Review

Self-Healing Nanocomposites—Advancements and

Aerospace Applications
Ayesha Kausar 1,2,3, * , Ishaq Ahmad 1,2,3 , Malik Maaza 2 and Patrizia Bocchetta 4, *

1 NPU-NCP Joint International Research Center on Advanced Nanomaterials and Defects Engineering,
Northwestern Polytechnical University, Xi’an 710060, China
2 UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology, iThemba LABS,
Somerset West 7129, South Africa
3 NPU-NCP Joint International Research Center on Advanced Nanomaterials and Defects Engineering,
National Centre for Physics, Islamabad 44000, Pakistan
4 Department of Innovation Engineering, University of Salento, Edificio La Stecca, via per Monteroni,
73100 Lecce, Italy
* Correspondence: [email protected] (A.K.); [email protected] (P.B.)

Abstract: Self-healing polymers and nanocomposites form an important class of responsive materials.
These materials have the capability to reversibly heal their damage. For aerospace applications,
thermosets and thermoplastic polymers have been reinforced with nanocarbon nanoparticles for
self-healing of structural damage. This review comprehends the use of self-healing nanocomposites
in the aerospace sector. The self-healing behavior of the nanocomposites depends on factors such
as microphase separation, matrix–nanofiller interactions and inter-diffusion of polymer–nanofiller.
Moreover, self-healing can be achieved through healing agents such as nanocapsules and nanocarbon
nanoparticles. The mechanism of self-healing has been found to operate via physical or chemical
interactions. Self-healing nanocomposites have been used to design structural components, panels,
laminates, membranes, coatings, etc., to recover the damage to space materials. Future research
must emphasize the design of new high-performance self-healing polymeric nanocomposites for
aerospace structures.

Keywords: self-healing; polymer; nanocomposite; nanocapsule; aerospace

Citation: Kausar, A.; Ahmad, I.;
Maaza, M.; Bocchetta, P. Self-Healing
Nanocomposites—Advancements
and Aerospace Applications. J.
1. Introduction
Compos. Sci. 2023, 7, 148. https://
doi.org/10.3390/jcs7040148 Among smart polymeric materials, self-healing polymers have gained significant
research interest [1]. Self-healing polymers have found applications in wide-ranging tech-
Academic Editor: Francesco
nical fields such as electronics, supercapacitors, batteries, membranes, biomedical, etc. [2].
Tornabene
The potential of self-healing nanocomposites has also been protracted to the aerospace
Received: 8 March 2023 arena [3]. In this regard, self-healing nanocomposites have been fabricated through the
Revised: 23 March 2023 incorporation of nanoparticles in polymers [4]. Nanocarbon nanoparticles, in particular,
Accepted: 3 April 2023 have been reinforced in space-related polymers [5]. Self-healing has been observed through
Published: 7 April 2023 the development of physical or chemical crosslinking in polymeric chains. Self-healing
may occur through several means such as via intrinsic phenomena, using nanoparticles or
nanocapsules or under the influence of external stimuli [6–8]. Morphology studies have
been performed for self-healing materials [9]. Exploration of the self-healing mechanism has
Copyright: © 2023 by the authors.
been found to be indispensable for the development of high-performance aerospace struc-
Licensee MDPI, Basel, Switzerland.
tures [10]. In particular, for large-scale processing of materials for commercial aerospace
This article is an open access article
applications, self-healing nanomaterials need to be industrialized [11].
distributed under the terms and
Self-healing materials were first developed 2000 years ago [12]. The Romans found
conditions of the Creative Commons
Attribution (CC BY) license (https://
self-healing in concrete structures. Microcracks were resisted due to intrinsic crystallization
creativecommons.org/licenses/by/
of minerals in concrete. Self-healing of different types of materials has been reported such
4.0/).

J. Compos. Sci. 2023, 7, 148. https://doi.org/10.3390/jcs7040148 https://www.mdpi.com/journal/jcs

J. Compos. Sci. 2023, 7, 148 2 of 26

as thermoplastic polymers [13], thermoset polymers [14], elastomers [15], shape mem-
ory polymers [16], polymer composites and nanocomposites [17]. Research on synthetic
self-healing materials focuses on fabrication of multifunctional materials to recover funda-
mental characteristics such as mechanical strength, electrical conductivity and corrosion
resistance [18]. Self-healing of synthetic materials expands the potential utility of these
materials [19]. The mechanism of self-healing has been categorized into extrinsic and
intrinsic phenomena [20]. The difference between these self-healing materials depends
on their chemistries. Extrinsic healing depends on external healing agents in the form of
capsules or vesicles. Thus, extrinsic self-healing involves the development of materials
relying on healing agents and catalysts. Intrinsic self-healing may occur without using
any external healing agent. In both approaches, the self-healing process is initiated by
external or internal damage in the polymer network. In extrinsic self-healing, microcap-
sules have been developed using polyurethane, poly(urea formaldehyde), poly(melamine
urea formaldehyde), poly(melamine formaldehyde), etc. [21]. Intrinsic self-healing materi-
als usually occur through non-covalent chemistries and develop π–π stacking, hydrogen
bonding and host–guest interactions [22]. Extrinsic self-healing may involve non-covalent
bonding and covalent interactions such as Diels–Alder reaction, trans-esterification, radical
exchange reactions, etc. Self-healing polymers and nanocomposites have been found to
be advantageous relative to non-healing materials due to their better physical properties,
supramolecular forces and structural durability. Mechanisms of self-healing in polymers
nanocomposites have been investigated using theoretical studies and experimental investi-
gations. Self-healing polymers and nanocomposites have been used for multifunctional
applications such as electronics, energy, transportation, coatings, aerospace, etc. [23,24].
In this review, self-healing polymers, self-healing nanocomposites and their appli-
cations for the aerospace sector have been comprehended. Self-healing in space-related
nanocomposites has been observed through using nanoparticles and micro- or nanocapsules
as healing agents. Various polymers and nanocarbon nanofillers have been utilized to form
self-recovering aerospace nanocomposites. Future progression in self-healing nanocompos-
ite relies on new design inventions for enhanced healing efficiency for aerospace structures.

2. Self-Healing Polymer
For industrial-level structural applications, high-performance polymeric materials
need to be developed [25]. For the purpose, the physical properties of pristine polymers
need to be improved. Self-healing of polymers has been considered important for structural
uses [26]. Self-healing polymers have the capability to repair structural damage [27]. For
self-healing, polymer chain mobilization and crosslinking have been considered indispens-
able to reform the damage [28]. Self-healing can be initiated by external stimuli such as
temperature, force, pressures, etc. [29]. Self-healing mechanisms have been thoroughly
investigated in the literature [30,31]. Wang et al. [32] studied various physical and chemical
approaches for self-healing of structural damage. Self-recovery effects have been observed
in the thermosets [33] and thermoplastics [34]. In polyurethanes, healing has been ob-
served through reversible interlinking and bond formation in the polymer chains [35,36].
Gao and co-workers [37] considered self-healing of polyacylate using a self-healing agent
(bismaleimide/furfuryl alcohol). Reversible crosslinking via chemical bonding was ob-
served through the Diels–Alder reaction [38]. Recovery of the damaged structure was
perceived at a low temperature [39]. Self-healing has been observed through interdif-
fusion of polymer chains [40], stimuli responsive features [41], reformation of physical
links [42] and regeneration of covalent linking [43]. Figure 1 demonstrates key practices for
self-healing processes in polymers.
J. Compos. Sci. 2023, 7, 148 3 of 26

Figure 1. Self-healing mechanisms: (A) physical processes to understand self-healing include in-
terdiffusion of polymer chains, introduction of phase-separated morphologies, shape-memory and
introduction of active nanoparticles into the polymer matrix, and (B) physical and chemical processes
can be combined to perceive self-healing. Reprinted with permission from [32]. 2020, Nature.

Physical or covalent interactions at the molecular level have been found to be involved
in self-healing of polymers. Usually, physical interactions occur by developing van der
Waals forces [44], and chemical interactions mainly comprise covalent interactions [45].
In addition, micro or nanocapsules have been used to initiate the self-recovery process
in polymers [46,47]. During self-healing, these capsules rupture in the matrix to heal the
damaged surface or area [48].
Jin et al. [49] studied self-healing of epoxy materials using healing agents in the form of
microcapsules. (C2 H5 )2 O·BF3 was loaded in the microcapsules. The 1 wt.% (C2 H5 )2 O·BF3 -
containing microcapsules caused ∼80% self-recovery of impact-related cracked epoxy
surface. Epoxy with microcapsules was used as a self-healing adhesive for cohesive failure.
The adhesive was applied on the steel surface (Figure 2). According to scanning electron
microscopy images, crack tails were observed due to crack-pinning toughening of the
fractured sample. On the healed fracture surface, crosslinked polymer film could be
observed, initiating the in situ crosslinking of polymer chains for self-healing.
J.J.Compos.
Compos.Sci. 2023,7,7,148
Sci.2023, x FOR PEER REVIEW 44 of
of 26
26

Figure2.2.Quasi-static
Figure Quasi-static fracture
fractureplane
planeafter
afterhealing
healingofofself-healing
self-healingspecimen:
specimen: (a)
(a)optical
opticalimages
imagesofof
matingfracture
mating fracturesurfaces
surfacesshowing
showing cohesive
cohesive fracture;
fracture; (b)(b)
SEMSEM image
image of healed
of healed fracture
fracture surface
surface show-
showing
polymer film (blue) formed during self-healing; and (c) SEM image of fracture surface at end ofof
ing polymer film (blue) formed during self-healing; and (c) SEM image of fracture surface at end
sample created during imaging (unhealed) revealing crack tails indicative of toughening mecha-
sample created during imaging (unhealed) revealing crack tails indicative of toughening mechanism
nism SEM = scanning electron microscopy. Reprinted with permission from [49]. 2011, Elsevier.
SEM = scanning electron microscopy. Reprinted with permission from [49]. 2011, Elsevier.

