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Chapter

Self-Healing Polymer Composites

for Structural Application
Jeetendra Kumar Banshiwal and Durgesh Nath Tripathi

Abstract

Self-healing materials are the next-generation materials for high-performance

structures. To reduce the fatigue and subsequent probability of failure along with
extended service life of polymer and polymer composites, the self-healing concept
has great potential. Today, polymeric composites are structural matrix and prone
to failure against cyclic mechanical and thermal loading. Significant degradation
of polymeric structures at surficial sites can be measured by barely visible impact
damage (BVID), but internal micro-cracks are not easily detectable. Various dam-
age modes make major damage sites in composites and further lead to catastrophic
failure of the structure. On-site repairing of microscopic or macroscopic damages
in polymer composites is a value-added function that is offered by self-healing
techniques. Different extrinsic methods including encapsulation, hollow fiber
embedment, and vascular methods are preferred, and some intrinsic, dynamic
bonding is created by reversible covalent networks and supramolecular interaction
based on H-bonding, metal-ligand, and ionomers. This chapter is preferred on the
new trends and challenges regarding the structural health monitoring of polymeric
composites against external mechanical and environmental impacts and extended
service life and performance by utilizing self-healing strategies.

Keywords: intrinsic and extrinsic self-healing, covalent reversible network,

supramolecular interactions

1. Introduction

Polymers and fiber-reinforced polymers (FRPs) are common as structural

materials due to lightweight, easy processability, and constancy against adverse
environmental impacts. However, mechanical properties are associated with many
variables including service time, operating temperature and pressure, molecular
weight, and constitution of matrix. The long-term durability, high performance
and reliability are major challenges for polymeric architecture. Limiting factors of
polymer composite is relatively poor performance under impact loading due to lack
of plastic deformation, which is a most prominent aspect of any vehicle component
design. Low-velocity and high-velocity impacts are the critical issues for FRPs. These
impacts influence on mechanical strength and stiffness along with dimensional
stability. In metals, the impact energy is dissipated through elastic and plastic
deformations, so structural integrity is retained intact. However, in FRPs the impact
energy is dissipated in the form of damages in matrix. The impact damages in FRPs
affect mainly the internal integrity as compared to superficial visible zone. On cyclic
mechanical and thermal loadings, stress is applied on a matrix which released in the

1
Functional Materials

form of micro-cracking. Micro-cracks degrade polymeric properties inevitably and

result into the failure. Single or multiple damage modes result into damage sites and
are required to repair the components to continue to the service. If microcracks are
untreated, they lead to larger macroscopic cracks, and finally catastrophic loss of the
structure is an adverse outcome. To resist these failures, the new-generation materi-
als having autonomic healing capability to damage repair are needed to develop.
Conventionally, different lay-up repair techniques are adopted in thermoset.
Similarly, in thermoplastics which are known for their mechanical perfor-
mances, service temperature, and solvent resistance, fusion bonding techniques are
used to recover mechanical integrity.
However, these repair strategies are very costly, time-consuming, followed by
complicated procedure, and assisted only by expert technicians. So, we required such
unique functionality which intimates the damages at nascent stage and sometimes
repaired the damages. Self-healing of cracks is an eminent and efficient possible solu-
tion of these issues. In healing systems, a damage incident triggers the internal pro-
cesses that generate the healing response which cured the damages. The bio-systems
have damage detection and subsequent prevention techniques; those are source of
innovation to design such functionality by introducing the self-healing functionality
into artificial materials. These techniques are demanding for manned materials and
structures and assisted by the biomimetic approaches. The major concern is focused
on recovery of mechanical properties of polymer composites against quasi-static
fracture. Initially, Mercier developed a self-healing rubber that can reseal on puncture
damage [1]. The concept of healing is progressed with developing efficient vehicles
and other systems such as space suits to protect from micrometeoroid impacts [2].
Currently, damage healing of polymer structure is being demonstrated via different
approaches, which include extrinsic and intrinsic methodologies. Extrinsic methodol-
ogy is being performed via encapsulation [3–8], hollow fibers [9–11], microvascular
systems [12–16] and intrinsic damage healing is offered by reversible covalent
bonding [17–21] and supramolecular interactions [22–30]. In extrinsic methodol-
ogy, healing is restricted only once, and the delivery of healing precursor’s amount
is limited. To overcome the above concern, different intrinsic healing systems are
developed that offer multiple healing at macroscopic damages. Multiple healing of
the same crack is achieved by microvascular 3D system, thermoreversible networks,
and supramolecular interaction. These strategies help to design various self-healing
systems. In literature, various high-performance systems such as self-healing coating,
self-healing ceramics, and self-healing metals are reported. Self-healing nanocom-
posites are also reported. Self-healing technology provides public safety and reduced
maintenance cost of the structure. Healing approaches offer longer lasting with fault-
tolerant components across various fields including coatings, electronics, robotics,
transportations, energy, etc. In the following section, the author is mainly focused to
elaborate current trends and the leading research field of remendable polymers for
structural composites.

