersed into the com-
posite and the maximum pressure threshold, in order to avoid
premature capsule rupture was 0.3 bar. It must be pointed out that
the healing process is based on the swelling mechanism of the
polymeric matrix (Epon 828/DETA) in the presence of EPA solvent,
and lling the defects that have been created due to static loading
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119 95

Fig. 2. Thermal-switching of the vesicle-based gel. Photographs of a sample in aqueous solution: (a) before and (b) after heating. (c) Schematic illustration of the solegel transition
[16].
Reprinted from Colloid and Polymer Science, Vol. 291(7), 2013, pp. 1749e58, Thermal-responsive self-healing hydrogel based on hydrophobically modied chitosan and vesicle. Hao
X, Liu H, Xie Y, Fang C, Yang H., Figure 2, Original caption: Thermal-switching of the vesicle-based gel. Photographs of a sample of hm-chitosan (0.4%) and DTAB/5 mS (16 mM/
20 mM) in aqueous solution: a before and b after heating. Before heating, the sample is strongly viscoelastic and holds its weight in the inverted vial. After heating at 55
C for
10 min, the sample is transformed into a low viscosity uid that ows easily. c Schematic illustration of the solegel transition., Copyright Springer-Verlag Berlin Heidelberg 2013,
with kind permission from Springer Science and Business Media.

in Mode I and II. Using a single capsule, resin-solvent self-healing
chemistry, Jones and co-workers [35] managed to obtain a full re-
covery of interfacial shear strength (IFSS) for a glass/epoxy com-
posite. Microcapsules contained EPON 862 (diglycidyl ether of
bisphenol-F) dissolved in ethyl phenylacetate (EPA) while the
shell material consisted of poly(urea-formaldehyde) e pUF. More-
over, several parameters that can affect the healing efciency of the
system, like the resin-solvent ratio, the capsule coverage and the
Fig. 3. SEM micrographs of glass bers with varying capsule [35].
Reprinted from Composites Science and Technology, Vol. 79, Jones AR, Blaiszik BJ,
White SR, Sottos NR., Full recovery of ber/matrix interfacial bond strength using a
microencapsulated solvent-based healing system. pp. 1e7, Copyright (2013), with
permission from Elsevier.
capsules size were also examined. Results indicated that the critical
resin-solvent ratio in order to obtain submicron capsules (0.6 lm
diameter) was 30:70 in which a total 83% recovery of IFSS was re-
ported. Fig. 3 depicts SEM images of bers with varying capsule
coverage that have been used for the IFSS experiment.
Dual-component microcapsules also drew the attention of the
research community. The approach lies in fabricating a self-healing
epoxy composite by embedding a healing agent consisting of epoxy
and its hardener inside separate capsules. He Zhang and co-worker
[36] created two types of healing agent carriers, i.e. microcapsules
containing epoxy solution (Epolam 5015 and hardener 5015) and
etched hollow glass bubbles (HGBs) loaded with amine solution
(diethylenetriamine and ethyl phenylacetate) which they incor-
porated in self-healing epoxy system (Epolam 5015 and hardener
5015). Using TGA, SEM and optical microscopy they managed to
characterize both capsules and bubbles. The results indicate that
the amine in the etched HGBs shows high thermal stability during
the curing stage. A mathematical model has been also formulated
in order to calculate the available healants and the diffusion dis-
tance on the crack plane of a two-part epoxy-amine. Based on the
simple cubic array model, the diffusion distance of the released
healing agent was calculated to be inversely proportional to the
cubic root of the concentration of the healing agent carrier. In a
more recent study [37], Jin and his team focused on the encapsu-
lation of epoxy and amine reactants in separate polymeric micro-
capsules. In the case of the epoxy resin, a polyurethane (PU)-
poly(urea-formaldehyde) (PUF) double shell wall was used. The
core consisted of disphenol-A epoxy resin diluted with a low vis-
cosity reactive diluent (o-cresyl glycidyl ether). As for the amine
capsules, they were produced following a method of vacuum
inltration of polyoxypropylenetriamine (POPTA) into polymeric
hollow (PUF walled) microcapsules, demonstrating thus a simple
approach for the encapsulation of a highly reactive core material.
Both epoxy and amine microcapsules can be seen in Fig. 4.
96 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Fig. 4. (a) Epoxy capsules consist of a polyurethane e poly(UF) double shell wall and a DGEBA/o-CGE core. (b) Amine capsules contain a poly(UF) shell wall and a POPTA core [37].
Reprinted from Jin H, Mangun CL, Grifn AS, Moore JS, Sottos NR, White SR. Thermally stable autonomic healing in epoxy using a dual-microcapsule system. Advanced Materials.
26(2):282e7, Copyright (2013) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Afterward, the capsules were embedded into an epoxy matrix
system (Araldite/Aradur 8615) while taking into account the
required stoichiometry. Maintaining the total capsule concentra-
tion at 10 wt% while varying the ratio of epoxy to amine capsules,
they managed to obtain the highest average healing efciency
which was at an equal mass ratio of amine:epoxy capsules (5:5). It
was demonstrated, higher exposure temperature caused more loss
of core contents for both types of capsules leading to a poor mixing
of the reactants in the damaged area.
Apart from the well-known poly(urea-formaldehyde)-shell mi-
crocapsules, a generalized silica coating scheme was developed by
Jackson et al. in order to functionalize and protect sub-micron and
micron size dicyclopentadiene monomer-lled capsules and
Grubbs' catalyst particles [38]. Fluoride-catalyzed silica condensa-
tion chemistry was used for the construction of the protective and
functional silica coatings resulting to an improvement of the
dispersion of the capsules and catalyst particles inside the epoxy
matrix. Unlike many other studies, a successful incorporation of
both capsules into the epoxy was achieved without signicant loss
of healing agent. In Fig. 5, a TEM image of a silica coated DCPD-lled
capsule is presented.
In an effort to improve the self-healing efciency of epoxy
resin, Qi Li and his co-workers [39] prepared a dual-component
microcapsule of diglycidyl ether of bisphenol A epoxy (DGEBA)
(resin) and polyether amine (hardener) using a water-in-oil-in-
water emulsion solvent evaporation technique with polymethyl
methacrylate (PMMA) as shell material. They have shown that
the healing efciency of epoxy was affected by the content and
ratio of the dual-component microcapsules. Self-healing was
carried out successfully at room temperature, but as was indi-
cated, increase in temperature led to higher levels of the self-
healing efciency.
A very interesting concept developed by Dong Yu Zhu and his
team [40] constitutes the construction and development of a
multilayered microcapsules used for self-healing thermoplastics
(Fig. 6). By optimizing the synthesis conditions, robust
poly(melamine-formaldehyde) (PMF)-walled microcapsules con-
taining uidic glycidyl methacrylate (GMA) monomer with proper
size and core content were produced. Second and third (outer/
protective) layers consisted of living poly(methyl methacrylate)
(PMMA-Br) and wax respectively. Results concerning the perfor-
mance and stability (thermal and chemical) indicate that the
multilayered microcapsules might be applicable for manufacturing
not only self-healing thermoplastics but also self-healing
thermosets.
2.3. Vascular self-healing materials
Similar to blood vessels in biology, vascular self-healing systems
incorporate healing agents into a polymer matrix through micro-
channels. The original idea as proposed by Toohey et al. [41], con-
cerned the incorporation of a microchannel network containing
dicyclopentadiene (DCPD) in the material. Microchannels delivered
DCPD to an epoxy surface coating containing Grubbs' catalyst. Over
the years vascular self-healing materials were extensively studied
due to the variety of healing that can be used and the large scale of
damage that can be healed [42e47]. Patrick et al. [48] demon-
strated that in situ self-healing can be achieved in structural ber-
composites via microvascular delivery of isolated, reactive healing
reactants. Diglycidyl ether of bisphenol A (DGEBA) based epoxy
resin (EPON 8132) and aliphatic triethylenetetramine (TETA) based
hardener (EPIKURE 3046) were used as healants due to their re-
action kinetics and their post-polymerized mechanical properties.
In order to create the microvascular network, pre-vascularized
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119 97

Fig. 5. A representative TEM image of a microtomed cross-section of a silica coated DCPD-lled capsule. The DCPD core is removed during the microtoming process [38].
Reprinted from Aaron C. Jackson, Jonathan A. Bartelt, Kamil Marczewski, Nancy R. Sottos, Paul V. Braun. Silica Protected Micron and Sub-Micron Capsules and Particles for Self-
Healing at the Microscale. Macromolecular Rapid Communications. Copyright (2010), Wiley Periodicals. Inc.