3.3.Self-Healing
Self-HealingNanocomposites
Nanocomposites
Similartotopolymers,
Similar polymers, self-healing
self-healing polymer-based
polymer-based composites
composites and nanocomposites
and nanocomposites have
have been investigated [50]. Self-healing materials have been
been investigated [50]. Self-healing materials have been successfully manufacturedsuccessfully manufactured for
for aerospace
aerospace relevance
relevance [51,52].
[51,52]. Self-healing
Self-healing in epoxy/glass
in epoxy/glass fiber composites
fiber composites has beenhas been
studied
studied
via via UV
UV curing. curing.
Hollow Hollow
glass fibersglass
were fibers werehealing
filled with filled with
agents healing agents
for damage for damage
repair [53,54].
repair [53,54].
Damage Damage fiber
in epoxy/glass in epoxy/glass
composites fiber
wascomposites
self-healed was under self-healed
the influenceunder the influ-
of UV light
encerelease
and of UV light and release
of healing agent of healing
from agent
fibers fromMoreover,
[55,56]. fibers [55,56]. Moreover, microcapsules
microcapsules with healing
with healing
agent have beenagent have been
introduced inintroduced in epoxy[57].
epoxy composites composites [57]. aerospace
In structural In structural aerospace
composites,
composites,
large amountslarge amounts
of healing of healing
agent have been agent have been
required required
for damage for damage
repair. repair.
In addition In ad-
to micro-
dition to nanoparticles
capsules, microcapsules,have nanoparticles
also been have
foundalso been found
to cause to cause the
the self-healing self-healing [58].
phenomenon phe-
nomenon
In aerospace,[58].self-healing
In aerospace, self-healing nanocomposites
nanocomposites have been found have tobeen foundfor
be useful to be useful for
engineered
structures,
engineered adhesives,
structures, coatings, etc. [59,60].
adhesives, coatings,Self-healing
etc. [59,60].features of epoxy/carbon
Self-healing nanotube
features of epoxy/car-
nanocomposites have been examined
bon nanotube nanocomposites have been[61].examined
For self-healing,
[61]. Forreversible
self-healing, hydrogen
reversible bondhy-
formation has been observed between the matrix and nanofiller
drogen bond formation has been observed between the matrix and nanofiller [62]. The [62]. The self-healing
mechanism
self-healingwas dependent
mechanism wasondependent
the polymer on chain mobility
the polymer or effect
chain of external
mobility stimuli
or effect [63].
of external
Both the[63].
stimuli physical
Both and covalentand
the physical interactions have been perceived
covalent interactions have beenfor the self-healing
perceived of
for the self-
thermosets or thermoplastic
healing of thermosets nanocomposites
or thermoplastic [64].
nanocomposites [64].

4.4.Self-Healing
Self-HealingNanocomposites
Nanocompositesfor forAerospace
Aerospace
Research
Research on self-healing has continuously grown
on self-healing has continuously grown in
inlast
lastthree
threedecades
decades[65–67].
[65–67]. Pri-
Pri-
marily, self-healing polymer/fiber composites were developed [68–70]. The self-recovery
marily, self-healing polymer/fiber composites were developed [68–70]. The self-recovery
effect
effecthas
hasalso
alsobeen
beenstudied
studiedfor
forpolymeric
polymericnanocomposites
nanocomposites[71,72].
[71,72]. In
In nanocomposites,
nanocomposites,
nanofillers have been used to enhance the self-healing effect [73–75]. Incidentally, the type
nanofillers have been used to enhance the self-healing effect [73–75]. Incidentally, the type
of nanofiller and contents have found to be essential factors to initiate the self-healing
of nanofiller and contents have found to be essential factors to initiate the self-healing
effect [76]. Here, self-healing agents have also been employed to facilitate the healing
effect [76]. Here, self-healing agents have also been employed to facilitate the healing pro-
process in nanomaterials. To incorporate healing agents, small vesicles or capsules have
cess in nanomaterials. To incorporate healing agents, small vesicles or capsules have been
been used, which may rupture during the recovery of the damaged surface or area [77].
used, which may rupture during the recovery of the damaged surface or area [77].
For the aerospace sector, self-healing polymeric nanomaterials have been developed
For the aerospace sector, self-healing polymeric nanomaterials have been developed
for various purposes such as engineering structures, adhesives, coatings, engines, fuselage,
for various purposes such as engineering structures, adhesives, coatings, engines, fuse-
etc. Pulikkalparambil and co-workers [73] designed an epoxy nanocomposite and the
lage, etc. Pulikkalparambil and co-workers [73] designed an epoxy nanocomposite and
 J. Compos. Sci. 2023, 7, x FOR PEER REVIEW 5 of 26
J. Compos. Sci. 2023, 7, 148 5 of 26

the self-healing
self-healing effecteffect was studied
was studied using
using the the nano-encapsulated
nano-encapsulated healing healing
agent. Theagent. The self-
self-healing
healing epoxy nanocomposite was used as a coating to protect the surface
epoxy nanocomposite was used as a coating to protect the surface damage. Figure damage. Figure
3
3 exhibits the self-healing mechanism of epoxy coating. During the recovery
exhibits the self-healing mechanism of epoxy coating. During the recovery process, the process, the
nanocapsuleswere
nanocapsules wereburst
burstto
torelease
releasethe
thehealing
healingagent
agent for
forrelated
related damage
damage recovery
recovery [78].
[78].
Thedamage
The damagewas wasalmost
almostcompletely
completelyhealed
healedusing
usingthe
thenanocapsules.
nanocapsules.Efficient
Efficientself-healing
self-healing
nanocompositeshave
nanocomposites havebeen
beensuccessfully
successfullyapplied
appliedininaerospace
aerospace[79].
[79].The
Theself-healing
self-healingeffect
effect
was initiated using various stimuli such as light, heat, moisture, impact, etc.
was initiated using various stimuli such as light, heat, moisture, impact, etc. [80]. Space[80]. Space
vehicleshave
vehicles havebeen
beenfound
foundtoto
bebe continuously
continuously affected
affected by by environmental
environmental factors.
factors. Self-heal-
Self-healing
ing of aerospace structures can be caused by external heat, UV radiation, etc.,
of aerospace structures can be caused by external heat, UV radiation, etc., thus preventing thus pre-
ventingstructural
possible possible structural damage effects.
damage effects.

Figure3.3.Self-healing
Figure Self-healingmechanism
mechanismininpolymer
polymernanocomposite
nanocompositeusing
usingnanocapsules.
nanocapsules.Reprinted
Reprintedwith
with
permission from [73]. 2018, Elsevier.
permission from [73]. 2018, Elsevier.

Zhuand
Zhu andco-workers
co-workers [81]
[81] industrialized
industrialized aerospace
aerospace nanocomposites
nanocomposites withwith UV-respon-
UV-responsive
sive nanocapsules. The self-healing materials revealed fine performance
nanocapsules. The self-healing materials revealed fine performance for aerospace structures for aerospace
facing radiation damages [82,83]. In addition, the nanocapsules caused self-healingself-
structures facing radiation damages [82,83]. In addition, the nanocapsules caused of
healing oforscratched
scratched damagedoraerospace
damagedstructures
aerospace[84].structures
Paolillo [84].
andPaolillo and co-researchers
co-researchers [23] explored [23]
explored self-healing
self-healing in epoxy nanomaterials
in epoxy nanomaterials for aerospace. forThe
aerospace.
self-healingThemechanism
self-healingwas mechanism
studied
wasfound
and studied toand found to
be reliant onbereversible
reliant on physical
reversibleorphysical
chemical or crosslinking
chemical crosslinking in the
in the matrix.
matrix. Polyethylene-co-methacrylic
Polyethylene-co-methacrylic particlesparticles
were also were
foundalsotofound to effectively
effectively heal theheal the dam-
damages in
ages
the in the
epoxy epoxy[85].
matrix matrix [85].
Graphenenanofiller
Graphene nanofillerhas hasbeen
beenused
usedforforthetheself-healing
self-healing of of epoxy
epoxy materials
materials [86,87].
[86,87].
Graphene
Grapheneisisa two-dimensional
a two-dimensional nanostructure
nanostructure consisting
consisting of2 sp
of sp hybridized
2 hybridizedcarbon atomsatoms
carbon [88].
In 2004,
[88]. Andre
In 2004, GeimGeim
Andre and andKonstantin
Konstantin Novoselov
Novoselov prepared
prepared andandreported
reportedsingle-layer
single-layer
graphene
graphene[89].[89].However,
However,theoretically,
theoretically, graphene
graphene waswasreported
reportedearlier in 1947
earlier (P. R.
in 1947 (P.Wallace)
R. Wal-
and
lace)then
andexperimentally
then experimentallyexplored in 1962 [90].
explored in 1962Graphene revealedrevealed
[90]. Graphene excellent excellent
structuralstruc-
and
physical properties. Self-healing vitrimer epoxy/graphene oxide
tural and physical properties. Self-healing vitrimer epoxy/graphene oxide nanocompo- nanocomposites have
been
sitesfabricated
have been[91–93]. The [91–93].
fabricated self-healing
The features of these
self-healing nanomaterials
features were due to thewere
of these nanomaterials ex-
changeable
due to thecovalent network
exchangeable formation
covalent in the vitrimer
network formation epoxy resin
in the [94]. Krishnakumar
vitrimer epoxy resin and [94].
co-workers
Krishnakumar [95] also
and studied
co-workers the self-healing effect in
[95] also studied thevitrimer/graphene
self-healing effectoxide nanocom-
in vitrimer/gra-
posites. The self-healing
phene oxide effect was
nanocomposites. Thestudied at 60 ◦effect
self-healing C. Recovery occurred
was studied in 5°C.
at 60 min. Inclusion
Recovery oc-
ofcurred
0.5–1 inwt.% graphene oxide caused 80–88% self-healing of the
5 min. Inclusion of 0.5–1 wt.% graphene oxide caused 80–88% self-healing nanocomposites, relative
of the
tonanocomposites,
the neat epoxy matrixrelative(60–73%).
to the neat Hu et al. matrix
epoxy [96] also tested self-healing
(60–73%). Hu et al. [96] epoxy/graphene
also tested self-
oxide nanocomposites. The epoxy resin was reacted with
healing epoxy/graphene oxide nanocomposites. The epoxy resin was reacted β-cyclodextrin and azobenzene
with β-cy-
functional
clodextringraphene oxide via
and azobenzene free radical
functional copolymerization.
graphene oxide via free The self-healing
radical effect was
copolymerization.
studied through ultraviolet
The self-healing curing and
effect was studied the thermal
through ultravioleteffect. β-cyclodextrin/azobenzene
curing and the thermal effect. β-
functional
cyclodextrin/azobenzene functional graphene oxide acted as a well
graphene oxide acted as a photothermal agent as a macro-crosslinking
photothermal agent as well
agent. Figure 4 shows the self-healing phenomenon in epoxy
a macro-crosslinking agent. Figure 4 shows the self-healing phenomenon in epoxy nano- nanocomposites with
β-cyclodextrin/azobenzene functional graphene oxide. The
composites with β-cyclodextrin/azobenzene functional graphene oxide. The nanofillers nanofillers initiated poly-
mer chain polymer
initiated mobility chain
in the mobility
damagedinareas to cause self-healing.
the damaged areas to cause In addition, these
self-healing. Inmaterials
addition,
had fine mechanical properties. Table 1 shows the healing efficiency of the epoxy/graphene
these materials had fine mechanical properties. Table 1 shows the healing efficiency of the
 J. Compos. Sci. 2023, 7, x FOR PEER REVIEW 6 of 26
J. Compos. Sci. 2023, 7, 148 6 of 26

