Polymer Reviews

ISSN: 1558-3724 (Print) 1558-3716 (Online) Journal homepage: https://www.tandfonline.com/loi/lmsc20

Self-Healing Polymer Composites: Prospects,

Challenges, and Applications

Iee Lee Hia, Vahdat Vahedi & Pooria Pasbakhsh

To cite this article: Iee Lee Hia, Vahdat Vahedi & Pooria Pasbakhsh (2016) Self-Healing Polymer
Composites: Prospects, Challenges, and Applications, Polymer Reviews, 56:2, 225-261, DOI:
10.1080/15583724.2015.1106555

To link to this article: https://doi.org/10.1080/15583724.2015.1106555

Published online: 10 Mar 2016.

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POLYMER REVIEWS
2016, VOL. 56, NO. 2, 225–261
http://dx.doi.org/10.1080/15583724.2015.1106555

REVIEW

Self-Healing Polymer Composites: Prospects, Challenges,

and Applications
Iee Lee Hia, Vahdat Vahedi, and Pooria Pasbakhsh
Mechanical Engineering Discipline, School of Engineering, Monash University Malaysia, Selangor, Malaysia

ABSTRACT ARTICLE HISTORY

Self-healing polymer composites possess the inherent ability to heal Received 4 May 2015
the damage event autonomically or non-autonomically with external Accepted 28 September 2015
intervention. These advanced materials can be commercialized if the KEYWORDS
challenges and limitations of different self-healing mechanisms are Self-healing; intrinsic self-
well known and considered. These include capsule-based healing healing mechanism; extrinsic
systems, vascular healing systems, and intrinsic healing systems. To self-healing mechanism;
date, most of the reviews have studied and reported on different self- vascular self-healing
healing mechanisms including their response to impact, fatigue, and network; epoxy composite
corrosion tests. This review focuses mostly on extrinsic and intrinsic
self-healing polymer composites which have been reported during the
past five years by comparing their healing efficiency, advantages, and
challenges in the prospect of their future development as well as their
possible applications across various industries such as aerospace,
automobile, coating, electronics, energy, etc.

1. Introduction
Inaccessible damage in a polymer system such as brittle microcracks ingress from the envi-
ronment can be difficult to control and repair, which eventually can lead to material failure.1
Traditionally, damaged polymers were repaired through welding or patching which only
limited to visible damages. Moreover, these methods are not autonomic nor instantaneous
as inspection is needed. Thus, to overcome these limitations, self-healing polymers have
been introduced and have become an intense field of research for the past decade. They are
designed to have the inherent ability to recover from damages in order to prolong their ser-
vice life, require less maintenance, and possible cost reduction. Over the past decade, differ-
ent means of self-healing mechanism for polymer composites were reported, including
autonomous self-healing and healing through external intervention.2-13 Autonomous self-
healing includes capsule5,13,14 and vascular-based11,15,16 healing systems where cracks are
being healed through polymerization of healing agent that is being released during crack for-
mation. Consequently, self-healing through external intervention, also named intrinsic self-
healing, is based on the materials inherent ability to increase the structure mobility in the

CONTACT Pooria Pasbakhsh pooria.pasbakhsh@monash.edu Mechanical Engineering Discipline, School of Engi-

neering, Monash University Malaysia, Jalan Lagoon Selatan, 47500 Bandar Sunway, Malaysia.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lmsc.
© 2016 Taylor & Francis Group, LLC
226 I. L. HIA ET AL.

presence of external stimuli, followed by restoring its chemical or physical properties for
unlimited times in principle.17-19
For each self-healing mechanism, there are underlying limitations or gaps for
improvements. For instance, most of the studies on capsule-based healing systems
showed one-time healing event only.6,7,20 The scale of healing that could be achieved
by this system is limited and the possibility to heal micro- or nano-cracks is low as the
capsules sizes are within the range of 100-200 mm.3,13,14 The other challenge for a cap-
sule-based healing system is where the ratio between the monomer and hardener is
crucial and will affect the healing efficiency.21 In contrast, vascular-based healing sys-
tem is able to show multiple healing events, but to maintain high healing efficiency at
higher healing cycles is still a challenge. Unlike the capsule-based self-healing mecha-
nism, the manufacturing process for scaffolds of microvascular network is complicated
and blockage of interconnected network by cured healing agent has been reported. On
the other hand, though few studies have been done to crosslink intrinsic self-healing
functionality into thermoset materials,19,22 the mechanism is still mostly limited to ther-
moplastic materials23 which also limits its applications.
In this review, the recent development progress of both extrinsic and intrinsic self-
healing polymer composites especially during the past five years were reported. For
each self-healing mechanism, their healing efficiency, healing conditions, assessment
methods, limitations, as well as their possible or existing applications were discussed
and compared.

2. Types of self-healing mechanism

Self-healing mechanisms can be generally categorized into two main groups: extrinsic
and intrinsic self-healing mechanisms. These two mechanisms are differentiated by the
self-healing chemistries that the polymer composite undergo in response to the damage.
For extrinsic self-healing mechanism, the damage is recovered by the sequestered heal-
ing agent from the embedded containers in the matrix. Although most healings are
desired at room temperature, heating is still required sometimes for the healing process
to be carried out and / or to enhance the healing. In contrast, intrinsic self-healing
mechanism is driven by the chemical bonding of the matrix itself which has the ability
to restructure after a drastic damage in the presence of external stimuli such as UV
light, heat, or chemicals. The development of self-healing polymeric materials for each
category is summarized at the end of this review from Table 1 to Table 7.