composite textile reinforcement was produced by stitching
catalyst-infusion, in a precise pattern of aerospace-grade woven
fabric. The ber composite preform was then consolidated into a
structural laminate via vacuum assisted resin transfer molding
(VARTM) of a thermoset epoxy matrix. It is noteworthy that after
the nal thermal PLA evacuation step (three-dimensional (3D)
microvasculature), no signicant change to fracture properties was
observed. They have also shown that vascular architectures not
only provide efcient and repetitive delivery of healing agents, but
they also contribute to increased resistance to delamination initi-
ation and propagation. The self-healing cycle of the aforemen-
tioned microvascular system is depicted in Fig. 7.
The effect of microvascular channels on the in-plane tensile
properties and damage propagation in a 3D orthogonally woven/
glass epoxy has been successfully described by Coppola et al. [49].
Using Vaporization of Sacricial Components (VoSC) process they
managed to produce composites consisted of two part epoxy ma-
trix (EPON 862 epoxy/EPIKURE W curing agent) with straight and
wave shaped channels (Fig. 8). Sacricial bers (SF) were prepared
using poly(lactic acid) (PLA) monolament bers treated with
tin(II) oxalate (SnOx) catalyst so as to decrease their thermal
degradation temperature. SF removed during the post-curing pro-
cess leading to an insignicant alteration on the tensile properties,
strength and modulus of the composite material. In another work,
A. R. Hamilton et al. [95] reported the use of active pumps that can
deliver a two-part healing system (Epon 8132/Epikure 3046) inside
a material through microvascular networks. This technique allows a
small vascular system to deliver large volumes of healing agent to
the damaged area. Moreover, dynamic pumping leads to an
enhancement of component's mixing in the target region,
improving with that way the self-healing efciency.
The construction of self-healing materials with embedded
ternary interpenetrating microvascular networks by direct-write
assembly of fugitive inks has been reported by Hansen and his
team [50]. The matrix of the material consisted of a two part epoxy
system diglycidyl ether of bisphenol-A resin (EPON 8132) and an
aliphatic amidoamine (Epikure 3046) as hardener. It was note-
worthy that they managed to accelerate the recovery of mechanical
properties of the resin by exploring the effect of temperature on the
healing reaction kinetics of the healing agent. They report a

Fig. 6. Prole of multilayered microcapsule [40].

Reprinted from Polymer, Vol. 54 (16), Zhu DY, Rong MZ, Zhang MQ. Preparation and characterization of multilayered microcapsule-like microreactor for self-healing polymers. pp.
4227e36, Copyright (2013), with permission from Elsevier.
98 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119

Fig. 7. Life-cycle of a self-healing microvascular ber-composite. Pristine woven composite laminate showing stacked textile reinforcement with dual-channel (red/blue), liquid
lled vascular network [48]. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
Reprinted from Patrick JF, Hart KR, Krull BP, Diesendruck CE, Moore JS, White SR, et al. Continuous self-healing life cycle in vascularized structural composites. Advanced materials.
26(25):4302e8, Copyright (2014) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fig. 8. (aec) Schematics of the unit cell of the preforms. Optical micrographs show surfaces (def) normal to the warp direction and surfaces (gei) normal to the weft direction. Scale
bars represent 1 mm [49].
Reprinted from Composites Part A: Applied Science and Manufacturing, Vol. 59, Coppola AM, Thakre PR, Sottos NR, White SR. Tensile properties and damage evolution in vascular
3D woven glass/epoxy composites. pp. 9e17, Copyright (2014), with permission from Elsevier.
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
reduction in healing times by over an order of magnitude. In
attempting to improve the performance of self-healing materials,
Richard S. Trask and co-workers [51] presented the construction of
a combined sensing and healing vascular network within an
advanced ber-reinforced composite. Poly(tetrauoroethylene)
(PTFE)-coated steel wires used in order to create the microvascular
network inside a ber reinforced polymer composite. A low-
pressure sensor was directly connected within the perceived
damage zone, while the output signal of the sensor was monitored
via open-source microprocessors. The laminates were subjected to
a 10-J energy impact and the healing agent was delivered through a
pump from an external reservoir. Two different healing chemistries
were tested, a commercial system ResinTech RT151 and the well-
known epoxy based system of diglycidyl ether of bisphenol-A
(DGEBA), ethyl phenylacetate (EPA) and diethylenetriamine
(DETA) resulting to a recovery of 91% and 94% in post-impact
compression strength respectively.
The use of Hollow Glass Fibers (HGFs) lled with a single
component epoxy resin (Envirez 70301) in e-glass/epoxy compos-
ites has been reported by S. Zainuddin et al. [52]. The matrix con-
sisted of a two part epoxy system. Part-A was a blend of diglycidyl
ether of bisphenol-A (DGEBA), aliphatic deglycidylether and epoxy
terminated polyether polyol. The curing agent (Part-B) was a
mixture of 70e90% cycloaliphatic amine and 10e30% poly-
oxylalkylamine. A commercially available woven fabric oriented in
two directions (warp at 0
and ll at 90
) was used as reinforce-
ment. Fig. 9 depicts the fabrication of composite embedded with
HGFs. Using this methodology the managed to achieve signicant
regaining of the mechanical properties after multiple Low Velocity
Impact (LVI).
Koralagundi Matt et al. [53] produced a vascular network within
a conventional glass ber reinforced polymer matrix composites
(PMC) in order to address self-healing capability to a composite
Fig. 9. Filling of HGFs and fabrication of e-glass/epoxy composite [52].
Reprinted from Composite Structures, Vol. 108, Zainuddin S, Aren T, Fahim A, Hosur MV, Tyson JD, Kumar A, et al. Recovery and improvement in low-velocity impact properties of
e-glass/epoxy composites through novel self-healing technique. pp. 277e86, Copyright (2014), with permission from Elsevier.
99
structure that can be used in wind turbine blades. Via dynamic
mechanical analysis (DMA), they proved that the vascular network
does not affect the dynamic mechanical properties of the nal
composite. Moreover, it has been shown that the most effective
way to produce vascular self-healing structures is to arrange the
tube network parallel to the resin ow direction during the vacuum
infusion process.
3. Material properties as a means to self-healing evaluation
The challenge in the design of self-healing materials is to create
a new composite material with an autonomous or externally
stimulated damage healing capability in order to extend the per-
formance life time of the newly developed material or product. The
presence of local regions in the material with lower or degraded
performance than that of the surrounding areas can be dened as
damage [38]. Thermal or electrochemical degradation can also be
included under this denition.
The incorporation of self-healing agents (SHA) in a material such
as a typical polymer matrix would certainly alter its properties.
Hence it is crucial to monitor those changes in order to assess the
performance of the new composite material. These changes can
also be used as a mean to characterize qualitatively or quantita-
tively the healing performance. In the most favorable scenario, the
new material properties will be equal or better to that of the un-
modied one. The researcher or engineer should study the modi-
ed self-healing material as compared to the unmodied, virgin
material in order to assess its performance.
The following sections are dedicated to the presentation of
several methods, techniques, and specimen geometries to describe,
either qualitatively or quantitatively, the unmodied and modied
self-healing material properties and damage focusing on those that
can be used to characterize the healing performance.
100 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119

3.1. Self-healing modied and neat material's physical properties

Prior to the evaluation of the self-healing properties and per-

formance of the modied material, comparative tests are typically
employed in order to assess the modied and unmodied material
properties. Most of the self-healing systems that are reported in the
literature consist of a polymeric matrix and the self-healing agents.
These consist of microcapsules, vascular networks or other poly-
mers in the form of additives. The most frequently used charac-
terization techniques for these materials are Dynamic Mechanical
Analysis (DMA), Differential Scanning Calorimetry (DSC) and
Thermogravimetric Analysis (TGA).
DMA is a widely used technique for materials characterization
and it is mostly used to determine the glass transition temperature
of the constituent materials [44], the viscoelastic properties in
terms of storage and loss moduli or shear storage modulus [54] and
measure the coefcient of thermal expansion (CTE) [55].
DSC is also used to measure the glass transition temperature for
the matrix and the self-healing agents (SHA) [56], monitor the self-
healing process [39] and the curing process.
TGA is commonly used to determine selected characteristics of
materials that exhibit either mass gain or loss. In self-healing
studies, TGA is employed for the SHA thermal stability evaluation
[57] and the evaluation of the amount of encapsulated SHA. It is
also useful for decomposition and maximum weight loss temper-
ature measurements [58].
Other techniques that are employed in self-healing materials Fig. 10. Schematic of the tensile test specimen [49].
characterization include Fourier Transform Infrared Spectroscopy Reprinted from Composites Part A: Applied Science and Manufacturing, Vol. 59, Cop-
(FTIR) [58], Nuclear Magnetic Resonance (NMR) [59,60] and pola AM, Thakre PR, Sottos NR, White SR. Tensile properties and damage evolution in
RAMAN spectroscopy [61]. These techniques are widely used for vascular 3D woven glass/epoxy composites. pp. 9e17, Copyright (2014), with permis-
sion from Elsevier.
monitoring the self-healing process and will be further discussed in
later sections.
both of these standards in order to study the effect of vascular
3.2. Mechanical properties channels on the in-plane tensile properties and damage pro-
gression of three-dimensional woven textile composites. Com-
The following sections are dedicated to the presentation of posites specimens were prepared and tested according to
mechanical performance evaluation and the respective techniques ASTM D3039 while epoxy dog bone shaped specimens were
employed. It should be noted that apart from the information that prepared and tested according to ASTM D 638. A similar standard
these properties and techniques provide regarding the healing ef- is the ASTM D 1078 [66] which describes the microtensile dog
ciency, they can offer quantitative and qualitative means for bone specimen geometry but has the limitation that it cannot
comparing the modied and unmodied materials. It is also com- provide data for the determination of modulus of elasticity
mon that the mentioned techniques are complimented with other (Fig. 12) [67].
qualitative techniques like scanning electron, transmission elec-
tron, acoustical, and/or optical microscopy.