epoxy/graphene
oxide nanocomposites oxideusing
nanocomposites usingand
both the thermal both the thermal effects.
photoinduced and photoinduced effects.
The photothermal
The photothermal self-healing efficiency was found to be higher than that of the
self-healing efficiency was found to be higher than that of the heating effect. The strength heating
effect. The
recovery strength
rates recovery rates
of the photothermal of the photothermal
self-healed samples wereself-healed
also foundsamples werethan
to be higher also
found to be higher than those of the heated samples. In both the effects, self-healing
those of the heated samples. In both the effects, self-healing was improved with an increase was
inimproved
time. with an increase in time.

Figure4.4.Schematic
Figure Schematicillustration
illustrationofofself-healing
self-healingmechanism
mechanismofofepoxy
epoxynanocomposite
nanocompositefilms.
films.Reprinted
Reprinted
with permission from [96]. 2022,
with permission from [96]. 2022, ACS. ACS.

Table1.1.Heating
Table Heatingor orphotothermal
photothermaleffect
effecttriggered
triggeredself-healing
self-healingefficiencies
efficienciesofofepoxy
epoxynanocomposite
nanocomposite
films at different times EAG = epoxy/functional graphene oxide. Reprinted with permission from from
films at different times EAG = epoxy/functional graphene oxide. Reprinted with permission [96].
[96]. 2022, ACS.
2022, ACS.
Self-Healing Efficiencies (%)/Recovered Tensile Stress (MPa)
Self-Healing Efficiencies (%)/Recovered Tensile Stress (MPa)
Sample Heating (120 °C) Photothermal Effect (NIR, 2 W)
Heating (120 ◦ C) Photothermal 5Effect
Sample 5 Min 15 Min 30 Min 1 Min Min(NIR, 2 W) 10 Min
EAG-5 5 Min
17.3/4.1 15 Min
33.4/7.8 30 Min
37.0/8.7 1 Min
−/− 518.9/4.4
Min 1023.1/5.4
Min
EAG-5
EAG-10 17.3/4.1
33.1/6.9 33.4/7.8
70.5/14.7 37.0/8.7
79.2/16.5 −/−
22.6/4.7 18.9/4.4
52.8/11.0 23.1/5.4
59.4/12.4
EAG-10 33.1/6.9 70.5/14.7 79.2/16.5 22.6/4.7 52.8/11.0 59.4/12.4
EAG-15 45.3/6.1 73.2/9.9 85.1/11.5 29.4/4.0 55.3/7.5 63.4/8.6
EAG-15 45.3/6.1 73.2/9.9 85.1/11.5 29.4/4.0 55.3/7.5 63.4/8.6
Self-healing polymer/carbon nanotube nanocomposites have been designed for aer-
Self-healing
ospace polymer/carbon
applications nanotube nanocomposites
[97]. In the nanomaterials, addition of carbonhave been designed
nanotube may formfor re-
aerospace applications [97]. In the nanomaterials, addition of carbon
versible hydrogen bonding interactions in the polymers [98,99]. Consequently, nanotube may theform
self-
reversible hydrogen bonding
healing phenomenon relies oninteractions in thethrough
damage repair polymersthe[98,99]. Consequently,
bond formation. the self-
In addition to
healing phenomenon relies on damage repair through the bond formation.
physical interactions, functional carbon nanotube may develop covalent bonds with the In addition
to physical interactions, functional carbon nanotube may develop covalent bonds with
polymers [100]. Depending on functionalities, carbon nanotube may act as an electron do-
the polymers [100]. Depending on functionalities, carbon nanotube may act as an electron
nor or acceptor in relation to polymers for the formation of covalent bonding. Wang et al.
donor or acceptor in relation to polymers for the formation of covalent bonding. Wang
[101] fabricated self-healing epoxy/carbon nanotube nanocomposites. The composite lam-
et al. [101] fabricated self-healing epoxy/carbon nanotube nanocomposites. The composite
inates consisted of layers of carbon nanotube sheets with intervening layers of carbon fi-
laminates consisted of layers of carbon nanotube sheets with intervening layers of carbon
bers. Composite laminates with copper foam sheets were also formed. Carbon-nanotube-
fibers. Composite laminates with copper foam sheets were also formed. Carbon-nanotube-
based nanosheets have fine nanoparticle dispersion in the laminates [102,103]. Figure 5
based nanosheets have fine nanoparticle dispersion in the laminates [102,103]. Figure 5
shows the healing efficiency of the layered epoxy/carbon nanotube nanocomposite. The
shows the healing efficiency of the layered epoxy/carbon nanotube nanocomposite. The
nanocomposite with a carbon nanotube nanosheet revealed an average healing efficiency
nanocomposite with a carbon nanotube nanosheet revealed an average healing efficiency
of 107.7% for fracture energy and 96.22% healing efficiency for peak load. Here, the max-
of 107.7% for fracture energy and 96.22% healing efficiency for peak load. Here, the
imum healing efficiency (fracture energy) was 141% for a carbon nanotube nanosheet-
maximum healing efficiency (fracture energy) was 141% for a carbon nanotube nanosheet-
basedsample.
based sample. The
The composite
composite withwith copper
copper foam
foamsheet
sheethad
hadaverage
averagehealing
healingefficiencies
efficienciesof
63.2% (fracture energy) and 58.8% (peak load). The maximum healing
of 63.2% (fracture energy) and 58.8% (peak load). The maximum healing efficiency efficiency (fracture
(frac-
energy) was 128% for composite with copper foam sheet. The healing
ture energy) was 128% for composite with copper foam sheet. The healing efficiency efficiency of aofcar-
a
bon-nanosheet-based nanocomposite
carbon-nanosheet-based nanocompositewas wasfound
foundtotobe
be much
much elevated compared to
elevated compared tothethe
copperfoam
copper foamsheet
sheetmaterial
material[104–106].
[104–106].An
Anenhanced
enhancedself-healing
self-healingeffect
effectofofthe
theepoxy/carbon
epoxy/carbon
nanotube nanocomposite was observed owing to the matrix–nanofiller
nanotube nanocomposite was observed owing to the matrix–nanofiller interactions and interactions and
interface formation [107].
interface formation [107].
J.J. Compos.
Compos. Sci. 2023, 7,
Sci. 2023, 7, 148
x FOR PEER REVIEW 77 of
of 26
26
J. Compos. Sci. 2023, 7, x FOR PEER REVIEW 7 of 26

Figure 5.
Figure 5. Healing
Healing efficiency
efficiency of
of nanocomposites
nanocomposites with
with CNS
CNS and
and CFS
CFSnanomaterial.
nanomaterial. CNS
CNS == carbon
carbon
Figure 5. Healing efficiency of nanocomposites with CNS and CFS nanomaterial. CNS = carbon
nanotube nanosheet;
nanotube nanosheet; CFS
CFS == copper
copper foam
foam sheet.
sheet. Reprinted
Reprinted with
with permission
permission from
from [101].
[101]. 2016,
2016, Royal
Royal
nanotube nanosheet; CFS = copper foam sheet. Reprinted with permission from [101]. 2016, Royal
Society
Society Open Science (Creative Commons Attribution License).
SocietyOpen
Open Science (Creative Commons
Science (Creative CommonsAttribution
AttributionLicense).
License).

Guadagno
Guadagno
Guadagno and and co-workers
and co-workers[108]
co-workers [108]industrialized
[108] industrializedepoxy
industrialized epoxy
epoxy nanocomposites
nanocomposites
nanocomposites with with
non-non-
with non-
functional
functional carbon
functionalcarbon nanotube,thymine
carbonnanotube,
nanotube, thymine
thymine functional
functional
functional carbon
carbon
carbon nanotube
nanotube
nanotube andand
and barbiturate
barbiturate
barbiturate func-
functional
func-
tional
tional carbon
carbon nanotube
carbon nanotube foraerospace.
aerospace.
for aerospace.
nanotube for Thestructures
The structures
The structures
and and and interactions
interactions aofthymine
of aofthymine
interactions a thymine
ligand ligand
ligand func-
functional
tional carbon nanotube and epoxy/thymine functional carbon
functional carbon nanotube and epoxy/thymine functional carbon nanotube nanocompo- are
carbon nanotube and epoxy/thymine functional carbon nanotube
nanotube nanocompo-
nanocomposite
site
site are
given in given
are Figurein6.Figure
given Figure
Hydrogen6.6.Hydrogen
Hydrogen bondinginteractions
bondingbonding
interactionsinteractions
were observedwere
were observed
between
observed between
C=O
between and
C=O C=O
O–H
and
and O–H
O–H functionalities
functionalities
functionalities of epoxy and ofofepoxy
epoxy
N–H and andN–H N–Hfunctionalities
functionalitiesfunctionalities of carbon
of carbonofnanotube
carbon nanotube
nanotube
[109,110]. [109,110].
[109,110].
The forma-
The
Theof
tion formation
formation
reversible reversibleinteractions
of interactions
reversible interactions
was suggested wassuggested
was suggested
for forfor
thethe
the self-healing self-healing
self-healing
phenomenon phenomenon
phenomenon
in the epoxy
in the
in the epoxy
epoxy nanocomposites.
nanocomposites. nanocomposites. Figure 7 7establishes
Figurethe
Figure 7 establishes establishes
self-healingthethe
self-healing
self-healing
efficiency efficiency
efficiency
of various of various
of various
nanocomposite
nanocomposite
nanocomposite
samples. Among samples.
samples. Among
Amongall
all nanocomposite allnanocomposite
nanocomposite
samples, 0.5 wt.% samples,
samples, 0.50.5
contents wt.%
wt.%
of contents
contents
thymine of thy-
of thy-
functional
mine functional
carbon
mine functional
nanotubecarbon
led to nanotube
carbon nanotubeled
enhanced ledtotoenhanced
self-healing self-healing
properties
enhanced dueproperties
self-healing toproperties duedue
the existence to of
the exist-
toreversible
the exist-
ence
hydrogenof reversible
bonding hydrogen bonding
interactions [111]. interactions
ence of reversible hydrogen bonding interactions [111]. [111].