2. The basic principle and theory of damage healing

Mimicking biosystems, in synthetic materials, damage repair is performed by

three steps including actuation of healing, later transport of healing precursors
to the damage site, and finally chemical repair process occurring with contact of
catalyst or curing species at an angstrom level in which matrix is restructured by
bonding of cleaved bonds at the damage site. Macroscopically, healing is proceeding
by two consecutive mechanics; these included physical and chemical process. In
physical process, the flow of healing precursors or segmental movement of chains is

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mandatory for damage repair. These events proceed continuously and are controlled
by kinetics and thermodynamics. The repair event is determined by the kinetic
energy of chains and entropy changes meanwhile by chain diffusions. These intrin-
sic properties have a great impact on entropy contribution to Gibbs free energy
during repair event [31]. Another considerable factor is a free volume in a matrix
which is desirable to the mobility of polymeric chains [32]. To obtain free volume,
some stimuli-responsive units are also incorporated into nonreversible systems by
copolymerization, and during mechanical stress, the entropy ∆S increased due to
segmental mobility, and finally rebonding of cleaved sites is possible [33]. During
self-healing process, voids/free volume facilitated segmental mobility of chains
and matrix macromolecular chains. Void-less system are rigid and subsequently
damage sensitive. Heterogeneities are critical parameters which offer the design of
self-repair concept. Different types of polymers like block, branched, and/or star
polymers showed self-repairs in range of nm to μm. Microphase separation and
microcapsules and inorganic particles are embedded into polymers and responsible
for macrodamages. In polymeric systems, heterogeneities are developed by phase
separation utilized by copolymers or composite materials [27, 28, 34] and shape
memory polymers [35]. In chemical process, different polymerization reactions of
healing precursor or entanglement of polymer chains or reversible covalent bonding
according to base matrix materials is dominant. All these stages are balanced by the
damage rates to healing rate. The rate of damage is defined by various factors such
as loading frequencies, strain rate, and the amplitude of stress. However, healing
rate can be monitored by concentrations of precursor species and/or intrinsic tem-
perature using varying reaction kinetics. In thermoset, encapsulation is an effec-
tive healing strategy, but in thermoplastics induced-healing is reported in which
healing is possible on heating of polymers above its glass transition temperature
(Tg) or using solvents by depression of the effective Tg as compared to below room
temperature [36]. In autonomic healing, the healing agent is incorporated or phase
separated by matrix so that the healing of crack/failure takes place without external
intervention at ambient temperature. It is fully self-contained and responds to
external stimuli. Healing is achieved by one-capsule system, dual-capsule system,
and hollow fiber and vascular network-based system. In non-autonomic healing,
human intervention is mandatory. It is inherent and intrinsically similar to biologi-
cal structures. It is a partially self-contained healing system. Healing functionality
is an intrinsic part of base matrix, but additional heat or radiation is required to
proceed. Generally, for high healing efficiency, the healing agent forms a homoge-
neous mixture although it is difficult to process in terms of large-scale production in
industries. The healing efficiency represents the recovery of mechanical integrity of
components. To quantify healing efficiency, many definitions have been proposed.
Basically, healing efficiency (η) is a ratio of change in a property of interest of
materials as shown in equation no. 1.

fhealed − fdamaged
η = ___________ (1)
fvirgin − fdamaged

where f is the property of interest of material, and fhealed, fdamaged, and fvirgin are
the property of interest of healed sample, the damaged sample, and the virgin
sample, respectively.
Damage volume is a deciding factor of maximum healing efficiency of various
repair systems. Each technique demonstrated diverse healing efficiency for differ-
ent damage volume. Intrinsic systems are preferred to heal small damage volume
and heal at molecular level due to the close proximity of damaged site which is
mandatory for re-bonding of the cleaved site. Microvascular network heals large

3
Functional Materials

damage volume and potentially attempts highest healing efficiency. Encapsulation

strategy covered the regime between intrinsic and vascular systems. Most of the
repair systems established high damage volume to low healing rate. To achieve
high healing efficiency, the damage rate should be equal to damage healing. Only
some systems based on capsule and intrinsic system are matched to healing rate to
damage rate. The exact nature of the self-healing method to be deployed depends
upon (i) the nature and location of the damage, (ii) the choice of repair resin, (iii)
the influence of the operational environment, and (iv) proximity of damage site
and healing precursor container. The stability and durability of the final material
can be increased by repairing the damage in an autonomic way. Currently, a more
dynamic strategy based on damage acceptance and management has been explored
and growing exponentially shown in Figure 1.
Multiple healing is possible through the intrinsic approaches which have
intrinsic functionality. This approach can be practical to thermoplastic, thermoset
polymers and elastomers. Intrinsic self-healing is achieved by the recovery of the
former interactions, with or without an external trigger. A certain magnitude of
stress (i.e., chemical, mechanical, or thermal) enhanced the mobility of polymer
network. On impact, the sudden drop of viscosity in matrix occurs due to transfer
of impact energy in the form of heat to localized zone, which allows the local
deformation and mobility of polymer chains or network. Upon cooling, network
restores the initial values of viscosity, and materials achieved virgin mechanical
and thermal stability. Moreover, to increase mechanical properties of intrinsic
system, more than one chemical healing principle may be required to combine.
The damage interfaces disappear when chain entanglements and chemical or
physical cross-links formed a network as strong as the bulk material. This process
can be obtained by physical and chemical interactions and a combination thereof.
The most accepted theory leading to interfacial physical healing is proposed by
Wool and O’Connor [37] which is based on molecular interdiffusion leading to
chain entanglements. This process can occur at higher temperatures as compared
to the bulk polymer glass transition temperature or through local external trigger
such as a solvent and temperature beyond the melting point in thermoplastics
(welding) [38]. In the case of reversible chemistries, the enhanced mobility leads
to a viscous flow of the material in the vicinity of the damage site. It is remarkable
that chain interdiffusion has been observed also at temperatures theoretically
below the bulk Tg which highlights the potential difference in Tg between the
bulk and the surface in freshly damaged materials influencing the healing pro-
cess. From a mechanical and theoretical point of view, up to 100% healing of an

Figure 1.
The concept of damage healing using intrinsic methodology.