3.2.1. Static damage

Static damage can occur in structural materials in the form of
cracks anywhere in the 3D structure and depending on the appli-
cation, loading conditions and type of damage, can occur over the
span of multiple length scales. For instance cracks in a ber com-
posite structure can initiate on the berematrix interface, propa-
gate to the matrix phase and result in the failure of the structure
through ber eruption, pull out etc. The mechanical properties,
damage initiation and propagation and healing performance have
been extensively studied under universal testing machines under
various loading conditions and scenarios.
Tensile testing is one of those loading conditions and has been
used extensively for measuring stressestrain relations, ultimate
tensile strength and Young modulus [39]. Specimen geometries
for such tests include rectangular shaped specimens (Fig. 10) and
dog bone specimens [62,63] where ASTM D 3039 [64] and D 638
[65] are the respective standards that describe these Fig. 11. Representative stressestrain curves of virgin and repeatedly repaired
IDHPEG800-0.5 specimen [63].
two geometries along with all the variables included in the Reprinted from Polymer, Vol. 53(13), Ling J, Rong MZ, Zhang MQ. Photo-stimulated
testing procedures, while a representative graph obtained self-healing polyurethane containing dihydroxyl coumarin derivatives. pp. 2691e8,
from such tests can be seen in Fig. 11. Coppola et al. [49], refers to Copyright (2012), with permission from Elsevier.
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Ultimate tensile strength can be used in order to compare the
neat material properties with the modied ones [68] or to provide a
metric of the healing performance as described in the works of
Yuan et al. [14]. In their work, self-healing is characterized by quasi-
static tensile tests performed on rectangle shaped specimens. The
specimens are tested till fracture, then put together to heal and re-
tested. The ratio of tensile strength of the healed specimen to that
of the virgin one provides the healing efciency. The improper
alignment of the fractured surfaces and surface roughness effects
are challenges for the tensile tests because they can lead to porosity
of the healed specimens. In addition, tensile tests are inherently
designed to characterize bulk continuous deformation leading up
to failure and the tensile stress and strain values might be
misleading as the material necks prior to failure. Elongation at
break, yield point stress [69] and force displacement curves [70]
have also been used to quantify and characterize the self-healing
performance but due to the aforementioned challenges, these
metrics do not fully reect the healing quality.
Tensile loading conditions can be used to study the adhesion
behavior of adhesives or composites via lap shear tests. In such a
conguration, a thin slice of a self-healing adhesive is sandwiched
between two plates and the sample is tested under tension till the
lap joint fails and the maximum shear strength can be used as a
self-healing efciency in multiple cycles (Fig. 13) [71e73]. Another
approach is according to ASTM D 897 [74] where shear testing is
performed under compressive loading conditions. ASTM D 3846
[75] refers to reinforced plastics and is concerned with the deter-
mination of in plane shear strength of reinforced thermosetting
plastics in at sheet form in thicknesses ranging from 2.54 to
6.60 mm and is adopted by Hondred et al. [76] in order to examine
the adhesive properties of thermosetting polymers modied with
rare earth triates.
A major advantage of the lap shear tests is that fractured sur-
faces can be brought into contact in a more controlled manner
compared to tensile tests and the alignment and clamping condi-
tions are easily reproducible and less sensitive to topological
effects. In addition for self-healing systems with reversible chem-
istries, the lap shear tests can be designed to study experimental
parameters of controlled force, curing temperature, and multiple
healing cycles. However the distinction between adhesive and
cohesive failure is of paramount importance.
Fig. 12. Microtensile test specimens [67].
Reprinted from Grande AM, Castelnovo L, Landro LD, Giacomuzzo C, Francesconi A,
Rahman MA. Rate-Dependent Self-Healing Behavior of an Ethylene-co-Methacrylic
Acid Ionomer Under High-Energy Impact Conditions. Journal of Applied Polymer Sci-
ence. Copyright (2013), Wiley Periodicals. Inc.
101
The cohesion recovery is related to the ability of the material to
exhibit temperature-activated mending within its volume. To
investigate the cohesive healing ability, Lafont et al. [17] cut their
self-healing samples into four pieces using a sharp razor blade. The
pieces of material were put back together until visual contact and
were placed between two glass slides. The initial cut width and area
was recorded under an optical microscope. During the healing
procedure, the samples were visually inspected at various intervals
in order to measure the evolution of the cut width and area for the
healing efciency quantication.
Bending and compressive loading can also be used to provide
insight on the healing efciency and the structural integrity
restoration recovery. Wu et al. [77] used for the healing perfor-
mance evaluation of a self-healing carbon ber/epoxy composite
system (Fig. 14), the stiffness recovery ratio (SRR%) dened as:
healed flexural stiffness
SRR % ;
Initial flexural stiffness
The SSR was derived from rectangular shaped specimens under
3 point bending testing according to the ASTM D 790 [78] standard.
In addition load-deection curves are used in order to evaluate the
core shell nano-bers effect on the mechanical properties of the
laminates. Li et al. [79] adopt the 3 point bending xture with single
edge notched beam (SENB) specimens, that are described in the
ASTM D 5045 [80] standard, to evaluate the healing behavior of a
modied DGEBA epoxy resin. Healing is presented as a function of
load recovery for the modied and unmodied resins.
The SENB specimen geometry is also used by Meure et al. [81].
The healing efciency is determined by comparing fracture
toughness KIC values of fractured specimens after healing with
those of pre-fractured specimens. The primary advantage of using
the fracture toughness values for healing performance evaluation is
that it yields a quantitative measure of healing efciency that is tied
to the recovery of an inherent material property. However, the
calculations of KIC with the SENB geometry require accurate
knowledge of the initial crack length and the crack length after
healing.
The tapered double cantilever beam (TDCB) specimen geometry
can be used in order to overcome the crack length measurement
difculty mentioned for the SENB specimen geometry [24]. The
primary feature of this geometry is that it exhibits a linear rela-
tionship between critical load P and fracture toughness KIC inde-
pendent of crack length (Fig. 15). In addition, the short groove of the
geometry requires small amounts of self-healing material and the
crack initiates and propagates in a more controlled manner. In
addition, if it is required, the test can be stopped in a desired crack
length. A detailed comparison between the SENB and TDCB ge-
ometries is presented in the works of Brown [82]. The TDCB spec-
imens are widely used in self-healing applications for healing
performance evaluation either by comparing KIC values [59] or
critical peak loads values [83,84].
The TDCB specimens can also be used in fatigue loading sce-
narios like in the work of Neuser and Michaud [85]. In their work,
epoxy TDCB specimens with microcapsules and shape memory
alloy wires were subjected to tensionetension fatigue and tension
testing. Fatigue testing was conducted in order to compare the
behavior of pure epoxy, epoxy with microcapsules, and epoxy with
SMA wires while tension testing provided the virgin and healed
peak load data for the healing efciency evaluation.
However, a major disadvantage of the TDCB geometry is that the
fracture behavior of the specimens, show an important dispersion
and unstable fracture behavior that must be taken into account to
obtain accurate results [86].
102 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119

Fig. 13. Adhesion recovery as function of the healing temperature and cross-linker type at 65
C using (a) 4-SH or (b) 3-SH [73].
Reprinted from Lafont U, van Zeijl H, van der Zwaag S. Inuence of cross-linkers on the cohesive and adhesive self-healing ability of polysulde-based thermosets. ACS applied
materials & interfaces. 4(11):6280e8. Copyright (2012) American Chemical Society.

Fig. 14. (a) Three-point bending test set up, (b) three-point bending specimens [77].
Reprinted from Wu X-F, Rahman A, Zhou Z, Pelot DD, Sinha-Ray S, Chen B, et al. Electrospinning Core-Shell Nanobers for Interfacial Toughening and Self-Healing of Carbon-Fiber/
Epoxy Composites. Journal of Applied Polymer Science. Copyright (2012), Wiley Periodicals. Inc.

An alternative geometry to the TDCB geometry is the width- WTDCB geometry under quasi static fracture and fatigue testing.
tapered double cantilever beam (WTDCB) (Fig. 16). The WTDCB Specimens of steel adherents bonded with self-healing epoxy ad-
provides a crack length independent measurement of mode I hesive were prepared and tested on a universal testing machine
fracture toughness like the TDCB geometry. Jin et al. [27] uses the under quasi static loading and cyclic loading conditions. The

Fig. 15. TDCB specimen geometry and dimensions in mm [86].