Figure 6. Representation of supramolecular network generated into the cured sample ETCNT TCNT
Figure 6. Representation of supramolecular network generated into the cured sample ETCNT
= carbon nanotube functionalized with thymine; ETCNT = epoxy/carbon nanotube functionalized
TCNT
Figure =6.carbon nanotube
Representation
with thymine-based
functionalized
of
ligand.
with
supramolecular thymine;
network ETCNTinto
generated
Reprinted with permission
=2021,
from [108].
epoxy/carbon
theElsevier. nanotube
cured sample ETCNTfunction-
TCNT
alized with
= carbon thymine-based
nanotube ligand. Reprinted
functionalized withETCNT
with thymine; permission from [108]. 2021,
= epoxy/carbon Elsevier.
nanotube functionalized
with thymine-based ligand. Reprinted with permission from [108]. 2021, Elsevier.
J.J.Compos.
Compos.Sci. 2023,7,7,148
Sci.2023, x FOR PEER REVIEW 8 of
of2626

Figure 7. Self-healing efficiency for the nanocomposite samples containing non-functional CNT
Figure 7. Self-healing efficiency for the nanocomposite samples containing non-functional CNT
(ECNT 0.5 wt.%), thymine functional CNT (ETCNT 0.5 wt.%; ETCNT 2.0 wt.%) and barbiturate
(ECNT 0.5 wt.%), thymine functional CNT (ETCNT 0.5 wt.%; ETCNT 2.0 wt.%) and barbitu-
functional CNT (EBCNT 0.5 wt.%; EBCNT 2.0 wt.%) as function of: (a) time and (b) number of cy-
rate
cles.functional
ETCNT =CNT (EBCNT 0.5nanotube
epoxy/carbon wt.%; EBCNT 2.0 wt.%)with
functionalized as function of: (a) time
thymine-based and EBCNT
ligand; (b) num-=
ber
epoxy/carbon nanotube functionalized with barbituric-acid-based ligands. Reprinted with ligand;
of cycles. ETCNT = epoxy/carbon nanotube functionalized with thymine-based permis-
EBCNT = epoxy/carbon
sion from[108]. nanotube functionalized with barbituric-acid-based ligands. Reprinted with
2021, Elsevier.
permission from[108]. 2021, Elsevier.
Guadagno and co-researchers [112] fabricated tetraglycidyl methylene dianiline
epoxyGuadagno
(cured and
withco-researchers [112] fabricated
carboxyl-terminated tetraglycidyl
butadiene methylene
acrylonitrile, dianiline epoxy
1,4-butanedioldiglyc-
(cured with
idylether- carboxyl-terminated butadiene acrylonitrile, 1,4-butanedioldiglycidylether-
and 4,4′-diaminodiphenyl sulfone)-based nanocomposites. The barbiturate
and 4,40 -diaminodiphenyl
functional sulfone)-based
multiwalled carbon nanotube wasnanocomposites. The barbiturate
used as a nanofiller. functional
A self-healing effect in
multiwalled
epoxy nanocomposites was observed due to the inclusion of barbiturate-modifiedepoxy
carbon nanotube was used as a nanofiller. A self-healing effect in nano-
nanocomposites was observed due to the inclusion of barbiturate-modified nanofiller [113].
filler [113]. The functional multiwalled carbon nanotube formed reversible hydrogen
The functional multiwalled carbon nanotube formed reversible hydrogen bonding, causing
bonding, causing a self-healing effect in the nanomaterial (Figure 8). Variation in mor-
a self-healing effect in the nanomaterial (Figure 8). Variation in morphology and interfacial
phology and interfacial regions were also observed for the self-healing nanocomposites. a
regions were also observed for the self-healing nanocomposites. a self-healing phenomenon
self-healing phenomenon was observed in the epoxy matrix with 0.5 wt.% of functional
was observed in the epoxy matrix with 0.5 wt.% of functional as well as non-functional
as well as non-functional nanofiller. The storage modulus of the epoxy nanocomposites
nanofiller. The storage modulus of the epoxy nanocomposites with modified nanofiller
with modified nanofiller and different temperatures has been studied (Figure 9). With
and different temperatures has been studied (Figure 9). With increasing temperature from
increasing temperature from −50 to 120 °C, the storage modulus of the nanocomposites
−50 to 120 ◦ C, the storage modulus of the nanocomposites was found to decrease. The
was found to decrease. The addition of modified filler positively affected the storage mod-
addition of modified filler positively affected the storage modulus of the nanocomposite
ulus of the nanocomposite due to the presence of reversible crosslinking in the matrix–
due to the presence of reversible crosslinking in the matrix–nanofiller.
nanofiller.
J. Compos. Sci. 2023, 7, 148 9 of 26
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Figure8.8.The
Figure Thebarbiturate-modified
barbiturate-modifiedMWCNT
MWCNTfor forreversible
reversibleopening
openingand
andclosing
closingof
ofhydrogen
hydrogenbonds
bonds
Figure
during8.damage
The barbiturate-modified
and healing event.MWCNT
MWCNT for
= reversible opening
multiwalled carbon and closingReprinted
nanotube. of hydrogen bonds
with per-
during damage and healing event. MWCNT = multiwalled carbon nanotube. Reprinted with
during
missiondamage
from and 2019,
[112]. healing event.(Creative
Elsevier MWCNTCommons
= multiwalled carbon nanotube. Reprinted with per-
CC-BY).
permission
mission from from [112].
[112]. 2019,
2019, Elsevier
Elsevier (Creative
(Creative Commons
Commons CC-BY).
CC-BY).

Figure 9. Storage modulus of nanocomposites at three different temperatures TCTBD = tetraglycidyl

Figure
Figure 9. Storage
9.
methylene Storage modulus
modulus
dianiline ofof
modified nanocomposites
nanocomposites at three
at three different
different
with carboxyl-terminated temperatures
temperatures
butadiene TCTBD TCTBD = tetraglycidyl
= tetraglycidyl
acrylonitrile, methy-
1,4-butanedioldi-
methylene
lene dianiline
glycidylether dianiline
modified modified with carboxyl-terminated
with carboxyl-terminated
and 4,4′-diaminodiphenyl butadiene
sulfone; MWCNT butadiene acrylonitrile,
acrylonitrile, 1,4-butanedioldi-
1,4-butanedioldiglycidylether
= multiwalled carbon nanotube. Re-
glycidylether
and and 4,4′-diaminodiphenyl
4,40 -diaminodiphenyl
printed with permission sulfone; 2019,sulfone;
MWCNT
from [112]. =Elsevier MWCNT
multiwalled carbon
(Creative = nanotube.
multiwalled
Commons carbonwith
Reprinted
CC-BY). nanotube. Re-
permission
printed with permission from [112]. 2019, Elsevier (Creative Commons CC-BY).
from [112]. 2019, Elsevier (Creative Commons CC-BY).
5. Significance of Self-Healing Nanocomposites in Space Sector
5. Significance
5. Significance of ofSelf-Healing
Self-HealingNanocomposites
Nanocompositesin inSpace
SpaceSector
Sector
5.1. Aerospace Engines
5.1.
5.1. Aerospace
Aerospace Engines
Engines
Traditionally, engines have been developed using ceramic and metallic materials
Traditionally,
Traditionally, engines
engineshave
have been developed
been developed using ceramic
using and metallic
ceramic materials [114].
[114]. Afterward, polymeric materials and composites have beenand
usedmetallic materials
in high-tempera-
Afterward, polymeric
[114]. Afterward, materials
polymeric and composites
materials and composites have have
been been
usedused
in high-temperature-
in high-tempera-
ture-resistant jet engine components [115,116]. Moreover, using composite materials has
resistant jet engine
ture-resistant components
jet engine [115,116].
components Moreover,
[115,116]. using composite
Moreover, materials
using composite has prohib-
materials has
prohibited
ited structural
structural damage damage
related related
to to impact/failure.
impact/failure. In In turbine
turbine bladesblades
of of engines,
engines, com-
composite
prohibited structural
posite materials have damage related
been successfully to impact/failure.
used. In turbine
In the combustion blades
chamber of engines, com-
of spaceengines,
vehicle
materials have been
posite materials havesuccessfully used. Inused.
been successfully the combustion chamberchamber
In the combustion of space of
vehicle
space vehicle
engines,
ceramic ceramic
fibers fibers
havefibers have the
the capability capability
tocapability to
withstandtovery withstand very high
high temperatures temperatures (1000–
(1000–1350 ◦ C)(1000–
[117].
engines,
1350 °C) ceramic
[117]. have
Consequently, the self-healing withstand
nanocomposites very high
have temperatures
been used to produce
Consequently,
1350 °C) [117].self-healing
Consequently,nanocomposites have been used to
self-healing nanocomposites produce
have been fixed
used and mobile
to produce
fixed and mobile jet engine components [118,119]. In particular, for aerospace combustion
fixed and mobile jet engine components [118,119]. In particular, for aerospace combustion
J. Compos. Sci. 2023, 7, 148 10 of 26
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jet engine components [118,119]. In particular, for aerospace combustion chambers, self-
chambers,
healing self-healing nanocomposites
nanocomposites have been designed have[120,121].
been designed [120,121].
In addition In addition
to high to high
temperature,
temperature, pressure, and damage resistance, self-healing nanomaterials
pressure, and damage resistance, self-healing nanomaterials revealed corrosion resistance revealed corro-
sion resistance properties for engine components [122]. The superior
properties for engine components [122]. The superior properties of self-healing nanocom- properties of self-
healing
posites nanocomposites
have enhanced thehave enhanced
efficiency the efficiency
of turbine enginesof turbine
[123]. Tongengines [123].proposed
et al. [124] Tong et al.
[124] proposed
nanomaterials fornanomaterials
the compressor for casing
the compressor casing of
of aero engines oraero
gas engines
turbinesortogas turbines
attain highto
attain high efficiency and low fuel consumption. Using self-healing
efficiency and low fuel consumption. Using self-healing materials enhanced the scratch materials enhanced
the to
force scratch
resist force
bladeto resist blade
vibrations andvibrations
engine jams.andEpoxy-based
engine jams.materials
Epoxy-based
with materials with
31 wt.% hol-
31 wt.% hollow microspheres possess high bonding strength. However,
low microspheres possess high bonding strength. However, such materials may have 63% such materials
may have
porosity and63% porosityofand
a hardness 33.aFigure
hardness of 33. Figure
10 shows features10 of
shows features
pristine of pristine
material material
and material
anduse
after material after use
in an engine. in an engine.
Porosity was foundPorosity was found
to increase in theto increaseThe
material. in the material.
tensile The
fracture
tensile
crack wasfracture
found to crack was found
propagate withto propagate
a large with a large diameter.
diameter.