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interface can only be obtained if the new interface has exactly the same properties
as the bulk material.

3. Passive self-healing based on extrinsic techniques

In passive mode, healing is generated by incorporation of foreign functionalities.

The extrinsic healing process is based on the use of a healing agent contained in the
matrix as a separate phase. The healing agent is usually in the liquid state, placed
into reservoirs which may be microcapsules or hollow fibers or microvascular net-
work. In most approaches, the healing agent is used with a catalyst, which can also
be encapsulated or dissolved in the matrix. Different extrinsic healing approaches
are explored. In some cases, the catalyst is not required to initiate the healing
process; the healing agent can also react to itself. The extrinsic healing concept is
based on the response after or at the onset of damage. Current research is concerned
with the improvement of healing agents in terms of compatibility and catalyst-free
system with some new encapsulation techniques.

3.1 Microcapsule embedment

Encapsulation strategy is mainly studied for polymers and coating. The basic
principle of strategy is healing by incorporated healing functionality or reactive
constituents into capsules followed by chemical reactions. These reactions take
place by various mechanisms including ring opening metathesis polymerization
(ROMP) [3], cycloreversion [39], cycloaddition [40], cross-linking reactions [41],
or a mechanochemical catalytic activation [42]. Damage acts as a stimulus to initiate
the healing process. Damages rupture the microcapsule, and subsequent release of
the core material (healing agent) is possible. The healing precursor reached at the
damage site by capillary action and spreads itself over the two fracture surfaces due
to the surface tension. Further, precursors interact with embedded adjacent catalysts
(Figure 3) leading to a network formation by following the above chemistries, which
terminate the further growth of crack or damage and restore mechanical integrity.
White et al. [3] designed a “dicyclopentadiene (DCPD) Grubbs’ system” based on
capsule healing which achieved 75% recovery of virgin fracture toughness of TDCB
specimens. Capsule- and hollow fiber-based healing systems are shown in Figure 2.

Figure 2.
Demonstration of healing phenomenon. (a) Capsule-based healing [3] and (b) hollow fiber embedment [11].

5
Functional Materials

Mainly, the adhesive and cohesive mechanisms are responsible for the failure of
interfaces. Better healing efficiency can be achieved by improving the adhesive ten-
dency of the poly-(DCPD) with fracture surface of the matrix without compromise
with the cohesive strength of the poly-(DCPD) (shown in Figure 4). The average
diameter of the microcapsule is ranging from ∼300 to ∼700 μm and shell walls with
thicknesses from 5 to 20 μm. Generally, the core materials of microcapsules are made
of poly(urea-formaldehyde) (PUF) [43]. The controlled release of the precursor
is the typical job of encapsulation strategy. Some of the eco-friendly catalyst-free
healing methods are also introduced because the catalyst-based approach is cost-
ineffective and related to some compromise of mechanical properties of matrix.
Various critical factors define the performance of encapsulation strategy [44, 45].
There are various different ways to proceed capsule healing; that is, (i) the encap-
sulated liquid agent can be combined with a dispersed catalyst, (ii) both the healing
agent and the catalyst can be embedded in different capsules, (iii) the healing agent
can also directly react with a functionality of the matrix under an external stimulus,
and (iv) the healing agent and the catalyst can be placed in the matrix as a separate
phase. Different capsule-based healing systems are summarized in Table 1.
The encapsulation strategy is mainly focused on meltable dispersion and in situ
and interfacial encapsulation techniques for capsules. Meltable dispersion is the
method of dispersing the healing agent in a melted polymer to form the capsules after
solidification of the polymer [47]. In situ and interfacial techniques have been used
for PUF or TETA microcapsules. In this technique, the shell is developed by polymer-
ization at the interface of healing agent droplets and the oil-in-water emulsion.
The triggering mechanism of encapsulation strategy is validated by optical
microscopy of a fracture plane showing ruptured capsules, by infrared spectros-
copy (IR), scanning electron microscopy (SEM), and energy-dispersive X-ray
spectroscopy (EDS) of the fracture plane. Different microencapsulation methods
are optimized such as physical methods, chemical methods, and physicochemical
methods. Robust, in terms of mechanically and thermally stable, microcapsules
having healing precursor have been synthesized for self-healing polyurethane
matrix [48]. Triethylenetetramine (TETA) microcapsules for wear-resistant
polymer composites [49] and poly(methyl methacrylate) microcapsules with high
storage and thermal stability [50] have been manufactured and implemented. The
switching behavior of microcapsule geometry between dry and wet condition is a
critical healing phenomenon. Polydimethylsiloxane-based self-healing elastomers

S.N. Healable systems Healing mechanism Ref. (s) Healing

efficiency
(%)

1 DCPD/PUF-microcapsules/Grubbs ROMP [3, 43] 99

catalyst
2 Epoxides/amine Curing mechanism [4] 91

3 Epoxy/DCPD-WCl6 catalyst ROMP [5] 20

4 Epoxy/mercaptan Curing mechanism [6] >100

5 Polysiloxane Polycondensation reaction [7] >100

(polydimethylsiloxane)/Pt catalyst

6 Thiol/maleimide Michal addition reaction [46] >100

7 Woven glass fabric/epoxy laminates Epoxy/ [8] 68–79

CuBr2(2-methylimidazole)4

Table 1.
Various self-healing systems based upon encapsulation strategy.