mez D, Gilabert FA, Tsangouri E, Van Hemelrijck D, Hillewaere XKD, Du Prez FE, et al. In-depth
Reprinted from International Journal of Solids and Structures, Vol. 64e65, Garoz Go
numerical analysis of the TDCB specimen for characterization of self-healing polymers. pp. 145e54, Copyright (2015), with permission from Elsevier.
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Fig. 16. (a) Geometry of WTDCB specimen consisting of adhesively bonded A36 steel
adherents. (b) Optical microscopy of cross section of a self-healing adhesive incorpo-
rated with Grubbs' catalyst and DCPD microcapsules [27].
Reprinted from Polymer, Vol. 52(7), Jin H, Miller GM, Sottos NR, White SR. Fracture and
fatigue response of a self-healing epoxy adhesive. pp. 1628e34, Copyright (2011), with
permission from Elsevier.
healing efciency is assessed by the ratio of the healed fracture
toughness to the virgin fracture toughness while the fatigue per-
formance of the self-healing adhesive was investigated under cyclic
loading.
Another specimen geometry that can be used for fracture
toughness calculations in the form of opening mode I interlaminar
fracture toughness GIC [87,88], is the double cantilever beam (DCB)
[89] as described in ASTM 5528 [90] standard for ber reinforced
composite materials and depicted in Fig. 17. It is widely used in self-
healing vascularized materials research because it has the advan-
tage that the test can be stopped at any prescribed crack length
[91]. However, mode I critical strain energy release rate calculations
require that applied load, crack opening displacement and crack
length values are recorded [92]. The accurate crack length mea-
surement is a disadvantage like in the SENB geometry. DCB speci-
mens can be tested under different testing geometries and loading
scenarios like mode II end loaded split (ELS) [43] as seen in Fig. 18 or
end notched exure under three point bending (Fig. 19) [34,93,94]
Fig. 17. Schematic showing the interplay locations of the EMAA bers and the
delamination fracture plane in the carbon bereepoxy laminates [92].
Reprinted from Composites Part A: Applied Science and Manufacturing, Vol. 43(8),
Pingkarawat K, Wang CH, Varley RJ, Mouritz AP. Self-healing of delamination cracks in
mendable epoxy matrix laminates using poly[ethylene-co-(methacrylic acid)] ther-
moplastic. pp. 1301e7, Copyright (2012), with permission from Elsevier.
103
providing information for mode II strain release energy rate GII
calculations.
The double cleavage drilled compression (DCDC) specimen or
open hole specimen (OHS) under compressive load is selected from
Hamilton et al. [95]. They study vascular epoxy specimens in order
to evaluate the healing performance of pumping protocols as
manifested by the recovery of fracture toughness after each healing
cycle. The DCDC geometry is more appropriate for studying the
fracture toughness of brittle materials like the epoxy matrices and
their ber reinforced composites. Under a uniform axial compres-
sion load, the Poison effect produces a tensile stress concentrated
around the central hole which induces the initiation of two sym-
metric mode I cracks at each crown of the hole propagating along
the mid-plane of the sample.
3.2.2. Impact damage
Impact damage is more difcult to describe compared to static
and fatigue damage. The impact damage is a dynamic response of
the impacted material, the impacting material, as well as the sup-
porting jig. Impact events in ber reinforced composites can cause
signicant reduction in mechanical performance whilst leaving
little visual evidence of the impact event. Self-healing of impact
damage in ber-reinforced composites is regarded as one of the
most difcult areas of ongoing research because of the large
damage volume and multiple failure modes. In such cases the
testing procedures involve secondary testing for determining the
mechanical properties after the impact event like compression af-
ter impact (CAI) testing [96] and/or non-destructive techniques,
like ultrasonic C-scan, in order to assess the damage and the
healing process as well.
The impact event can be generated with different testing
apparatus like impact drop tower devices on e-glass/epoxy samples
(Fig. 21) [97] or glass ber composites with microcapsules [98],
falling weight impact test machine [99] or ballistic pendulum set-
up on ionomeric polymers [100] covering a wide range of impact
energies and projectile velocities [67,98]. These types of tests can
provide data for peak load, energy to maximum load and absorbed
energy which can be used for the healing performance evaluation
(Fig. 20). The impact testing apparatus and procedure are described
in standards like ASTM D 7136 [101] while CAI testing can be found
in ASTM D 7137 [102].
Norris et al. [96,79] employ the previous mentioned standards
(D 7136, D 7137), in order to investigate the impact behavior of a
vasculature design in a ber reinforced composites and the post
healing compressive strength of the proposed system is used for
the healing performance evaluation. Ultrasonic C-scanning pro-
vided information on the delamination location and helped to
assess the different proposed vascular networks.
Haase et al. [100] investigates the behavior of a self-healing
ionomer under dynamic puncture testing. An impactor with a
similar shape to the ballistic impact tests projectiles is pushed
through a self-healing polymer sheet at a constant speed. The main
focus of this research is the temperature rise caused by the
impactor which was recorded by three thermocouples embedded
in the polymer sheet.
3.3. Corrosion resistance and protection
Most metals in natural environments exist in their oxidized
form, which means that metals tend to corrode, leading to loss of
mechanical and esthetic properties. The easiest way to protect
metals from undesired corrosion is to apply protective coatings that
offer active protection, passive protection, or both. The failure of the
protective layer leads unavoidably to corrosion of the underlying
metal. The self-restoration of this protective coating is a typical self-
104 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Fig. 18. Mode II ELS specimen geometry [43].
Reprinted from Composites Science and Technology, Vol. 71(6), Norris CJ, Bond IP, Trask RS. Interactions between propagating cracks and bioinspired self-healing vascules
embedded in glass ber reinforced composites. pp. 847e53, Copyright (2011), with permission from Elsevier.
healing functionality. In order to explore if a system shows self-
healing functionalities the creation of an articial defect in the
coating system, and evaluation of the ability of the system to sup-
press or decrease corrosion to desired levels and restore the pro-
tective functionality has been broadly used. A detailed review
regarding the employed self-healing corrosion protection meth-
odologies can be found in Ref. [103].
One of the most used techniques in corrosion science to
monitor local corrosion damage is the Electrochemical Imped-
ance Spectroscopy (EIS) via bod plots (Fig. 22) [104e106]. In or-
der to access the charge transfer resistance or polarization
resistance that is proportional to the corrosion rate at the
monitored interface, EIS results have to be interpreted with the
help of a model of the interface. An important advantage of EIS
over other laboratory techniques is the possibility of using very
small amplitude signals without signicantly disturbing the
properties being measured. To make an EIS measurement, a small
amplitude signal is applied to a specimen over a range of fre-
quencies. The EIS instrument records the real (resistance) and
imaginary (capacitance) components of the impedance response
of the system. Depending upon the shape of the EIS spectrum, a
circuit model or circuit description code and initial circuit pa-
rameters are assumed and input by the operator. EIS can provide
quantitative information about the electrochemical state of a
coating. The EIS set up is used by Garcia et al. [29] in order to
assess the healing performance of their proposed self-healing
anticorrosive organic coating. Scanning Vibrating Electrode
Technique (SVET) is also employed in order to provide further
verication on the EIS results.
Corrosion activity maps can be obtained by using the SVE
Technique [107]. SVET uses a single wire to measure the voltage
drop in a solution. This voltage drop is a result of local current at
the surface of a sample. Measuring this voltage in the solution,
Fig. 19. End notched exure specimen geometry as adopted by Ref. [94].
Reprinted from International Journal of Solids and Structures, Vol. 46(13), Ouyang Z, Li
G. Nonlinear interface shear fracture of end notched exure specimens. pp. 2659e68,
Copyright (2009), with permission from Elsevier.
the current at the sample surface is mapped. Current can be
naturally occurring from a corrosion or biological process, or the
current can be externally controlled using a galvanostat. A key
application of SVET is to study corrosion process of bare or
coated metals. Hollamby et al. [30] employ SVET in order to
evaluate the anticorrosive and self-healing behavior of their
proposed hybrid polyester coating. Control and coated specimens
were scratched and immersed in NaClaq solution and the current
density maps from SVET measurements were charted as seen in
Fig. 23.
Vimalanandan et al. [108] employed the Scanning-Kelvin-Probe
(SKP) technique in order to investigate the self-healing perfor-
mance and the corrosion-driven catholic delamination progress of
a conductive polymer (CP) based nano-capsule system. SKP is a
scanning probe method where the potential offset between a probe
tip and a surface can be measured using the same principle as a
macroscopic Kelvin probe (Fig. 24).
For the SKP measurements, a scratch was introduced to the
CP-coating, this defect was then covered with KCl and introduced
to the SKP chamber. The behavior of the corrosion potential and
the progress of the delamination were studied. The corrosion
potential in the electrolyte defect was monitored by positioning
the SKP tip close to the electrolyte drop serving as a reference
electrode. The cathodic delamination progress was monitored by
scanning the coatings from the defects to reect the potential
Fig. 20. Energy vs. time curves for microcapsules contained glass ber reinforced
composites [98].
Reprinted from Chowdhury RA, Hosur MV, Nuruddin M, Tcherbi-Narteh A, Kumar A,
Boddu V, et al. Self-healing epoxy composites: preparation, characterization and
healing performance. Journal of Materials Research and Technology. 2015;4(1):33e43.
Copyright (2015), with permission from Elsevier.
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Fig. 21. Target mounting in the impact chamber [97].
Reprinted from Advances in Space Research, Vol. 51(5), Francesconi A, Giacomuzzo C,
Grande AM, Mudric T, Zaccariotto M, Etemadi E, et al. Comparison of self-healing
ionomer to aluminum-alloy bumpers for protecting spacecraft equipment from
space debris impacts. pp. 930e40, Copyright (2013), with permission from Elsevier.
distribution as a function of the distance from the defect and
time.
Scanning Electrochemical Microscopy (SECM), can provide in-
formation about the redox activity, redox mode and topography,
feedback mode of liquid/gas, liquid/solid and liquid/liquid in-
terfaces. SECM measurements can be used in order to yield topo-
graphic information and to probe the surface reactivity of solid-
Fig. 22. (a, b) Bode plot and phase angle, (c) of specimens coated with nanocapsules loaded with various types of corrosion inhibitors [106].
Reprinted from Progress in Organic Coatings, Vol. 76(10), Choi H, Kim KY, Park JM. Encapsulation of aliphatic amines into nanoparticles for self-healing corrosion protection of steel
sheets. pp. 1316e24, Copyright (2013), with permission from Elsevier.
105
state and electro-catalyst materials. The long term anticorrosive
efciency of a damaged epoxy coating containing silyl-ester mi-
crocapsules on an aluminum substrate is studied via SECM testing
in the works of Gonzalez-Garcia et al. [28]. Combining redox and
feedback modes, the long term healing of the coating was
demonstrated (Fig. 25).
3.4. Electrical conductivity
The self-healing concept has also been implemented and ach-
ieved for materials with electrical functionality. Such materials are
able to recover conduction paths at different scales and most in-
vestigations of conductivity recovery in the literature deal with the
healing of such conductive paths.
A qualitative way to monitor the recovery of conductivity in
self-healing materials can be found in the works of Palleau et al.
[109]. Here a simple electronic circuit consisting of a LED, a voltage
source and a self-healing stretchable (SHS) wire in series is
monitored and captured in video (Fig. 26). The SHS wires are a
combination of a self-healing polymer structured with micro-
channels lled with EGaIn. Scissors are used to cut the wire so
that the circuit continuity is lost. When the wires are aligned, the
liquid metal components merge together forming a continuous
and conductive wire.
For studies where a very small change in resistivity is to be
monitored, a Wheatstone bridge set-up is preferred. This technique
measures an unknown resistance by using an electrical circuit. The
106 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119