Figure 10. Schematic diagram of (a) original material and (b) tensile fracture surface after use in
Figure 10. Schematic diagram of (a) original material and (b) tensile fracture surface after use
engine. HMS = phenolic resin hollow microspheres. Reprinted with permission from [124]. 2021,
in engine. HMS = phenolic resin hollow microspheres. Reprinted with permission from [124].
Elsevier.
2021, Elsevier.
5.2.
5.2. Space
Space Structures
Structures
Self-healing
Self-healing nanocomposites
nanocomposites havehave been scrutinized
been scrutinized for aerospace
for aerospace structures
structures [125,126].
[125,126]. In high-performance aerospace structural parts, self-healing
In high-performance aerospace structural parts, self-healing fiber-reinforced composites fiber-reinforced
composites
have have been
been applied [127].applied [127]. Thematerials
The composite composite materials
have have an
an aptitude aptitude
for capablyfor capably
healing
healing
micro micro
cracks andcracks
fatigueand fatigue damage.
damage. In addition In addition to self-healing,
to self-healing, these materials
these materials have supe-have
superior
rior mechanical
mechanical features features for aerospace
for aerospace structures.
structures. Aerospace-grade
Aerospace-grade laminates laminates
have beenhave
been developed
developed using self-healing
using self-healing epoxy/E-glass
epoxy/E-glass fiber composites.
fiber composites.
The self-healing epoxy/carbon fiber
The self-healing epoxy/carbon fiber laminates have laminates havealsoalsobeen
beenused
usedforfor aerospace
aerospace
structures [128]. Moreover, healing
structures [128]. Moreover, healing agents have agents have been used to
to enhance the self-healingef-
enhance the self-healing
ficiency of
efficiency ofepoxy-based
epoxy-basedspace spacematerials.
materials.For Forexample,
example,formaldehyde/urea
formaldehyde/ureamicrocapsules
microcapsules
have
have been
been usedused as healing
as healing agentsagents for diglycidyl
for diglycidyl ether ether of an bisphenol
of an bisphenol A epoxy A matrix
epoxy [129].
matrix
[129].
The epoxyThematrix
epoxywas matrix
found wasto found to be reversibly
be reversibly crosslinked crosslinked during self-healing,
during self-healing, with the help with
ofthe helpor
micro- of nanocapsules.
micro- or nanocapsules.
In this way,In this way, reformation
efficient efficient reformation
of matrix ofcracks
matrixhas cracks
beenhas
observed to regain the structural integrity. Kessler and co-researchers
been observed to regain the structural integrity. Kessler and co-researchers [130] fabri- [130] fabricated self-
healing
cated Bisphenol
self-healing A diglycidyl
Bisphenol ether epoxy-based
A diglycidyl ethermaterials.
epoxy-based Scanning electron
materials. micrographs
Scanning electron
ofmicrographs
fracture surfaces of self-healing
of fracture surfaces materials are given
of self-healing in Figure
materials 11.given
are In a delaminated
in Figure 11.matrix,
In a de-
self-healing
laminated agentmatrix,can be observed
self-healing to be
agent canbridging
be observedthe matrix strands the
to be bridging for matrix
the self-healing
strands for
process. The loading
the self-healing curvesThe
process. of neat and healed
loading curves samples
of neat andare healed
given insamples
Figure 12.areSelf-healing
given in Fig-
was observed at 80 ◦ C (48 h). For the self-healed sample, crack propagation was less
ure 12. Self-healing was observed at 80 °C (48 h). For the self-healed sample, crack propa-
prominent
gation was relative to the neatrelative
less prominent epoxy to sample.
the neatProminent
epoxy sample.crack development
Prominent crack mid-plane
develop-
was observed for pristine epoxy material. Thus, self-healing
ment mid-plane was observed for pristine epoxy material. Thus, self-healing epoxy,epoxy, epoxy/nanocarbon
nanomaterials
epoxy/nanocarbon and polymer/carbon
nanomaterialsfiber/nanocarbon
and polymer/carbon nanocomposites
fiber/nanocarbonhave nanocomposites
been exploited
forhave
aircraft
beenand space vehicles
exploited [131].
for aircraft and space vehicles [131].
J. Compos. Sci. 2023, 7, 148 11 of 26
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Figure 11. Scanning electron microscopy images of healed fracture surfaces of self-healing sample
Figure 11.Scanning
Figure11. Scanningelectron
electronmicroscopy
microscopyimages
imagesofofhealed
healedfracture
fracturesurfaces
surfacesofofself-healing
self-healingsample
sample
(30 min healing time). Reprinted with permission from [130]. 2003, Elsevier.
(30
(30min
minhealing
healingtime).
time).Reprinted
Reprintedwith
withpermission
permissionfrom
from[130].
[130].2003,
2003,Elsevier.
Elsevier.

Figure 12. Typical loading curves of pristine and healed self-healing samples (note: healing condi-
Figure 12. Typical loading curves of pristine and healed self-healing samples (note: healing condi-
Figure 48 hTypical
tions =12. loading
at 80 °C). curves
Reprinted withofpermission
pristine and healed
from [130]. self-healing samples
2003, Elsevier. (note: healing
tions = 48 h at 80 °C). Reprinted
◦ with permission from [130]. 2003, Elsevier.
conditions = 48 h at 80 C). Reprinted with permission from [130]. 2003, Elsevier.
Self-healing ability of materials have been achieved at the cost of sacrificing their me-
Self-healingability
Self-healing abilityofofmaterials
materials havebeenbeenachieved
achievedatatthe
thecost
costofofsacrificing
sacrificingtheir
theirme-
me-
chanical properties. Williams et al. have[132] designed epoxy/carbon fiber/hollow glass fiber
chanicalproperties.
chanical properties.Williams
Williamsetetal.al. [132]
[132] designed
designed epoxy/carbonfiber/hollow
epoxy/carbon fiber/hollowglassglassfiber
fiber
composites. Inclusion of glass fibers caused flexural strength recovery of 97%. However,
composites.Inclusion
composites. Inclusionofofglass
glassfibers
fiberscaused
causedflexural
flexuralstrength
strengthrecovery
recoveryofof97%.97%.However,
However,
the mechanical recovery was reduced in repeated testing. A reduction in flexural strength
themechanical
the mechanicalrecovery
recoverywas wasreduced
reducedininrepeated
repeatedtesting.
testing.AAreduction
reductionininflexural
flexuralstrength
strength
of the healed samples is given in Table 2. Flexural analysis showed that damaged and
ofofthe
thehealed
healedsamples
samplesisisgiven
givenininTable
Table2.2.Flexural
Flexuralanalysis
analysisshowed
showedthat thatdamaged
damagedand and
healed samples revealed considerable reduction in flexural strength relative to undam-
healedsamples
healed samples revealed
revealed considerable
considerable reduction
reduction in flexural
in flexural strength
strength relative
relative to undam-
to undamaged
aged samples. This effect was attributed to significant variation in fiber architecture after
aged samples.
samples. Thiswas
This effect effect was attributed
attributed to significant
to significant variationvariation in fiber architecture
in fiber architecture after
after healing.
healing. Effects of healing components on epoxy composite structures for aerospace struc-
Effects of Effects
healing. healingofcomponents on epoxy on
healing components composite structuresstructures
epoxy composite for aerospace structuralstruc-
for aerospace ap-
tural applications have been scrutinized [133]. The DGEBA/carbon composite with micro-
plications have been scrutinized [133]. The DGEBA/carbon composite with
tural applications have been scrutinized [133]. The DGEBA/carbon composite with micro- microcapsules,
capsules, with a healing agent and catalyst, revealed reduced mechanical properties. The
with a healing
capsules, withagent and catalyst,
a healing agent andrevealed reduced
catalyst, mechanical
revealed reducedproperties.
mechanicalThe mechanical
properties. The
mechanical properties of composites without a healing agent and catalyst were decreased.
mechanical properties of composites without a healing agent and catalyst were decreased.
However, fine recovery of mechanical properties was attained with healing agents. Teoh
However, fine recovery of mechanical properties was attained with healing agents. Teoh
J. Compos. Sci. 2023, 7, 148 12 of 26

J. Compos. Sci. 2023, 7, x FOR PEER REVIEW 12 of 26

properties of composites without a healing agent and catalyst were decreased. However,
fine recovery of mechanical properties was attained with healing agents. Teoh et al. [134]
proposed a self-healing
et al. [134] proposed aepoxy composite
self-healing withcomposite
epoxy a healing agent
with afor aerospace
healing structures.
agent The
for aerospace
specimens were damaged by indentation, and three-point bend flexural tests
structures. The specimens were damaged by indentation, and three-point bend flexural were applied.
After
testsself-healing,
were applied. good
Afterstrength recovery
self-healing, goodwas observed.
strength Epoxywas
recovery composites
observed.with E-glass
Epoxy com-
fiber
posites with E-glass fiber have been used to form aerospace structures [135]. Toohey etanal.
have been used to form aerospace structures [135]. Toohey et al. [136] developed
epoxy/fiber-based
[136] developed an self-healing system showing
epoxy/fiber-based autonomous
self-healing repair after
system showing repeated repair
autonomous damage af-
events. The healing agent was delivered into cracks of materials, which formed
ter repeated damage events. The healing agent was delivered into cracks of materials, a three-
dimensional
which formed microvascular network.microvascular
a three-dimensional The release ofnetwork.
healing agent causedof
The release bubbles
healinginagent
the
structure (Figure 13). The healing efficiency was found to be up to 70–80%. After repeated
caused bubbles in the structure (Figure 13). The healing efficiency was found to be up to
damage, 40% healing was observed.
70–80%. After repeated damage, 40% healing was observed.
Table 2. Results of flexural four-point bend testing of aerospace composites. Reprinted with permis-
Table 2. Results of flexural four-point bend testing of aerospace composites. Reprinted with per-
sion from from
mission [132].[132].
2007,2007,
Elsevier.
Elsevier.