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Self-Healing Polymer Composites for Structural Application
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Figure 3.
(a) Grubbs first generation, (b) Grubbs second generation, (c) Hoveyda-Grubbs first generation, and
(d) Hoveyda-Grubbs second generation.

Figure 4.
The ROMP of encapsulated DCPD by Grubbs catalyst [3].

also are reported [7]. Dual component self-healing epoxy system containing epoxy
(DGEBA) and different variants of hardener microcapsules are investigated [51].
Various catalysts for ROMP of DCPD are shown in Figure 3.
Encapsulation techniques offered single healing due to unavailability of healing
precursor into capsules which is earlier invested in damage repair. However, these
are limited by processing difficulties and inhomogeneous distributions of two com-
ponents. Deteriorates of some mechanical integrity is common due to the addition
of external chemical constituent’s limiting the strategy. To deliver a larger amount
of healing agent, hollow glass fibers were used. This fiber reinforcement is based on
the bleeding ability of bio-system. For polymer composite systems, the hollow fiber
embedment approach has been more appropriate (Figure 4).

3.2 Hollow fiber embedment

Hollow fibers are used to deliver a larger amount of liquid healing agent.
These are embedded within either glass fiber-reinforced plastic (GFRP) or carbon
fiber-reinforced plastic (CFRP) composites. Healing-agent-filled hollow fibers

7
Functional Materials

are introduced into the matrix by the vacuum-assisted resin transfer molding
(VARTM) process. Vascular self-healing materials have appropriate healing agent
in a network in the form of capillaries or hollow channels, which may be intercon-
nected one dimensionally (1D), two dimensionally (2D), or three dimensionally
(3D), upon damage. One-dimensional system is designed by glass pipettes that
are embedded in epoxy resins [52]. Resin-filled hollow glass fibers impart healing
capability on low-velocity impact damage in CFRP [9]. Large-diameter capillaries
are not feasible to demonstrate damage healing. Smaller hollow glass fibers filled
with resin have been also used, but they were unable to deliver the resin into the
crack due to the high-viscous epoxy resins. Later, borosilicate hollow glass fibers
(with diameters from 30 to 100 μm with 55% of hollowness) were produced to
store the healing precursor resin. This approach offered certain advantages, such
as the higher volume of healing agent to deliver, performed by different activation
methods; visual inspection of the damaged site is possible, and embedment of
hollow fibers to conventional reinforcing fibers is easier. The fracture of hollow
fibers is mandatory to release healing precursors which limited the approach. The
low viscosity of healing agent is favorable to facilitate fiber infiltration, which
is necessary. The reinforcement of hollow glass fibers into CFRP also affects the
coefficient of thermal expansion so that multistep fabrication stages of the hol-
low fiber are another challenge. A novel hybrid multi-scale carbon fiber/epoxy
composite reinforced with self-healing core-shell nanofibers at interfaces has been
demonstrated [10]. The ultrathin self-healing fibers were fabricated by means of
co-electrospinning, in which liquid DCPD as the healing agent was enwrapped into
polyacrylonitrile (PAN) to form core-shell DCPD/PAN nanofibers. To enhance
the healing efficiency, vascular method is adopted in which a 3D microvascular
network is developed into the matrix to store the healing agents for transport in
longer distance.

3.3 The microvascular embedment

A microvascular technique is inspired from the respiratory system of livings.

The incorporation of micro-channels with a diameter ranging from 1 μm to 1 mm
within a polymer composite offers multiple healing. Self-healing materials that use
hollow fibers or a mesoporous network are called vascular materials. Microvascular
fabrication is possible by various techniques including laser micromachining, soft
lithography, electrostatic discharge, fugitive inks, and hollow glass fibers. Healing
precursors have been introduced into these channels either by pumping or through
capillary forces. However, hollow glass fibers are restricted to the 1D network, but
in order to obtain 2D and 3D interconnected networks, steel wires of ca. 0.5 mm
could be used [53]. For the interface between plies in laminated composites,
two-dimensional networks are suitable. Microvascular channels into polymer
composites offer the benefits of added functionality and increased autonomy (i.e.,
the ability to distribute active healing material for crack healing which is difficult
by conventional methods into monolithic materials). The introduction of sacrificial
fibers into woven preforms enables the continuous fabrication of 3D microvascular
composites that are both strong and multifunctional [12, 13]. To employ damage
healing in microvascular systems, functional fluids that act as a healing agent are
released upon fracture of vascular network. Further, the healing agent polymerized
with adjacent catalyst formed a network and restricts the growth of damage. Active
cooling microvascular systems continuously circulate a fluid into, through, and
out of the matrix in order to absorb and remove excess heat. Replacement of some
reinforcement fibers of FRPs by individual hollow fibers is a well-known method to
achieve microvascular composites [54]. Schematic diagram of self-healing materials