Fig. 23. (A) SVET current density map and (inset) visual appearance of the scratched control sample. (B) SVET current density map and (inset) appearance of the scratched NPs_BTA-
a sample [30].
Reprinted from Hollamby MJ, Fix D, Donch I, Borisova D, Mohwald H, Shchukin D. Hybrid polyester coating incorporating functionalized mesoporous carriers for the holistic
protection of steel surfaces. Advanced materials. 23(11):1361e5, Copyright (2011) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

set up consists of an electrical source with a known voltage, three
resistors with known values, and a galvanometer. In self-healing
studies, the Wheatstone bridge set up allows monitoring of both
the creation and the healing of damage since when the damage
occurs the system's resistivity will increase [110].
Blaiszik et al. [111] employ the Wheatstone bridge set up in
order to in situ monitor a four point bending test conducted on
specimens of microencapsulated metal dispersed in a dielectric
material. The specimen acts as one resistor on the Wheatstone
bridge circuit. The circuit is monitored throughout the four-point
bend test using a Wheatstone bridge with the specimen as one
bridge arm. The performance of the circuit is evaluated by
measuring the normalized bridge voltage:
Vnorm Vh  V =Vo  V ;
where Vo is the bridge voltage before damage, V is the bridge
voltage measured for a fully broken circuit, and Vh is the instan-
taneous bridge voltage of the circuit. The value of Vnorm ranges
from zero for a specimen with no electrical conductance to one for

Fig. 24. (A) Scheme depicting the model-coating system and the experimental set-up used to evaluate the self-healing performance of the coating system. (B) Corrosion potential
monitored by SKP in the defect. (C) Delamination proles recorded by SKP [108].
Reprinted from Vimalanandan A, Lv LP, Tran TH, Landfester K, Crespy D, Rohwerder M. Redox-responsive self-healing for corrosion protection. Advanced materials. 25(48):6980e4,
Copyright (2013) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119 107

Fig. 25. (a) Optical micrograph of AA2024-T3 sample with bare and silyl-treated surface. (b) SECM image of the transition area on (a) using the electroreduction of oxygen. (c)
Approaching-curves performed on the bare metal (black line) and on the silyl-covered area (red line). (d) Overlapped approaching-curves corresponding to measurements using
electrochemical mediator (red-dashed line) and oxygen reduction (black-solid line) [28]. (For interpretation of the references to color in this gure legend, the reader is referred to
the web version of this article.)
Reprinted from Electrochemistry Communications, Vol. 13(10), Gonza
lez-Garca Y, Garca SJ, Hughes AE, Mol JMC. A combined redox-competition and negative-feedback SECM
study of self-healing anticorrosive coatings. pp. 1094e7, Copyright (2011), with permission from Elsevier.

a fully conductive specimen. The efciency of conductivity
restoration, hc, is dened for each specimen as Vnorm after fracture
(Fig. 27).
Another interesting approach where mechanical and electrical
properties are simultaneously recorded and analyzed can be
found in the works of Bailey et al. [112]. Here apart from the EIS
technique, the authors employ an in-situ electro-tensile tech-
nique in order to assess the degree of mechanical and electrical
self-healing efciency of a composite coating. This technique
involves the controlled introduction of a crack by pulling the
coating in tension while measuring the changes in electrical
conductivity on-line. Complementing the EIS results, it was
demonstrated that when microcapsules possessing an EPA:ECNT
(ethyl phenylacetate: epoxy with carbon nano-tubes) core were
incorporated into the coating, electrical conductivity and me-
chanical properties were restored to 64% (23) and 81% (39)
respectively (Fig. 28). Furthermore, sequential cracking and
healing events were noticed while the coating was pulled in
tension and both EIS and in situ tensile loading and electrical
conductivity test revealed a 24 h restoration of this coating
analogous to pure ECNT.
4. Characterization of self-healing systems and monitoring of
their healing efciency
Next to the technical challenge of realizing a self-healing sys-
tem, there is an inevitable need both for characterizing the func-
tional components that constitute it and monitor the whole process
of self-healing. A variety of characterization techniques can be
found in the literature. However, the methods for monitoring the
self-healing process are limited.
More specically, in the area of characterization the most
common techniques are Fourier Transform Infrared Spectroscopy
(FTIR), Nuclear Magnetic Resonance Spectroscopy, Optical and
Scanning Electron Microscopy (OM and SEM), Transmission elec-
tron microscopy (TEM), Atomic Force Microscopy (AFM), X-ray
108 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Fig. 26. a) Schematics illustrating the disconnection and reconnection of a simple electronic circuit using a self-healing wire. b) Variation of the resistance of SHS wires during
connection/disconnection/reconnection experiments [109].
Reprinted from Palleau E, Reece S, Desai SC, Smith ME, Dickey MD. Self-healing stretchable wires for recongurable circuit wiring and 3D microuidics. Advanced materials.
25(11):1589e92, Copyright (2013) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
diffraction analysis and rheological studies. In the eld of moni-
toring, the reported techniques include Raman spectroscopy,
acoustic emission and ultrasonics.
The following section presents an overview of the research
conducted by several groups, with specic examples for each
technique.
4.1. Characterization techniques
4.1.1. Fourier transform infrared spectroscopy (FTIR)
FTIR is a well-established technique based on molecular in-
teractions. In the eld of self-healing materials, this technique is
by far the mostly employed methodology in order to conrm
the healing functionality, compare the virgin and healed mate-
rials, as well as to monitor the process of self-healing reactions.
It has been employed both for the characterization of micro-
capsules [26,39,113e115] and intrinsic self-healing systems
based on DielseAlder cycloadditions [11,116e118]. FTIR has also
been used in other self-healing systems such as self-healing
gels [118], intrinsic reversible crosslinked networks healed via
photocyclization or on disulde links [119], mendable epoxy
networks and 3D braided composites with vascular channels, or
polyurethane/graphene self-healable nanocomposites [120].
An interesting example of the use of FTIR can be found in the
work of Araya-Hermosilla et al. [7] who presented a novel revers-
ible thermoset with tunable Tg based on chemical modication of
aliphatic polyketones and furan and/or amine groups. In this ma-
terial system they monitored the cycloaddition through the spec-
tral band of CeO stretching around 1000e1300 cm1. As the molar
ratio between furan and maleimide groups increased, the intensity
of the band centered around 1180 cm1 (corresponding to CeOeC
ether peak) also increased, thus testifying the occurrence of the
DielseAlder reaction.
In another case concerning anti-corrosive self-healing organic
coatings Szabo
et al. [121] investigated the application of linseed oil
e a lm former healing material e and octadecylamine (ODA) e a
corrosion inhibitor in the core of microcapsules which were added
in a self-healing paint using FTIR. Moreover, they tried to specify
the inuence of Co-octoate, used as a drier in order to reduce so-
lidication time and thus improve the self-healing ability of the
paint. They found out that seven days were needed by the linseed
oil lm in order to dry completely and additionally that this amount
of time decreased to several hours with the addition of Co-octoate.
Regarding the self-healing functionality they encountered some
difculties with the addition of ODA which weakened the healing
process. This difculties were overcame by increasing the Co-
octoate concentration.
In another encapsulation attempt, Garcia et al. [29], utilized FTIR
in order to conrm the hydrolysis of a water reactive silyl ester
which had been encapsulated in a self-healing anticorrosive organic
coating. Through the use of FTIR and contact angle measurements
they showed that this silyl ester, after its hydrolysis, had the ability
to completely coat a metallic surface and form a hydrophobic pro-
tective layer, which actually became denser with time.
Yuan et al. [122] produced a self-healing system based on
cyanate ester resins (CE) with the addition of low molecular weight
poly(phenylene oxide) resins (PPO). This CE/PPO system was
studied via FTIR in order to quantitatively estimate the extent of
conversion, a, of the cyanate ester groups (eOCN) and the amount,
x, of unreacted eOCN groups according to the FTIR spectra of un-
cured and cured CE resin/PPO resin, as is shown in Fig. 29. They
used as a reference peak the vibration band of the phenyl ring at
1510 cm1 and chose the vibration bands of eOCN at 2280/
2238 cm1 to calculate x and a. Moreover, they attributed the
improved exural strength of CE/PPO systems to the higher con-
version (a) of eOCN detected by FTIR spectroscopy.
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
4.1.2. Near-infrared spectroscopy (NIR)
Near infrared spectroscopy has been utilized by Varley et al. [56]
as a convenient technique to compare the concentration of
different functional groups and determine whether there was any
impact on a mendable epoxy network as a result of thermoplastic
addition, which may affect the healing process.
Using this technique the aforementioned group demonstrated
that the modication of their mendable epoxy system, with different
healing agents, had a negligible impact upon the network formation,
or, the chemistry of polymerization after curing had occurred. This
was assumed as NIR did not reveal any changes neither between the
spectra of the unmodied and the modied material, nor between
the spectra acquired before and after healing of the modied epoxies.
In conclusion, they conrmed that healing was more likely via
physical processes namely diffusion through free volume and repu-
tation across a crack plane during thermal activation.
4.1.3. Nuclear magnetic resonance spectroscopy (NMR)
This experimental technique is typically used in order to exploit
the magnetic properties of certain atomic nuclei. Relying on the
phenomenon of nuclear magnetic resonance it can provide detailed
information about the structure, dynamics, reaction state and
chemical environment of the molecules.
In the case of self-healing materials numerous studies have used
NMR in order to identify interactions between atoms and to
conrm the formation of self-healing systems through various
chemical reactions. These studies include not only intrinsic chem-
istries such as the nano-composite self-healing gel produced by
Fig. 27. Evolution of the normalized bridge voltage and force during four-point bend tests of a self-healing specimen (a) and a control specimen (b). (c) The percentage of samples
where healing was observed [111].
Reprinted from Blaiszik BJ, Kramer SL, Grady ME, McIlroy DA, Moore JS, Sottos NR, et al. Autonomic restoration of electrical conductivity. Advanced materials. 24(3):398e401,
Copyright (2012) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
109
Sharma [118] et al., the supramolecular self-healing gels exhibited
by Zhang et al. [123].
An example of NMR utilization in microcapsule based self-
healing systems is the work of Zhu et al. [40] who, through the
use of NMR, conrmed that capsule rapture led to polymerization
achievement, thus conrming that the produced multilayered
capsules enclosed the monomer needed for self-healing reaction to
occur.
Furthermore, Kakuta et al. [15] employed NMR to trace a reason
why the formation of inclusion complexes plays such an important
role in the formation of their supramolecular preorganized
hydrogel system. This system was based on non-covalent hoste-
guest interactions between polymers and was produced by radical
copolymerization of monomers of a complex of a cyclodextrin (CD)
host and aliphatic guest in aqueous solution. The group of Kakuta
showed that the inclusion complexes undergo a dissolving effect
between the CD and guest monomers causing homogeneous
radical copolymerization which results to the production of a su-
pramolecular self-healing hydrogel system.
Jinhui et al. [124] also, used NMR in order to conrm the suc-
cessful modication of a commercial epoxy resin with furan groups
as well as the occurrence of the self-healing DielseAlder reaction
between the modied epoxy and bismaleimide.
4.1.4. Optical microscopy (OM), scanning electron microscopy
(SEM) and transmission electron microscopy (TEM)
Microscopy is widely used to conrm the self-healing compo-
nents and structures, after the production step, optical microscopy
110 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119