Damaged
Damaged (CV%)
(CV%) Healed
Healed (CV%)
(CV%)
Specimen
SpecimenType
Type Properties
Properties Undamaged
Undamaged(CV%)
(CV%)
@1700
@1700 N N @1700
@1700 N N
Plain
PlainCFRP
CFRP Strength (MPa)
Strength (MPa) 583.3
583.3 538.6
538.6 – –
% undamaged
% undamaged 100%
100% 92%92% – –
Composite
Composite Strength
Strength (MPa)
(MPa) 568.8
568.8 490.1
490.1 523.4523.4
% undamaged
% undamaged 98%
98% 84%84% 90% 90%

Figure 13. (a) Schematic of microvascular substrate; (b) optical image of actual microvascular system
Figure 13. (a) Schematic of microvascular substrate; (b) optical image of actual microvascular system
after damage. Reprinted with permission from [136]. 2007, Nature.
after damage. Reprinted with permission from [136]. 2007, Nature.

5.3. Aerospace Fuselage

An important use of polymer/fiber composites has been experiential for aerospace
fuselage [137]. Here, the epoxy/carbon fiber composites and epoxy/glass fiber composites
have been operated [138,139]. In particular, these materials have been utilized in fuselage
J. Compos. Sci. 2023, 7, 148 13 of 26

5.3. Aerospace Fuselage

An important use of polymer/fiber composites has been experiential for aerospace
fuselage [137]. Here, the epoxy/carbon fiber composites and epoxy/glass fiber composites
have been operated [138,139]. In particular, these materials have been utilized in fuselage
J. Compos. Sci. 2023, 7, x FOR PEER REVIEW 13 of 26
of civil and military crafts and aerospace structures. In fuselage, self-healing composites
have been found to have the scope to overcome load, fracture, fatigue, impact and sustain-
ability issues [140,141]. In this regard, self-healing epoxy/carbon fiber/carbon nanotube
of civil and military
nanocomposites havecrafts
beenandused
aerospace structures.
to develop In fuselage, self-healing
aerospace-grade composites
fuselage [142]. Inclusion of
have been found to have the scope to overcome load, fracture, fatigue, impact and sus-
nanoparticles such as carbon nanotube and graphene may further enhance the impact
tainability issues [140,141]. In this regard, self-healing epoxy/carbon fiber/carbon nano-
resistance of epoxy/fiber nanocomposites. The fuselage materials have the capability
tube nanocomposites have been used to develop aerospace-grade fuselage [142]. Inclusion
toofself-heal various damage to the main body parts of aircraft. Relative to metal alloy-
nanoparticles such as carbon nanotube and graphene may further enhance the impact
based structures, a healing
resistance of epoxy/fiber efficiency of >90%
nanocomposites. has been
The fuselage observed
materials havefortheself-healing
capability topolymer
nanocomposites.
self-heal various damage to the main body parts of aircraft. Relative to metal alloy-basedreplaced
Consequently, metal-based space fuselage has been successfully
with the composite
structures, a healing structures
efficiency ofwith
>90%superior
has beendamage-healing properties
observed for self-healing [143].nano-
polymer
composites. Consequently, metal-based space fuselage has been successfullyof
Studies have focused on analyzing impact and mechanical properties epoxy/carbon
replaced
fiber self-healing composites [144]. Bond et al. [145] prepared self-healing epoxy/carbon
with the composite structures with superior damage-healing properties [143].
Studies have
fiber laminates to focused
overcome on impact
analyzing impact and
resistance. mechanical
The propertiesofofa epoxy/car-
flexural strength 16-ply aerospace-
grade composite with hollow glass fibers was investigated.self-healing
bon fiber self-healing composites [144]. Bond et al. [145] prepared epoxy/car-recovery
A 97% strength
bon observed
was fiber laminates
aftertoquasistatic
overcome impact resistance.
indentation The flexural
damage. The strength
epoxy/glassof a 16-ply
fiberaero-
composites
have been used in aerospace fuselage as self-healing composites, with 92%recov-
space-grade composite with hollow glass fibers was investigated. A 97% strength recovery or
ery was observed after quasistatic indentation damage. The epoxy/glass fiber composites
healing observed after impact damage. To further improve impact properties of self-
have been used in aerospace fuselage as self-healing composites, with 92% recovery or
healing epoxy/glass fiber or epoxy/carbon fiber composites for aerospace applications,
healing observed after impact damage. To further improve impact properties of self-heal-
super-elastic
ing epoxy/glass self-healing NiTi alloy wires
fiber or epoxy/carbon were usedfor
fiber composites along with carbon
aerospace or glass
applications, fiber fillers.
super-
The stacking
elastic sequences
self-healing of fiber
NiTi alloy wireslaminates
were usedand along resin
withhave
carbonbeen designed
or glass for this
fiber fillers. Thepurpose.
Inclusion of self-healing
stacking sequences of fiberwires enhanced
laminates and resinthehave
damage tolerancefor
been designed ofthis
aerospace
purpose.composites
In-
under
clusionrepeated impacts.
of self-healing wiresSelf-healing
enhanced thepolymer composites
damage tolerance have been
of aerospace investigated
composites un- as an
alternative
der repeated to impacts.
metal alloys for protecting
Self-healing polymerspace structures
composites havefrom
beenspace debris as
investigated [146].
an al-Figure 14
ternative
shows to metal alloyspropulsive
a turbo-electric for protecting space structures
fuselage from space
aircraft design debrisin
developed [146]. Figure validation
a concept 14
showsfor
study a turbo-electric propulsive propulsion
fuselage wake-filling fuselage aircraft design developed
integration (CENTRELINE)in a concept valida-
[147]. It has twin-
tion study
engine, for fuselage systems,
turbo-electric wake-filling propulsion
a fuselage fanintegration
powered(CENTRELINE)
through a generator,[147]. Itandhas geared
twin-engine, turbo-electric systems, a fuselage fan powered through
turbofan power plants podded under the wings. The fuselage internal thermal shielding a generator, and
geared turbofan power plants podded under the wings. The fuselage internal thermal
requirements and internal/external noise and vibration were reduced by using advanced
shielding requirements and internal/external noise and vibration were reduced by using
self-healing nanocomposites. Figure 15 shows that the maximum vertical displacement at
advanced self-healing nanocomposites. Figure 15 shows that the maximum vertical dis-
the fuselageattip
placement theremains
fuselagewithin 57 mm.
tip remains More
within thanMore
57 mm. 60% loads
than 60%caused
loadslocal
caused wrinkling.
local The
study indicated that using self-healing nanomaterials caused structural
wrinkling. The study indicated that using self-healing nanomaterials caused structural safety and buckling
resistance. Thus, theresistance.
safety and buckling load-carrying capability
Thus, the was enhanced
load-carrying capability using an advanced
was enhanced using an structural
design concept.
advanced structural design concept.

Figure 14. Turbo-electric propulsive fuselage aircraft design. Reprinted with permission from [147].
Figure 14. Turbo-electric propulsive fuselage aircraft design. Reprinted with permission from [147].
2021, MDPI.
2021, MDPI.
J. Compos. Sci. 2023, 7, 148 14 of 26
J. Compos. Sci. 2023, 7, x FOR PEER REVIEW 14 of 26

Figure15.
Figure 15.Displacement
Displacementmap
mapforforfuselage
fuselagenacelle
nacelleand
andintegration
integrationstructure
structureunder
underload.
load.Reprinted
Reprinted
with permission from [147]. 2021, MDPI.
with permission from [147]. 2021, MDPI.

Nonstructural aircraft
Nonstructural aircraft parts
parts such
such asas seals
seals and
andgaskets
gasketsemploy
employelastomer-based
elastomer-basedmate-
ma-
rials with high flexibility and elasticity [148]. These materials have
terials with high flexibility and elasticity [148]. These materials have low low density, highhigh
density, duc-
tility, moderate
ductility, moderatecostcost
andand
corrosion resistance.
corrosion Thermosets
resistance. Thermosetshave not not
have been used
been in seals
used and
in seals
gaskets.
and Nevertheless,
gaskets. Nevertheless,polymer
polymer composites
composites have
havebeen
beenpreferred
preferredin
in these applications.
applications.
Some research
Some researchhashasbeen
beenconducted
conductedon onself-healing
self-healingmaterials
materialsconsisting
consisting of
ofpolymer
polymerand and
naturalfibers
natural fibersfor
forgaskets
gaskets[149].
[149].However,
However,future
futureresearch
researchisisdesirable
desirableto
toexpand
expandthis
thisfield.
field.