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Self-Healing Polymer Composites for Structural Application
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Figure 5.
Schematic diagram of self-healing materials with 3D microvascular networks. (a) Capillary network in skin
having a cut in the epidermis layer. (b) Vascular network into epoxy coating having catalyst in a four-point
bending configuration monitored with an acoustic emission sensor. (c) Crack propagation toward micro-
channel. (d) Optical image of released healing agent in the coating [15].

with 3D microvascular networks is shown in Figure 5. The effect of optimum size

and orientation of hollow fibers in microvascular architecture in the epoxy matrix
has been studied [14].
A novel type of hollow fiber called “compartmented fibers” has been developed
[55]. However, hollow fibers have a greater influence on the mechanical properties
of composites than microcapsules. Indeed, using this type of fibers, a localized
healing response can be activated. Vasculature-based healing allowed the efficient
delivery of the healing agent and additionally healed a large area. The large-scale
production of self-healing fiber-reinforced composites is not feasible due to com-
plex vasculatures and lack of scalability. After the first healing, the network may
be refilled for the next healing. Initially, a brittle polymer coating is applied to a
more ductile polymer substrate which contains the interconnected network of
micro-channels. In contrast, synthetic self-healing composites have high strength-
to-weight ratios with less dynamic functionality.
Ultralow-temperature damage healing is achieved by incorporating a 3D micro-
vascular network (Figure 6). Hollow vessels are used to deliver healing agents, and

Figure 6.
(a) Internal structure of the composites and (b) damage-bleeding healing process [16].

9
Functional Materials

a porous conductive wire defrosts the system by internal heating, and further heal-
ing reactions are proceeded [16]. The concept may be used to develop self-healing in
aerostructure at high altitude having low temperature.

4. Active self-healing based on intrinsic methodology

Structurally dynamic polymers are a macromolecular system in which dynamic

bonds are responsible for the restructuring of molecular architecture upon to
external stimuli. Reversible bonding chemistry (i.e., covalent and non-covalent)
is used to design structurally dynamic polymer systems produced to respond on
macroscopic changes of material’s architecture. Repeatable damage healing is
demonstrated by various non-covalent interactions (reversible physical bonding),
the covalent chemistries (reversible chemical bonding), and recently by their
varied combination. Dynamic bonds are sensitive to specific stimulus and selec-
tively undergo reversible bonding and de-bonding under equilibrium conditions.
Intrinsic healing systems are programmed to respond to macroscopic damages.
Basically, it is active methodology; healing is achieved by dynamic bonding of the
polymer matrix. Intrinsic healing has specific properties of certain materials, such
as molecular structures and chemical or physical bonds. The intrinsic self-healing
requires human/external intervention to perform in most of the cases. The healing
is possible via temporary local mobility enhancement of polymeric chains. Various
modes of energy (e.g., temperature, static load, UV) are critical factors for the
mobility of polymeric chains. Some chemical principles with multiple chemistries
are responsible for macroscale healing. Reversible supramolecular interactions are
low-energy interactions and based on hydrogen bonding, ionomer bonding, π-π
interactions, or metal coordination. Two other categories of intrinsic healing sys-
tems combining physical and chemical approaches can be included: shape memory
polymers and polymer blends.

4.1 Thermodynamic covalent bonding-based Diels-Alder (DA) and Retro-DA

(r-DA) reactions

Cross-linked polymer networks have superior mechanical properties and ther-

mal as well as chemical resistance as compared to their uncross-linked and linear
analog. But, due to high cross-linked density, these systems are rigid and susceptible
to mechanical damage. By incorporation of some dynamic covalent functional-
ity into matrix backbone and/or in side chains, we achieved stimuli-responsive
systems. Dynamic cross-linked systems have improved service life and energy
efficiency and resist to foreign object impact. Basically, thermoreversible bonding is
a more useful technique to load-bearing structures. It is accomplished by reversible
chemical reactions upon an external stimulus. Typical dynamic bond chemistry is
belonging to disulfide [56], hindered urea [57], and alkoxyamine [58] that are hav-
ing flexible bonding units. A polymer (3M4F) system demonstrated self-repairing
by subjecting it to heating/cooling cycles [18] shown in Figure 7.
In contrast, cycloaddition reaction is an efficient method to design carbon-carbon
linkage without the use of catalyst. An electron-rich diene and electron-poor dieno-
phile species play a key role to succeed DA/r-DA cycloaddition reaction. A product
of DA reaction is known as DA adduct. DA adduct is the mixture of endo- and exo-
diastereomers. Due to the temperature of the r-DA reaction, the exo-diastereomer
is a major adduct. DA adducts have norbornane-type covalent functionality which
is slightly weaker than other covalent linkages in matrix. Upon excess mechanical
loading, the excess stress is transferred to weak bonding of adducts, and de-bonding

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Self-Healing Polymer Composites for Structural Application
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Figure 7.
Reversible cross-linked furan-maleimide-based polymer network [18].