Fig. 28. Stress and normalized electrical resistance of an ECNT coating (a) without capsules, with (b) hexyl acetate capsules, (c) EPA:EPON microcapsules, and (d) EPA:ECNT [112].
Reprinted with permission from Bailey BM, Leterrier Y, Garcia SJ, van der Zwaag S, Michaud V. Electrically conductive self-healing polymer composite coatings. Progress in Organic
Coatings. 2015;85:189e98, Copyright (2015), with permission from Elsevier.

(OM), scanning electron microscopy (SEM) or transmittance elec-

Fig. 29. Fourier transform infrared spectra of poly(phenylene oxide) (PPO) and the
uncured and cured cyanate ester (CE)/poly(phenylene oxide) systems [122].
Reprinted from Yuan L, Huang S, Hu Y, Zhang Y, Gu A, Liang G, et al. Poly(phenylene
oxide) modied cyanate resin for self-healing. Polymers for Advanced Technologies.
Copyright (2014) John Wiley & Sons Ltd.
tron microscopy (TEM) are employed depending on the size of the
studied morphology.
Numerous researchers employed SEM to study various features
including epoxy/hardener containing microcapsules [23,33], frac-
ture surfaces of microcapsules [114], mendable epoxy resins [125],
unhealed and healed CFRPs [126], polyurethane/graphene self-
healing nanocomposites [95], solvent-lled microcapsules incor-
porated into a polyurethane layer which is deposited atop a silver
ink line for restoring electrical conductivity of the ink [88], shape
memory polymers [104] as well as healing agent containing micro/
nanocapsules embedded in anticorrosive coatings [105].
A very interesting analytical study using SEM in order to view a
three-dimensional image of both the inner and outer surface and
morphology of various capsules ranging from several tens of mi-
crons to below 100 nm in size, has been published by Hodoroaba
et al. [127]. In this study SEM was used in the Transmission Mode
and the samples were prepared on thin supporting foils (on TEM
grids). Fig. 30 shows SEM micrographs with corresponding EDX
analyses presented in their study.
Li et al. [128] produced a cement based system containing self-
healing microcapsules. Then, they studied those microcapsules
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119 111

composed of diglycidyl ether of bisphenol A epoxy resin as the core
material and polystyreneedivinylbenzene as the shell material and
the fracture surfaces of them via OM and SEM. SEM was also
employed by the group of Jinhui et al. [124] in order to assess the
self-healing process of the produced self-healing epoxy system.
TEM is mostly used in self-healing systems which incorporate
carbon allotrope nanoinclusions as well as in some capsule based
self-healing systems with sub-micron sized capsules.
Specically, TEM was used in a study published by Leterrier et al.
[112] who synthesized an electrically conductive partially cured
epoxy coating incorporating a microcapsule based healing mech-
anism. The microcapsules contained a mixture of ethyl phenyl-
acetate and a nanoreinforced epoxy resin, the matrix was also
reinforced with nanoinclusions. TEM facilitated to the visualization
of the carbon nanotube distributions into the core of the
microcapsules.
4.1.5. AFM (Atomic Force Microscopy)
Atomic force microscopy is generally utilized in self-healing
systems in order to assess their healing performance in terms of
temperature, time and local mobility of the atoms of the studied
materials.
Brancart et al. [8] performed an extensive study in order to
assess self-healing coatings based on reversible polymer networks
using AFM. They studied the self-healing ability of the coatings
through the healing of well-dened and reproducible nanosized
scratches and other defects applied by nanolithography.
The group of Dikic [129] produced a self-replenishing hydro-
phobic coating based on peruoroalkyl dangling chains covalently
bonded to a cross-linked polymer network through a polymeric
spacer. They used AFM to assess the self-replenishing process by
comparing the uorine end groups concentration at the virgin and
healed specimen. The decrease in the Force Displacement mean
value measured by AFM depicting an increase in uorine content in
the healed materials showed that the prerequisite for replenishing
is the mobility of the species within the coating network. This
mobility was triggered by annealing.
In a another study, Faghihnejad et al. [130] employed AFM to
characterize self-healing lms with multiple hydrogen bonding
groups with respect to changes in the Relative Humidity (RH) of the
lms. During this contact mechanic testing they observed a tran-
sition from elastic to viscous failure. Characteristic proles are
presented in Fig. 31.
4.1.6. X-ray diffraction analysis
X-ray diffraction as a technique can be utilized in order to
identify certain interactions between molecules and stacking in-
teractions exhibited as a diffraction pattern. Roy et al. [131] pro-
duced an amino-acid-based (11-(4-(pyrene-1-yl)butanamido)
undecanoic acid) self-repairing hydrogel which contained carbon
nanoparticles (graphene and single wall carbon nanotubes) for the
incorporation of semiconducting behavior. X-ray diffraction anal-
ysis was used in order to evaluate the bonding interactions of the
produced hydrogel. The conclusions of their study declared that the
gelator molecules being used in their system are self-assembled
through hydrogen-bonding interactions between the amide moi-
eties and pep stacking interactions. They, also, recognized the
presence of pep stacking interactions of the pyrene p planes of the
hydrogelator molecules with the p planes of the graphene, as well
as the p walls of the Pr-SWCNTs, in the hybrid gel state.
4.1.7. X-ray photoemission spectroscopy (XPS)
XPS is a surface-sensitive quantitative spectroscopic technique
that measures the elemental composition at the parts per thousand