5.4.
5.4.Coatings/Adhesives
Coatings/Adhesives
Coatings
Coatingsfor formetallic
metallicalloys
alloyssuch
such asas
aluminum,
aluminum, titanium
titaniumandandmagnesium
magnesium are are
impor-
im-
tance for civil and military aircrafts because such structures need corrosion
portance for civil and military aircrafts because such structures need corrosion protection. protection.
Self-healing
Self-healingcoatings
coatingsandandadhesives
adhesiveshavehavebeen
beenfocused
focusedfor foraerospace
aerospacestructures
structures[150].
[150].The
The
self-healing coatings and adhesives may efficiently heal the damage
self-healing coatings and adhesives may efficiently heal the damage of substrates of substrates [151,152].
In particular,
[151,152]. In anticorrosion coatings may
particular, anticorrosion easily may
coatings self-heal corrosion
easily self-healdamage.
corrosionYang and
damage.
co-workers [153] developed
Yang and co-workers [153] self-healing epoxy coatings
developed self-healing epoxy with urea formaldehyde
coatings micro-
with urea formalde-
capsules. The coatings were applied on the aerospace-grade aluminum
hyde microcapsules. The coatings were applied on the aerospace-grade aluminum surface surface [154–157].
Similarly,
[154–157].epoxy nanocomposite
Similarly, adhesives have
epoxy nanocomposite been applied
adhesives have been to heal aerospace
applied to healstructural
aerospace
damage
structural damage [158]. Self-healing epoxy/graphene nanocomposite-basedhave
[158]. Self-healing epoxy/graphene nanocomposite-based adhesives been
adhesives
effectually reported for space structures [159–161]. Adhesives and coatings
have been effectually reported for space structures [159–161]. Adhesives and coatings have been used
to cure and prevent aerospace structural damage in primary and
have been used to cure and prevent aerospace structural damage in primary and second-secondary structures
of
aryaircrafts, helicopters,
structures aero-engines
of aircrafts, helicopters,and spacecraft and
aero-engines components
spacecraft[162]. For inspection
components of
[162]. For
large aerospace components, infrared thermography has been efficiently used as a rapid
inspection of large aerospace components, infrared thermography has been efficiently
and accurate non-destructive means of evaluation (Figure 16). This method can measure
used as a rapid and accurate non-destructive means of evaluation (Figure 16). This
and analyze damage to aluminum, composites and hybrid fiber metal laminates such as
method can measure and analyze damage to aluminum, composites and hybrid fiber
carbon-reinforced aluminum laminate and carbon/glass fiber-filled aluminum and epoxy
metal laminates such as carbon-reinforced aluminum laminate and carbon/glass fiber-
laminates. Material defects may occur at any stage of component usage or cyclic life. In-
filled aluminum and epoxy laminates. Material defects may occur at any stage of compo-
frared thermography has detected and quantify the material flaws from manufacturing to
nent usage or cyclic life. Infrared thermography has detected and quantify the material
in-service or maintenance operations. Almost all materials and components can be analyzed
flaws from manufacturing to in-service or maintenance operations. Almost all materials
using an infrared thermography technique. Studies have depicted that few designs have
and components can be analyzed using an infrared thermography technique. Studies have
been studied so far for aerospace adhesives and more research efforts are needed to design
depicted that few designs have been studied so far for aerospace adhesives and more re-
innovative coatings and adhesives for aerospace. Meure and co-workers [163] formed
search efforts
self-healing are materials
epoxy needed towith design innovative coatings andacid
polyethylene-co-methacrylic adhesives
particlesforinaerospace.
adhesive.
Meure and co-workers [163] formed self-healing epoxy materials
Figure 17 shows fractured and healed epoxy system with polyethylene-co-methacrylic with polyethylene-co-
methacrylic
acid particles.acid particles
Healing wasin adhesive.
observed at Figure
150 ◦ C.17 shows fractured and healedacid
Polyethylene-co-methacrylic epoxy sys-
caused
tem with polyethylene-co-methacrylic acid particles. Healing was
a pressure-driven healing mechanism of the epoxy system. Inclusion of nanocapsules observed at 150 °C. Pol-
yethylene-co-methacrylic
enhanced complete damage acid caused aduring
recovery pressure-driven
self-healing. healing mechanism ofburst
The nanocapsules the epoxy
and
system. Inclusion of nanocapsules enhanced complete damage recovery
released a healing agent for damage recovery. Therefore, efficient self-healing nanocompos- during self-heal-
ing.have
ites The nanocapsules
been applied in burst and released
aerospace a healing
structures. The agent for damage
self-healing recovery.
materials help toTherefore,
recover
efficient self-healing nanocomposites have been applied in aerospace structures. The self-
J.J. Compos.
Compos. Sci.
Sci. 2023,
2023, 7,
7, 148
x FOR PEER REVIEW 15
15 of 26
of 26

healing structures
aircraft materials help to recover
that have aircraftdamage
experienced structures
duethat havecycles,
to heat experienced damageatomic
UV radiation, due to
heat cycles,
oxygen, UVdebris,
space radiation, atomic oxygen, space debris, etc. [164].
etc. [164].

Figure 16. Illustration of typical material defects monitored by IRT for composite aircraft and space-
Figure 16. Illustration of typical material defects monitored by IRT for composite aircraft and
craft structures (a); jet engine turbine blades (b); honeycomb panels (c) and metallic aircraft and
spacecraft
spacecraft structures
components (a);(d).
jet engine turbine
Reprinted withblades (b); honeycomb
permission from [162].panels
2018, (c) and metallic aircraft and
MDPI.
spacecraft components (d). Reprinted with permission from [162]. 2018, MDPI.

.
Figure 17. Schematic of healing agent delivery mechanism in epoxy-resin-containing healing agent
Figure 17. Schematic of healing agent delivery mechanism in epoxy-resin-containing healing agent
containing particles in
containing particles in adhesives.
adhesives.EMAA
EMAA = polyethylene-co-methacrylic
= polyethylene-co-methacrylic acid.
acid. Reprinted
Reprinted withwith
per-
permission from [163]. 2009, Elsevier.
mission from [163]. 2009, Elsevier.
6. Mechanism of Self-Healing in Space Nanocomposites
6. Mechanism of Self-Healing in Space Nanocomposites
The self-healing phenomena in these nanocomposites have been found to operate
The self-healing phenomena in these nanocomposites have been found to operate
through various mechanisms [19]. These mechanisms can repair the damage to struc-
through various mechanisms [19]. These mechanisms can repair the damage to structures
tures [165]. Depending on the capability of self-healing materials, they are often referred
[165]. Depending on the capability of self-healing materials, they are often referred to as
J. Compos. Sci. 2023, 7, x FOR PEER REVIEW 16 of 26
J. Compos. Sci. 2023, 7, 148 16 of 26

intrinsic or extrinsic self-healing materials. Intrinsic self-healing polymers undergo dy-

to as intrinsic or extrinsic self-healing materials. Intrinsic self-healing polymers undergo
namic covalent chemistry and non-covalent chemistry using secondary interactions (Fig-
dynamic covalent chemistry and non-covalent chemistry using secondary interactions
ure 18) [166]. Intrinsic self-healing is usually triggered by external stimuli such as temper-
(Figure 18) [166]. Intrinsic self-healing is usually triggered by external stimuli such as
ature, light, pressure,
temperature, pH, etc.pH,
light, pressure, Theetc.
healing may occur
The healing may through multiplemultiple
occur through cycles without
cycles
using any catalyst. However, intrinsic self-healing may have
without using any catalyst. However, intrinsic self-healing may have disadvantagedisadvantage that itthat
is re-
it
stricted to thermoplastic polymers that develop weak bonds, which decrease
is restricted to thermoplastic polymers that develop weak bonds, which decrease strength. strength. The
extrinsic
The healing
extrinsic process
healing reliesrelies
process on using healing
on using agent agent
healing as a phase in the polymer
as a phase matrix
in the polymer
[167]. In this regard, the healing agent can be used as a liquid component.
matrix [167]. In this regard, the healing agent can be used as a liquid component. For For such healing
agents,
such microcapsules
healing or hollow fibers
agents, microcapsules have usually
or hollow beenusually
fibers have filled with
been liquid compound
filled with liquid
[168]. In some cases, healing agents in liquid form can be directly incorporated
compound [168]. In some cases, healing agents in liquid form can be directly incorporated in poly-
meric
in matrices
polymeric to induce
matrices self-healing
to induce effects.effects.
self-healing Here, healing agent agent
Here, healing can becan
mixed with awith
be mixed cat-
aalyst and and
catalyst included in polymers
included for better
in polymers recovery
for better properties.
recovery Sometimes,
properties. Sometimes,catalysts can
catalysts
alsoalso
can be filled in microcapsules
be filled in microcapsules or hollow fibers
or hollow along
fibers withwith
along the the
healing agents
healing [169].
agents [169].

Figure 18. Covalent and non-covalent intrinsic mechanisms. Reprinted with permission from [165].
Figure 18. Covalent and non-covalent intrinsic mechanisms. Reprinted with permission from [165].
2022, Wiley.
2022, Wiley.
When any damage occurs to an aerospace structure, these microcapsules or hollow
When any damage occurs to an aerospace structure, these microcapsules or hollow
fibers break down to release the encapsulated healing agent and catalyst. The released
fibers break down to release the encapsulated healing agent and catalyst. The released heal-
healing agent not only heals the existing cracks but also prevents further crack growth
ing agent not only heals the existing cracks but also prevents further crack growth through
through its action. Consequently, the fracture failure of the space structure has been re-
its action. Consequently, the fracture failure of the space structure has been recovered.
covered. Using efficient healing agent, which itself reacts to recover the damage, means
Using efficient healing agent, which itself reacts to recover the damage, means there is no
there to
need is add
no need to addasaan
a catalyst catalyst as ancomponent.
additional additional component.
Accordingly, Accordingly,
catalysts docatalysts do
not initiate
not initiate the healing process of the damaged structures. It is important
the healing process of the damaged structures. It is important to mention that the shape of to mention that
the container
the shape of theusedcontainer
(capsuleused (capsule
or tube) or tube)
containing thecontaining
healing agent the healing
does notagent does the
influence not
influence the recovery process. Nevertheless, the type of healing compound
recovery process. Nevertheless, the type of healing compound used governs the recovery used governs
the recovery
process. When process.
damage When damage
occurs, occurs,containers
the hollow the hollowwithcontainers
compoundswith compounds
break downbreak
and
down and healing agent is released and delivered to the cracks. Thus,
healing agent is released and delivered to the cracks. Thus, the extrinsic healing the extrinsic healing
mechanism
mechanism
operates operates
through the through
responsetheuponresponse
the onsetupon the onset
of any damage. of any damage. Additionally,
Additionally, self-healing
self-healing materials employing extrinsic methods are susceptible
materials employing extrinsic methods are susceptible to repeated damage. to repeated
Thedamage.
healing
The healing
agents agents
released fromreleased from the
the containers cancontainers
only act acan only
single act and
time a single
then time and then
containers con-
become
tainers Then,
empty. become empty.
further Then,offurther
healing healing
structures ofpossible
is not structures is not
if there is possible
repeated ifdamage.
there isAn-
re-
peated
other damage.
extrinsic Another extrinsic
self-healing approachself-healing
is the use ofapproach
nanofillersisinthe theuse of nanofillers which
nanocomposites, in the
nanocomposites,
may which process,
trigger the recovery may trigger
insteadtheofrecovery process, instead
using encapsuled healing of usingInencapsuled
agents. the case of
healing agents. In the case of self-healing nanocomposites,
self-healing nanocomposites, nanofillers such as graphene and carbon nanotubenanofillers such asmay
graphene
cause
J. Compos. Sci. 2023, 7, 148 17 of 26