occurs. Upon elevated temperature, DA adducts can be dissociated into corresponding

diene and dienophile moieties through r-DA reaction within the cross-linked system.
Upon further cooling, re-bonding is preceded into DA adduct by reaction between cor-
responding diene and dienophile units. Due to thermal reversibility of DA reactions,
they are frequently applied to production of remendable and recyclable materials
[17–20]. The 4 + 2 cycloaddition Diels-Alder reaction is the most studied thermally
controlled reaction and belongs to the group of “click reactions” that are famous for
flexibility and well-organized, and selective chemical synthesis [21]. By utilizing r-DA
and following DA reactions, covalent network displays a dissociation and reformation
through void-filling thermoreversible process upon controlled heating. Chemically,
on the basis of utilized form of diene and dienophile functionalities for DA/r-DA
reaction, these systems are classified into three categories: furan-maleimide polymer
systems, dicyclopentadiene-based systems, and anthracene-functionalized polymer
systems. Graphene nanosheet-functionalized polyurethane-based composite has
shown infrared (IR) laser-assisted self-healing, which is advantageous to flexible
electronics [59]. Most of the DA cross-linked network is fabricated through step-
growth poly-addition or coupling reactions of polyfurans and polymaleimides. Furan
and maleimide pair is highly reactive for cycloaddition reaction and low-temperature
shifting of DA/r-DA equilibrium because these moieties exist in s-cis conformation,
which offered rigid system favorable for DA reaction. Furan group acts as diene, and
maleimide acts as dienophile based on DA/r-DA reaction chemistry. These reactions
still need an external heat source to initiate the healing process. Various healing
systems based on reversible covalent bonding are presented in Table 2.
If the amount of damage is microscopic, capsule-based or intrinsic systems may
be the best option. But, macroscopic damaged volume and vascular-based systems are

11
Functional Materials

S.N. Healable systems Healing Ref. Remarks

mechanism
1 Dicyclopentadiene-based DA/r-DA [17] Polymer side chains
polymers functionalized

2 3M4F polymer DA/r-DA [18] Multivalent star-shaped

systems

3 2ME4F polymer 4 + 2 DA reaction [20] Solvent-free synthesis

4 Anthracene-based polymers DA/r-DA [19] Polymer backbone

functionalized along itself

5 Thiol-modified poly Redox-reversible [60] Thiol-disulfide system

[N-acetylethylene-imine] hydrogel system (side-chain modification)

6 Polystyrene-based block Thiol-disulfide [61] Thiol-disulfide system

copolymer linkage (backbone modification)

Table 2.
Various self-healing systems based upon reversible covalent bonding.

efficient which allow large amounts of healing agent to be transported to the damage
site. The aforementioned self-healing techniques address the repairs, mitigations, crack
growth, and various damage conditions in polymer matrix. These techniques have
advantages and limitations specific to applications that are summarized as follows:
(i) These have slow healing rate.

(ii) Additional requirement of heat/light in intrinsic systems can be good or bad

depending on the application.

(iii) The use of foreign inserts in matrix leads to detrimental effects on matrix.

(iv) Complexity of vascular networks is a challenge.

(v) Do not address the ballistic or hypervelocity impacts, which are great promis-
ing to space exploration upon material puncture healing.

4.2 Supramolecular noncovalent interaction-based self-healing

In materials, microscopic damages are repaired by extrinsic technology in

which foreign species play a lead role in the healing process. These techniques
respond to damages autonomically or stimulus-assisted phenomenon and take a
shorter time to recover the strength of materials. But in the case of macroscopic
damages, these extrinsic techniques are poorer in performance. Additionally,
structurally covalent dynamic polymers are also requested with additional heat
to clear microdamages. To overcome these issues, some significant research in the
field of supramolecular systems is focused which respond to damages autono-
mously and recovered mechanical integrity without the addition of foreign reac-
tive species and human intervention. In high-performance materials, macroscopic
and energetic damage events are usual. These damages are healed by physical
interactions. The physical interactions are noncovalent in nature and cause
autonomic healing due to inherent origin. These recover about fully mechanical
properties but take longer time. These noncovalent interactions recover mechani-
cal properties almost completely but take longer time. These interactions are
reversible subjected to the thermodynamic equilibrium and show additional
impacts such as environmental-dependent switch properties, easy processability

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Self-Healing Polymer Composites for Structural Application
DOI: http://dx.doi.org/10.5772/intechopen.82420

S.N. Nature of Healing system Ref. Remarks

interactions
1 Hydrogen DCPD/DNE/epoxy systems [22] Adhesion promoter
bonding used

Polystyrene grafted with [23] Polyvalent H-bonding

poly(acrylate amide) sites

Ureidopyrimidinone bond— [24] Self-assembly

SupraPolix BV mechanism

2 π-π interaction Polydiimide/poly(siloxane) with [25, 26] Flexible and self-

pyrenyl end groups supporting material

Copolyimide/poly(amide) with [66] Thermoreversible

pyrenyl end groups system

3 Ionomers Poly(ethylene-co-methacrylic [27–30] Self-sealing shooting

acid)/Na + ion (EMAA) range targets, tires

Table 3.
Typical supramolecular interactions and relevant self-healing polymer systems.

and self-healing behavior as compared to traditional polymers. Reversible bonding

can be used to design supramolecular healable polymers and composites which
respond to external stimuli such as heat [62], pressure [63], water [64], or light
[65]. Various supramolecular interaction-based self-healing systems are shown in
Table 3.
Stimuli responsiveness [67] and a high diffusion rate of oligomeric compo-
nents [68] are the main characteristic of supramolecular polymers which make
them for rapid and controllable healing system. Oligomers are low-molecular-
weight species that make aggregates by self-assembling and perform rheologi-
cal or mechanical properties similar as polymers. The reversible non-covalent
interactions can be possible by hydrogen bonding, ionic bonding, metal-ligand
bonding, and π-π stacking.