Fig. 30. Upper (a) and in-transmission (b) SEM observation of SiO2 submicrocapsules prepared on lacey carbon foil on TEM grids. (c) EDX analysis conrming compositional
differences of the two particles [127].
Reprinted from Hodoroaba VD, Akcakayiran D, Grigoriev DO, Shchukin DG. Characterization of micro- and nanocapsules for self-healing anti-corrosion coatings by high-resolution
SEM with coupled transmission mode and EDX. The Analyst. 2014;139(8):2004e10. Published by The Royal Society of Chemistry.
112 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119

Fig. 31. Typical topographical AFM images of surface patterns associated with the detachment of two self-healing lms (thickness ~100 nm) from adhesive contact in contact
mechanics tests: a) more viscous state, bed) more elastic state, T 40
C [130].
Reprinted from Faghihnejad A, Feldman KE, Yu J, Tirrell MV, Israelachvili JN, Hawker CJ, et al. Adhesion and Surface Interactions of a Self-Healing Polymer with Multiple Hydrogen-
Bonding Groups. Advanced Functional Materials. 24(16):2322e33, Copyright (2014) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

range, chemical state and electronic state of the elements that exist
within a material.
Nowak et al. [104] prepared a self-healing polymer coating
which contained the organic corrosion inhibitors encapsulated
inside the polyelectrolyte nanocapsules. This coating was painted
onto the surface of AA2024 T3 alloy. They utilized XPS in order to
conrm the release of the inhibitor from a scratched coating and
thus the healing reaction of the produced coating. Fig. 32 shows
the acquired spectra from an unscratched surface, a dry scratched
surface and a wetted scratched surface of this self-healing organic
coating. The peak which appears at a binding energy of 163.5 eV
on the spectrum of the dry scratched surface was ascribed to the
inhibitor liberation from the destroyed capsules. The shift of this
peak to the lower value of 162.4 eV of binding energy in the
wetted sample conrms the formation of a sulfurealuminum
bond.
4.1.8. Rheometry, rheological studies and thixotropic behavior
Rheological measurements are being performed in self-healing
systems, mostly hydrogel systems, in order to determine the sol-
egel transition point of these systems and to measure the storage
(G0 ) and loss (G00 ) moduli as a function of temperature, in a certain
angular frequency, within a linear range of viscoelasticity. Some
research groups are also conducting measurements of the thixo-
tropic properties of their systems in order to evaluate the gel re-
covery time.
More specically, Sharma et al. [118] and Scheltjens et al. [117]
examined the linear viscoelastic properties to fully estimate the
thermo-mechanical behavior of their systems during healing.
They assessed which of their produced materials behaved
more like a solid behavior and which like a gel by measuring G0
and G00 in dependence with time. The solegel transition
temperature of their reversible covalent bonding self-healing
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Fig. 32. S 2p ionization spectra of a self-healing polymer coating with encapsulated
organic corrosion inhibitors. Unscratched coating (down), dry scratch (middle), wetted
scratch (top) [104].
Reprinted from Progress in Organic Coatings, Vol. 84, Kope
c M, Szczepanowicz K,
Mordarski G, Podgo
rna K, Socha RP, Nowak P, et al. Self-healing epoxy coatings loaded
with inhibitor-containing polyelectrolyte nanocapsules. pp. 97e106, Copyright (2015),
with permission from Elsevier.
polymer network in correspondence with equilibrium conditions
was determined.
Roy et al. [131] conducted a rheological study on an epoxy amine
based network modied with reversible bonds. This study which
conrmed the presence of a stable and stiff gel-phase material.
Interestingly, the stiffness of the native gel increased upon the
incorporation of Pr-SWCNTs (pristine single walled carbon nano-
tubes), RGO (reduced graphene oxide), and both Pr-SWCNTs and
RGO into the hybrid gel system. The study of the thixotropic
properties of the produced hydrogels revealed the gel-recovery
time was signicantly shortened from 7 min to 2.48 min,
3.25 min and 3 min by the incorporation of both SWCNTs and RGO,
and the individual inclusion of RGO and Pr-SWCNTs, respectively,
within the native gel. indicating fastest self-healing ability in the
case of the hybrid gel with RGO and Pr-SWCNTs, and the slowest
self-healing ability in the case of the native gel.
Another investigation of the rheological behavior of a self-
healing system is described in the work by Hao et al. [16]. This
attempt includes the determination of the sol gel transition point,
the G0 and G00 moduli as well as the recovery properties of a
thermal-responsive self-healing hydrogel based on hydrophobi-
cally modied chitosan and vesicle. They found that depending on
temperature and the consequent state of their material (solution,
viscoelastic gel etc.) there is a strong frequency dependence of G0
and G00 . Furthermore, the relaxation time, which reects the life
time of the cross-links, was further investigated, coming to the
conclusion that the behavior of their hydrogel was governed by the
interplay of the hydrophobic attractive interactions and the elec-
trostatic repulsive interactions, with the latter playing a negative
part. Fig. 33, depicts the relaxation times as a function of frequency
for various concentrations of 5-methyl salicylic (mS) acid at 25
C.
4.2. Monitoring techniques
4.2.1. Ultrasonics
Being a very effective non-destructive technique, ultrasonics
have been utilized by many researchers for self-healing process
monitoring. A study published by In et al. [132] employed diffused
113
ultrasound to monitor in situ the progression of self-healing of
cracks in concrete. Ultrasonics were employed to investigate fully
or partially fractured tensile tested specimens. Self-healing was
assessed via monitoring of distinct diffuse ultrasonic parameters
such as Arrival Time of Maximum Energy (ATME) and effective
ultrasonic diffusivity. The latter term refers to the ratio of the
amount of space per time that the ultrasound waves are able to
occupy during their diffusion by the scatterers included in a ma-
terial like cement. ATME has shown to be correlated with crack
width which in this system can represent the extent of healing. An
indicative diagram presenting their measurements is shown in
Fig. 34. A comparison of the measured crack width and diffusivity
over time is depicted in this diagram. The authors conclude by
stating an exponentialerecovery model which characterizes their
material and relates the measured diffusivity with the amount of
self-healing.
4.2.2. Acoustic emission
Acoustic emission is a non-destructive technique used in many
cases in order to detect damage evolution and propagation in
materials. In the case of self-healing materials, Coppola et al. [49]
utilized acoustic emission in order to assess the damage evolu-
tion in the vascular 3D woven glass/epoxy composites. In more
detail, they correlated the acoustic activity with strain data from
mechanical testing. Fig. 35 presents stress and acoustic emission
data in relation to the strain that the composites are subjected to.
They observed that, for all the specimens, tested acoustic events
initiated after a threshold strain was reached, denoted by AEi.
Moreover, acoustic activity initiated earlier for the vascular speci-
mens compared to the control ones (specimens without channels)
indicating earlier onset of damage. This early onset indicated that
other mechanisms were responsible for the reduction of strength in
the wave channel specimens (specimen in which the channels
follow a wave shape trajectory) although it did not directly corre-
late to reduced strength.
4.2.3. Raman spectroscopy
Raman spectroscopy is a valuable characterization tool which
has been utilized in different ways in order to evaluate the pro-
duced structures and assess the healing performance of self-heal-
ing systems. A short presentation of the several attempts of
different working groups during the most recent years can be found
in the next paragraphs.
In a review article by Zedler et al. [133], four different aspects
related to the use of resonance Raman spectroscopy in the study of
self-healing materials are presented. The rst aspect is concerned
with resonance Raman investigation of self-healing biopolymers
living in marine habitats. These biopolymers are presented as
model damage tolerant and self-repairing structures, in the work of
Holten-Andersen et al. [134].
Other aspects presented in the aforementioned review, concern
the use of traditional Raman spectroscopy for the investigation of
the role of protein conformational changes in the self-healing
behavior of the whelks egg capsules (WEC), along with some ex-
amples of monitoring temporally- and spatially-resolved changes
in the local chemistry, as well as the stereospecicity of Ring
Opening Metathesis Polymerization (ROMP) self-healing reactions.
Furthermore, it covers examples of in situ Raman characterization
of the epoxy based polymerization products formed in the cracked
surface of microcapsule- and micro-vascular based self-healing
materials, as well as an investigation and conrmation of Diel-
seAlder (DA), retro-DielseAlder (rDA) self-healing reactions of
coatings based on a polymer modied with terpyridineemetal
complexations.
114 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119

Fig. 33. Dynamic rheological study. (a) Storage modulus (G0 ) and loss modulus (G00 ) as a function of frequency for 0.4 wt% solution of hm-chitosan with different concentration of
5 mS at 25
C. (b) Relaxation of the concentration of 5 mS at 25
C [16].
Reprinted from Colloid and Polymer Science, Vol. 291(7), 2013, pp. 1749e58, Thermal-responsive self-healing hydrogel based on hydrophobically modied chitosan and vesicle. Hao
X, Liu H, Xie Y, Fang C, Yang H., Figure 5, Original Caption: Dynamic rheological study. (a) Storage modulus G0 (lled symbols) and loss modulus G00 (open symbols) as a function of
frequency for 0.4 wt% solution of hm-chitosan with different concentration of 5 mS (DTAB 16 mM) at 25
C. (b) The relaxation time as a function of the concentration of 5 mS at
25
C, the DTAB concentration is 16 mM., Copyright Springer-Verlag Berlin Heidelberg 2013, with kind permission from Springer Science and Business Media.