healing of the damaged surface [170]. Research must focus on the modification of healing
agents and catalysts used and also the release mechanism of these compounds under
damage. Moreover, recovery effects using nanoparticles need to be investigated in detail so
that the use of healing agents can be avoided in the case of polymeric nanocomposites.
Hence, self-healing polymeric materials and nanocomposites possess several promis-
ing aspects for aerospace structures. However, their utilization in real-world applications
obviously needs a high level of durability, mechanical stability and thermal performance.
Use of a few self-healing materials in real aircraft has been described in the fuselage, engine
and aerospace structure (Section 5). The nature of thermosets, thermoplastics, elastomers,
nanofiller type and healing agent plays a crucial role in ensuring spacecraft safety. However,
up till now, no universal standards have been developed for determining the self-healing
properties of aerospace structures. Moreover, comparative studies have not been performed
on the applicability of self-healing materials for aerospace applications. This has limited
the real applications of self-healing materials in the aerospace industry. There is a need
to develop standard protocols for estimating self-healing features of materials for space
structures. Without standard protocols, large-scale industrial applications and scalability of
self-healing materials are limited. Novel self-healing designs also need to be developed
with specific functionalities for particular applications.
On the other hand, intrinsic healing follows quite a different mechanism for damage
recovery compared to the extrinsic self-healing process [171]. In intrinsic healing, the inher-
ent properties of nanocomposite materials have been considered important. In this case,
external addition of a healing compound containing vesicles is not required. The particular
material properties include chemical bonding, physical interactions and molecular struc-
tural variations [172]. Intrinsic self-healing usually necessitates using an external stimulus
for damage recovery. Mostly, high-temperature conditions have been used to initiate the
intrinsic healing process [173]. However, in some cases, external stimuli are not required
to initiate the self-healing phenomenon; instead, the process intrinsically occurs upon a
damage event. The mechanism of intrinsic self-healing operates through supramolecular
chemistry, formation of reversible covalent bonds and also the development of thermos-
reversible physical interactions [172]. The reversible covalent linking mechanism functions
through reversible bond formation under damaging conditions. The mechanism of physical
interactions also functions through the formation of reversible crosslinks at the damaged
areas. The reversible physical interactions are usually low-energy interactions, which
may influence the healing and physical properties of the nanomaterials. Upon damage,
self-healing occurs by reformation of interactions and damage recovery. Thus, the general
mechanism of intrinsic self-healing works on the basis of reversible interactions in the
polymers or nanocomposite structures.
It is important to understand the relationship between the mechanical properties
and self-healing capabilities of the materials. Table 3 demonstrates the processing, self-
healing and mechanical performance of the nanocomposite systems. The self-healing
processes of polymers and nanomaterials depend upon surface rearrangement, surface
approach, wetting, diffusion and randomization [174]. These factors affect the chain
mobility, exchange rate of network structure and nature of reversible chemistry. Usually,
the more dynamic the reversible chemistry, the better the self-healing ability of the material.
Here, low association strength of reversible chemistry causes good self-healing ability of
polymers. However, the low association strength of a reversible self-healing network does
not allow it to resist external forces. Therefore, reversible chemistry endows polymers
with fine self-healing capability, but less resistance to external forces. Accordingly, better
reversible chemistry decreases the attainment of high tensile strength of materials during
potential applications. Consequently, producing self-healing materials that not only have
high mechanical properties but also high self-healing efficiency is challenging. In this regard,
various strategies have been adopted such as nanofiller addition, phase separation, multi-
networks and sacrificial bonds to form self-healing materials with high tensile strength
and fracture toughness. It has been observed that incorporating nanofillers into materials
J. Compos. Sci. 2023, 7, 148 18 of 26

may dissipate large amounts of energy through reversible bond rupture, leading to a
combination of high mechanical and self-healing properties. Inclusion of nanofillers may
promote sacrificial bonding, reversible hydrogen bonding interactions, ionic interactions,
etc. Covalent self-healing polymeric nanocomposites with nanofillers and sacrificial bonds
have also been developed. Hence, the mechanical performance of a non-covalent or
covalent self-healing network can be enhanced through nanofiller inclusion and sacrificial
bond formation.
Table 3. Design, processing, self-healing and mechanical properties of aerospace nanocomposites.

Nanocarbon/
Aerospace Matrix Processing Self-Healing Mechanical Properties Ref.
Healing Agent
Polyethylene-co-
Healing at 150 ◦ ;
Epoxy methacrylic acid In situ technique Scratch protection of 99% [78]
damage recovery
nanocapsule
Self-healing
activation by Joule’s
Mechanical mixing; Storage modulus 20% drop
Epoxy/polycaprolactone Graphene heating effect; [86]
sonication at 60 ◦ C
healing efficiencies of
40–70%
Stress–strain studies;
Molecular dynamics
Vitrimer epoxy Graphene oxide Simulations crosslinking maintained at [87]
simulations
0.5–1.0 strain
Flexural modulus before
Self-healing
Vitrimer epoxy Graphene oxide Solution dispersion healing of 31.7 MPa; after [95]
efficiency ~90%
healing of 34.7 MPa
Healing efficiency;
mechanical
Carbon nanotube properties; fracture Fracture toughness
Epoxy Hand-lay up [101]
sheet energy recovery of ~1783–2077 N mm
108%; peak load
recovery of 96%
Thymine and Hydrogen bonding;
Storage modulus increase
barbiturate damage repair;
Epoxy Ultrasonication with nanofiller loading at [108]
functional carbon self-healing efficiency
1900–2300 ◦ C
nanotube of 45%
Tetraglycidyl methylene
dianiline modified with
carboxyl-terminated Barbiturate modified Storage modulus increase
Solution; Reversible hydrogen
butadiene acrylonitrile, multiwalled carbon with nanofiller loading [112]
ultrasonication bonding
1,4-butanedioldiglycidyl- nanotube >1100 MPA
ether, and
4,40 -diaminodiphenyl sulfone
Vacuum-assisted
Diglycidyl ether of bisphenol Carbon Thermo-reversible Flexural strength of
resin transfer [128]
A epoxy fiber/graphene oxide bonds 652–723 MPa
molding
Microcapsule 9–100
Polysulfone
Solution mixing; µm; reversible Wear rate of
Epoxy microcapsule with [175]
solvent evaporation physical/chemical 13.10 × 10−14 m3 /Nm
tung oil
interaction
Self-healing of
corrosion damage;
Modulus increase with
Solution mixing; interac-
Vitrimer epoxy Carbon nanotube nanofiller contents of [176]
doctor blading tion/crosslinking;
5773–8602 MPa
self-healing efficiency
of 94–97%
No crack progression;
Carbon Hand lay-up;
Epoxy Recovery of 40–80% fracture toughness [177]
fiber/nanocarbon compression molding
2.79–3.58 MPa m1/2
Three-frame;
Carbon fiber/carbon Self-healing impact Young’s modulus of 72 GB;
Epoxy two-span [178]
nanotube damage >92% yield stress of 441 GB
manufactured
J. Compos. Sci. 2023, 7, 148 19 of 26

7. Prospects and Conclusions

The potential of self-healing nanocomposites has been researched for aeronautical
structures [179,180]. Different thermosets and thermoplastics have been used to develop the
self-healing nanocomposites [181]. In polymers, the inclusion of nanoparticles has enhanced
the self-healing effect [182], in addition to the mechanical properties [183,184]. Special self-
healing effects have been observed to reconcile the rusting, impact and ecological influences.
Advanced self-healing aerospace structural designs have been found to be indispensable
for future progression in this field [185]. In the future, self-healing polymer/nanocarbon
nanocomposites can be developed for damage sensing in aerospace structures [186,187]. In
aerospace, self-healing materials can be beneficial for desirable electronic components such
as batteries, circuits, sensors, supercapacitors, etc. [188,189]. Novel healing agents based on
nanocapsules and nanocarbon nanoparticles need to be designed with superior self-healing
efficiency under high temperature, pressure and impact conditions. Such materials may
enhance the durability of future space structures [190]. However, it is still challenging
to replace whole spacecraft parts with self-healing composite [191]. Similarly, the use of
ecofriendly self-healing materials based on sustainable polymers can be a research focus
for future efficient aerospace structures.
In short, this review article highlights the fundamentals and potential of self-healing
composites/nanocomposites for aerospace structural components. The self-healing effect
can be produced intrinsically or by using nanocapsules, nanotubes, nanofibers, vesicles or
nanocarbon nanoparticles. Literature studies have shown that self-healing polymers are
promising materials for repairing structural damage, cracks and defects. These materials
have remarkable mechanical, thermal and other physical features for industrial applica-
tions. Self-healing nanocomposites have also been used to recover damage related to the
strength, impact, fatigue, cracks, corrosion and environment. This overview particularly
covers self-healing materials for aeronautical applications. Investigations have been carried
out to analyze the improvements in crack properties of space structures. Consequently,
self-healing nanocomposites have been utilized for various aerospace structures, engines,
fuselage, coatings and adhesives. The mechanisms involved in self-healing also enhance the
healing efficiency and life cycle of these materials. During different phases of self-healing,
materials have been scrutinized to achieve long-time service life. The performance proper-
ties of self-healing materials have been improved by the inclusion of nanoparticles. More
advanced healing techniques have been proposed in literature studies to extend beyond
the intrinsic and extrinsic mechanisms and overcome the challenges involved in fabrication
and performance of self-healing materials. More emerging polymeric nanomaterials must
also be explored for the aerospace sector. However, studies on aerospace materials are still
in progress and further novel developments are needed.

Author Contributions: Conceptualization, A.K.; data curation, A.K.; writing—original draft prepa-
ration, A.K.; review and editing, A.K., I.A., M.M. and P.B. All authors have read and agreed to the
published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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