4.2.1 Supramolecular chemistry based on H-bonding

H-bonding is the most popular route to achieve supramolecular polymers. Upon

heat, interactions between the polymeric chains are decreased and reassembled
upon cooling, and finally the non-covalent cross-linking recovered the strength
and mechanical integrity. To achieve sufficient cross-linking density in polymer,
a high association constant between repeating units is needed. The association
constant and a reversible interaction have a reverse relation. In contrast, at the less
association constant, better reversibility is achieved but having smaller assemblies
and poor mechanical properties. However, individual supramolecular polymers are
suffered by low mechanical strength. The mechanical strength of supramolecular
system is enhanced by an increase in the number of non-covalent interaction [22]
and by reinforcement with nanofiller [26]. Significantly, the interactions of matrix
fiber are increased by the presence of hydrogen bond accepting functionality in
matrix polymer blend. Adhesion promoter increases the amount of H-bonding of
the matrix system [22]. These promoters are known as co-healing agents shown in
Figure 8. On fracture of capsules, the DCPD monomer penetrates the networks
of epoxy matrix and reacts with embedded catalyst. The formation of interpen-
etrated network is initiated by polymerization of DCPD which would strengthen
the matrix—poly(DCPD) surface. Higher strength is obtained by entangled

13
Functional Materials

Figure 8.
Supramolecular interactions with adhesion promoter [22].

networks, and H-bonding will also improve overall bonding strength and healing
efficiency. H-bonding-incorporated supramolecular system is shown in Figure 8.
The reinforcement of cellulose nanocrystals or cellulose nanowhiskers into polymer
matrix such as poly(ethylene oxide-co-epichlorohydrin) [69] and low-density polyeth-
ylene [70] has shown improved stiffness corresponding to parental matrix materials.

4.2.2 Metal-ligand supramolecular polymers

Optical and photo physical properties of metal complexes offer to design

advanced materials. Reversible behavior of metal ion and ligand bond in metal-
ligand complexes attract the research community to design stimuli-responsive
materials. Metallo-supramolecular polymers have low-molecular-weight species
known as telechelic. These are attached with ligand end group through metal-ion
linkage. These polymers can be healed upon contact of light [65, 71]. During the
whole healing mechanism, supramolecular interactions and light-heat conversion
happen subsequently. The temporary disentanglement of metal-ligand motifs is
possible when excited electronically upon contact with UV, and further, heat energy
is released. Subsequently, the average molecular weight and viscosity of system are
decreased, and defect healing is resulted. Local damages can also be recovered just
upon light exposure. A metallo-hydrogel based on histidine and Zn2+ ions is designed
using coordination-driven self-assembly [72]. The hydrogel formation is instan-
taneous, and it exhibits stimuli-responsive behavior with respect to pH, heat, and
external chemicals.

4.2.3 Supramolecular π-π interaction-assisted self-healing

A thermally triggered reversible network is achieved based on π-π stacking inter-

actions in which end-capped π-electron-deficient groups interact with π-electron-
rich aromatic backbone. The chain-folding co-polyimide (electron deficient) and
pyrenyl (electron rich) end-capped polyamide chains have such π-π interactions
[66]. The driving forces for producing tough, stable, healable homogeneous blend
of elastomers are interpolymeric π-π stacking complexes [73]. At higher tem-
peratures, the disengagement of the supramolecular (π-π stacking and hydrogen-
bonding) interactions is possible, which leads to change in the apparent molecular
14
Self-Healing Polymer Composites for Structural Application
DOI: http://dx.doi.org/10.5772/intechopen.82420

Figure 9.
Schematic diagram of ionomeric healing upon ballistic impact based on order-disorder theory of healing
presented by Fall [27].

weight of the homogeneous noncovalent polymer blend and further rapid change in
viscosity with temperature. A polymer blend recovered the mechanical strength by
refurbishing these supramolecular interactions.