Fig. 34. ATME and diffusivity plot with tension crack over exposure time for (a) 100% cement material, (b) 60% cement mass:35% slag:5% Metakaolin [132].
Reprinted from NDT & E International, Vol. 57, In C-W, Holland RB, Kim J-Y, Kurtis KE, Kahn LF, Jacobs LJ. Monitoring and evaluation of self-healing in concrete using diffuse ul-
trasound. pp. 36e44, Copyright (2013), with permission from Elsevier.
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Fig. 35. A sample plot of stress and cumulative acoustic emissions (AEcum) versus
strain. Locations used to record ultimate tensile stress (su), Young's modulus (E), and
strain at damage initiation (AEi) [49].
Reprinted from Composites Part A: Applied Science and Manufacturing, Vol. 59, Cop-
pola AM, Thakre PR, Sottos NR, White SR. Tensile properties and damage evolution in
vascular 3D woven glass/epoxy composites. pp. 9e17, Copyright (2014), with permis-
sion from Elsevier.
The group of Zhu et al. [40], who synthesized multilayered mi-
crocapsules in a production sequence of four steps, used Raman
spectroscopy for the characterization of the produced structures.
These multi-layered microcapsules are comprised of distinct layers
of glycidyl methacrylate (GMA) e loaded poly(melamine-formal-
dehyde) (PMF) microcapsules as the core, living PMMA as the
second layer, cuprous bromide/N,N,N0 ,N0 ,N00 -pentamethyldiethyl-
enetriamine catalyst system (CuBr/PMDETA) as the third layer and
a wax coat as the outer shell to protect the air sensitive Cu(I) in the
second layer.
The chemical structure of the microcapsules was veried via
Raman microscopy depth proling, depicted in Fig. 36. The prole
not only described the composition feature of the entire multilay-
ered microcapsule, but also facilitated for a rough measurement of
the thickness of each layer.
Patrick et al. [135] probed the chemical composition of the
healed fracture interfaces of their 3D vascular composites. They
Fig. 36. (a e left) Raman spectra of the substances used for composing the multilayered microcapsules. (b e right) Typical Raman spectra of a multilayered microcapsule z120 mm
in diameter collected at the scanning depths from top to bottom [40].
Reprinted from Polymer, Vol. 54(16), Zhu DY, Rong MZ, Zhang MQ. Preparation and characterization of multilayered microcapsule-like microreactor for self-healing polymers. pp.
4227e36. Copyright (2013), with permission from Elsevier.
115
produced two different architectures of vascularized composites,
namely an isolated-parallel and an interpenetrating-herring-
bone one. The epoxy system used was a diglycidyl ether of
bisphenol A (DGEBA) based epoxy resin (R) and aliphatic triethy-
lenetetramine (TETA) based hardener (H). Raman spectra at various
locations of the parallel conguration sample indicated the resin
and hardener rich regions corresponding to distinct stretching and
vibrating modes of different molecules, as well as a partially mixed
region. In addition, they conducted a series of ex situ, pre-mixed
Raman investigations, in order to construct a linear calibration
curve which assisted the quantication of the in-situ resin:-
hardener (R:H) mix proportions of the healed material based on the
ratio of phenyl to amide peak intensities. They acquired Raman
spectra from three different regions on the herringbone fracture
surface, which yielded calculated R:H ratios of roughly 3:1, 2:1 and
3:2, respectively. These values conrmed the ability of the inter-
penetrating vasculature of approximate intended uid delivery as
well as the ability of the selected healing chemistry to polymerize
under non-stoichiometric conditions, as can be seen in Fig. 37.
In the category of microcapsule self-healing materials Yuan et al.
[136] utilized Raman spectroscopy in order to acquire a live record
of the curing reaction of the released healing agent in their system
which comprised of glass fabric epoxy composites and epoxy/
mercaptan healing agent. Chipara et al. [137] used Raman spec-
troscopy in order to characterize a self-healing system containing
urea-formaldehyde microcapsules lled with dicyclopentadiene
(DCPD) and rst generation Grubbs' catalyst dispersed within
polyethylene oxide.
In another work, Ramachandran et al. [138] produced copol-
ymer lms that upon mechanical damage undergo color changes in
the damaged area, but upon exposure to sunlight, temperature and/
or acidic vapors, the damaged area is self-repaired, recovering the
initial colorless appearance. The aforementioned group used
Raman spectroscopy for monitoring the molecular repair processes
induced by visible light.
In the category of intrinsic photopolymerizable self-healing
materials Zhang et al. [61] used Raman spectroscopy in order to
estimate the appropriate time for photodimerization until equi-
librium would be reached in modied polyurethane network, in
which coumarin served as a photosensitive crosslinker. They veri-
ed the homogeneity of the photochemical reaction throughout
the entire polyurethane lm volume.
116 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
Fig. 37. In situ healing reaction characterization (single cycle, Da 70 mm) via uorescent images in combination with Raman spectroscopy [135].
Reprinted from Patrick JF, Hart KR, Krull BP, Diesendruck CE, Moore JS, White SR, et al. Continuous Self-Healing Life Cycle in Vascularized Structural Composites. Advanced materials.
Copyright (2014) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
In a very recent work, White et al. [139] produced a cross-linked
epoxy polymeric material which incorporated an imidazole poly-
merization initiator into the matrix volume. An aliphatic bond
formation shown as a peak at 1112 cm1 in the Raman spectrum of
the healed material compared to the original spectrum of the virgin
material conrmed the success of the healing process as well as the
proposed healing mechanism in the modied epoxy system.
5. Concluding remarks
A wide variety of novel chemistries regarding both extrinsic and
intrinsic self-healing approaches have been developed by the
research community over the last years. As has been shown, sig-
nicant effort has been made towards developing an ideal fully
autonomous intrinsic self-healing system capable of regaining its
initial properties rapidly at ambient temperature.
Reversible reactions and especially DielseAlder mechanism are
very promising for the synthesis of processible, remendable and
highly oriented polymers. This class of materials is capable of
regaining its initial properties at the molecular level, theoretically
for an innite number of repetitions without any further addition
of chemicals. However, only small volumes of damage can be
healed because material contact is required for healing, and cyclic
reactions reduce the healing efciency after repeated healing
cycles.
On the other hand, vascular self-healing materials are capable of
multiple healing of large damage volumes since the healing agent
can be repeatedly infused to the damaged area through the formed
networks. In this case, the challenge lies in the incorporation of a
microchannel network to a material. Signicant progress has been
made towards the integration of a vascular network that will not
affect the properties of the existing material through the optimi-
zation of the manufacturing process.
Apart from the decision for the selection of the self-healing
chemistry, the engineer or scientist needs to have an extensive
range of testing procedures in order to select the appropriate
one depending the application. Depending on the nal product,
stiffness, impact resistance, adhesion strength, electrical
conductivity, corrosion protection are of primary importance.
The novel healing material technologies target applications
in various sectors such as the aerospace, automotive, communi-
cations etc. However, a considerable impediment for their use is
the certication, particularly for aerospace afliated sectors.
The various specimen geometries or experimental congura-
tions range from the tapered double cantilever beam which is
widely applicable despite its fundamental disadvantages, to
typical Wheatstone bridge setups when electrical properties are
of interest. Self-healing corrosion resistant coatings can nd
excellent characterization procedures in electrochemical imped-
ance spectroscopy or cyclic potentiodynamic sweep in aggressive
environments. Moreover the available choices in experimental
 D.G. Bekas et al. / Composites Part B 87 (2016) 92e119
equipment and procedures enable the researcher to even
monitor the actual healing process gaining more insight on the
self-healing chemistry and engineering.
Characterization of self-healing materials through various
experimental techniques and evaluation of their self-healing ef-
ciency via monitoring of the occurring self-healing reactions is
naturally following the material production step. Microscopic
methods like OM, SEM and TEM serve the visualization of the
produced structures and are generally used before and after heal-
ing, thus conrming its success. These techniques are sometimes
combined with AFM when studying the local mobility of atoms and
generating topographical images of the virgin and healed materials.
Other characterization methods, including NMR, XRD and XPS, that
can study interactions in the atomic or molecular level, are also
being utilized in order to conrm successful healing.
A qualitative estimation of healing and conclusions about its
mechanism are also achieved through the use of NIR and FTIR with
the latter in some cases also leading to quantitative estimations of
healing efciency. Rheological studies are mostly being used in
modied systems, in which the modication accounts for the
healing functionality, in a comparative way as to the unmodied
ones. Monitoring of the various systems healing process can be
achieved via the utilization of ultrasonics, acoustic emission and
Raman spectroscopy with the former and the latter one being able
to estimate a quantitative value of the healing efciency.
Summarizing, self healing materials and related technologies
have substantially progressed in the recent years. However,
fundamental to their application is their integration in the
component design via the selection of the appropriate technology
while always taking in to account apart from the desired healing
functionality, production and certication issues.
Acknowledgments
This research has been co-nanced by the European Union
(European Social Fund e ESF) and Greek national funds through the
Operational Program Education and Lifelong Learning of the
National Strategic Reference Framework (NSRF) e Research Fund-
ing Program: THALES. Investing in knowledge society through the
European Social Fund. The authors also acknowledge the ACP3-
GA-20l3-6054l2-HIPOCRATES research programs for nancial
support.
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