4.2.4 Supramolecular self-healing ionomers

Ionomers are polymers in which the bulk properties are governed by ionic
interactions in discrete regions of the material [74]. Ionomers contain up to 15%
ionic groups and respond instantaneously and autonomously in absence of external
species, and additional heat or other stimuli make ionomers unique. Various bond-
ing interactions such as ionic, dipole-dipole, or ion-dipole bonds are key factors to
develop self-healing systems based on ionomers. Ballistic healing proceeds through
combination of an elastic response (i.e., attain pure shape) and a viscous response
(secondary polymer flow and chain entanglement) of intrinsic aggregates. Initially
after impact, projectile transfers some of the impact energy to ionomer system
which melts the matrix, and rest kinetic energy is stored elastically to movement,
and the projectile is ejected and leaves behind the matrix with some melted portion.
Finally, the hole is sealed and recovered some mechanical properties followed by
crystallization and reaggregation of ionomers at the damage site. Healing process
in ionomers is multistep. Initially upon high-energy impacts, the local deformation
proceeded to less ordered melt state and resultant the projectile is ejected. After
that, complex aggregates are formed via recrystallization of interdiffusion of inter-
molecular interactions. It is a quick process that happens within seconds to hours.
In the second step, restructuring of physical cross-linking leads the final stage of
healing; it takes longer duration as usually days to months. Some of commercial
products such as React-A-Seal, Surlyn, and Nucrel have EMAA as base matrix [27].
It is a copolymer of ethylene and a vinyl monomer with an acidic group. EMAA
ionomer exposed self-healing upon ballistic impact (Figure 9) [27, 28].
During whole mechanism “free volume” plays a great role which provides
enough mobility to polymer chain rearrangement and interdiffusion. Besides, many
other factors, such as impact energy, nature of ionic groups, and counterions, the
neutralization degree, increased temperature during impact, the content of ionic
groups and dielectric constant, and so on, also play a key role to succeed self-healing
by ionomers. To enhance the healing efficiency of ionomers composites, conductive
15
Functional Materials

S.N. Healing system Healing mechanism Ref. Remarks

(photoinduced)
1 1,1,1-tris(cinnamoyloxy-methyl) [2 + 2] Cycloaddition [40] Cycloaddition
ethane (TCE) monomer of cinnamoyl
groups

2 Pentaerythritol tetra Reversible cleavage of [76] Hemolytic

(3-mercaptopropionate) and allyl sulfide linkage photolysis
triethylene glycol divinyl ether
system

3 Pyridine-capped poly(methyl Light-induced cis-trans [77] Molecular

acrylate)s/SCS-cyclometalated isomerization switching
dipalladium

4 Epoxy/SiO2 microcapsule UV-triggered [78] Aerospace

polymerization coatings

5 Chitosan polyurethane networks Photoinduced reaction [79] Coating

applications

6 Epoxy/nano-TiO2 Photoabsorbing [80] Protection

microcapsules coatings

Table 4.
Photoinduced damage-healing system.

and magnetic fillers are added [29]. In addition to plasticizer such as zinc stearate
ionic domain, the matrix properties are intact [75].

5. Photochemically induced healing chemistry

Photoinduced healing is currently demanding because of rapid, eco-friendly

concept of healing of polymer matrix composites. It is induced by the application of
a strong light irradiation. To damage healing, the foreign healing inserts, catalyst, or
additional heat is neither required to comply with the healing process. Such system
based on photochemical reactions is developed (Table 4).

6. Significance of healing functionality

The objective of self-healing phenomenon is focused to respond upon fracture

based on quasi-static performance. In the future, self-healing materials can be used
in various applications including nuclear reactors, marine structures, and various
cutting tools. Self-healing aircrafts or spacecraft is currently desired in references of
micrometeoroids and orbital debris protection, low-temperature repairs for aero-
structures, and re-healable fuel tanks. Cost-efficient healable wind power blades
and wire insulation materials are also desirable based upon self-healing materials.
Durable targets for military personnels and training are also part of self-healing
ionomers which protect against ballistic penetrations.

7. Current scenario, challenges, and future perspective

Self-healing systems represent a wide interdisciplinary area and are performed

by different techniques. Understanding the basic mechanism and principle of
damage healing is also still a challenge for science community. Healing chemistries

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Self-Healing Polymer Composites for Structural Application
DOI: http://dx.doi.org/10.5772/intechopen.82420

have greater stabilization, higher reactivity, and fast kinetics, although many chal-
lenges still remain. Healing performance under long term in drastic environment is
advantageous. Additionally, increased healing efficiency with low-cost techniques
and least detrimental effect on base matrix is also challenging. To implement encap-
sulation technique, distribution of capsules is challenging and has adverse effects
on matrix. Similarly, the fabrication of vascular network is not easy to implement.
In microelectronics, optoelectronics, and robotics where damages are common as
nanostructures, self-healing concept is beneficiary. Long-lasting self-healing battery,
self-sealing fuel tank/tires, fad-resistant textiles, and anti-tamper electronics are
future significance of self-healing technique. Sensor design with healing concept
is used to structural health monitoring of components. The incorporation of self-
healing concept into aerostructures is challenging and required to establish because
the aerostructures always suffered mechanical and thermal loading continuously. In
the future, catalyst-free and UV- or light-oriented self-healing systems are desirable.

8. Conclusive remarks

Conclusively, the self-healing techniques explore the possibility of damage

detection and subsequent damage management in materials. Some technological
restrictions and possible solutions are also explored. Self-healing techniques inti-
mate damages at the early stage and recovered mechanical properties at some extent
which reduces the probability of replacement and loss of structures. Currently, we
are still waiting for fully self-healing systems that can show both stimuli responsive-
ness and healing characteristics.

Acknowledgements

The author would like to say thanks to Dr. Dibeyndu S. Bag and Dr. Ajit Shankar
Singh, DMSRDE, Kanpur, for their adequate suggestion to design the article.

Author details

Jeetendra Kumar Banshiwal* and Durgesh Nath Tripathi

Defence Materials and Stores Research and Development Establishment, Kanpur,
India

*Address all correspondence to: [email protected]

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

17
Functional Materials

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