2.1 Extrinsic self-healing mechanism

Extrinsic self-healing is also considered as autonomous self-healing where the damage within a
material structure is recovered by the prefilled healing agent as an isolated phase within differ-
ent types of container and then embedded in the matrix. In conjunction with the type of con-
tainers, the repair mechanism can be classified into (i) microcapsule self-healing mechanism,
and (ii) vascular network self-healing mechanism. The self-healing concept of these two mech-
anisms is similar in which when a crack is formed and eventually breaks the containers, the
healing agent within the containers will then be released and heal the crack planes.
Table 1. Summary of capsule and catalyst self-healing system.
Matrix Curing Agent Components Healing Condition Evaluation Method Measured Parameter Max. Healing Efficiency (%) Ref.
13
Epoxy- EPON 828 DETA DCPD (UF) - Grubbs 48 hr, RT Mode I, TDCB Fracture toughness 75
24
Epoxy Adhesive- EPON 828 DETA DCPD (UF) - Grubbs 24 hr, RT Mode I, TDCB Fracture toughness 56
27
Epoxy Adhesive -FM®73M - DCPD (PU/UF) - Grubbs 24 hr, RT Mode I, WTDCB Fracture toughness 58
32
Epoxy/ SMA wires DETA DCPD – Wax Grubbs 48 hr, 80 C Mode I, TDCB Peak fracture load 77
35
Epoxy Vinyl Ester BPO & DMA DCPD (UF) – Wax Grubbs 24 hr, RT Mode I, TDCB Peak fracture load 50
39
Epoxy- EPON 828 DETA DCPD (UF) – Tungsten Chloride (VI) 24 hr, RT Mode I, TDCB Fracture toughness 107
40
Epoxy- EPON 828 DETA DGEBA-EPA (UF) – Scandium III Triflate 48 hr, 80 C Mode I, TDCB Peak fracture load 86
43,44
Epoxy- EPON 828 DETA Epoxy (UF) – Hoveyda Grubbs 1st Gen 24 hr, 170 C Mode I, TDCB Fracture toughness 130
42
Epoxy-EPON 828 C Heloxy71 Ancamine K54 ENB (UF) – Hoveyda Grubbs 1st Gen 24 hr, RT Mode I, TDCB Peak fracture load 95
POLYMER REVIEWS
227
228 I. L. HIA ET AL.

2.1.1 Capsule-based self-healing mechanism

2.1.1.1 Capsule and catalyst self-healing system. Capsule-based self-healing polymer com-
posite first originated with White et al.13 in 2001 where the healing process is completed
through living ring-opening metathesis polymerization (ROMP). During crack formation,
the capsules are being ruptured, the healing agent, and the DCPD is sequestered and released
into the crack plane. Eventually when DCPD is in contact with Grubb’s catalyst, polymeriza-
tion is triggered, thus healing the crack faces and restoring the mechanical integrity as shown
in Fig. 1. This ROMP reaction has been studied and reviewed extensively due to its advan-
tages such as long shelf life, low monomer viscosity and volatility, rapid polymerization at
ambient conditions, and low shrinkage upon polymerization.13
The resin monomer, DCPD was microencapsulated within urea-formaldehyde (UF) shell
to isolate it from being polymerized by Grubbs’ catalyst.3,13 Subsequently, Jin et al.24 investi-
gated the same healing sytstem on thin layer of epoxy adhesive through both quasistatic frac-
ture and fatigue performance using width-tapered-double-catilever-beam (WTDCB)
specimen where a healing efficiency of 56% was achieved.
A significant improvement for capsules robustness is always sought in order to withstand
the harsh processing condition such as high temperature and mechanical shear. A modified

Figure 1. Healing capsules and catalyst are being embedded in the matrix and the crack is healed by the
polymerized healing agent as crack ruptures the capsules.13
 POLYMER REVIEWS 229

encapsulation process to produce double-walled polyurethane/poly(urea-formaldehyde)

microcapsules (PU/UF) was developed by Caruso et al.25 These double-walled microcapsules
showed better thermal stability and mechanical properties compared to single-walled UF
microcapsule. The new PU/UF microcapsule has been used to study the self-healing materi-
als.7,26,27 Jin et al.7 showed that these doubled-walled microcapsules are able to withstand
high curing temperature which is over 120 C without compensating its self-healing func-
tionalities compared to the previous capsule-based self-healing materials which were mainly
used to study polymers cured at  458C. Jin et al.27 then extended the work on self-healing
rubber toughened structural adhesive cured at elevated temperatures with embedded dou-
ble-walled (PU/UF) DCPD microcapsules. Besides, Fereidoon et al.28 improved the water
resistancy, thermal resistance, and surface morphology of UF capsules by incorporating sin-
gle-walled carbon nanotubes (SWCNTs).
Most of the reported microcapsules for capsule-based self-healing studies were in the
range of 100-200 mm at 10-20 wt% loading.3,13,29 This is to ensure that there are enough
healing agents to fill the crack volume in order to achieve high healing efficiency.30 However,
when we come across its possible applications such as adhesives and thin coatings, a lower
scale of capsule size is preferred. Blaiszik et al.31 developed nanocapsules with average size of
220 nm, whereas Kirkby et al.32 implemented shape-memory alloy (SMA) wire into the com-
posite to reduce the crack volume and increasing the crack fill factor.
At low catalyst loading (< 2.5 wt%)33 and small catalyst particle size,34 there are always
concerns on poor catalyst dispersion and catalyst deactivation which lead to catalyst reduc-
tion for further healing. Therefore, Rule et al.33 introduced wax coated Grubbs’ catalyst
where the catalyst’s reactivity is preserved.35 Patel et al.36 developed an autonomic self-heal-
ing composite by incorporating DCPD capsules and wax coated Grubbs’ catalyst in a glass
reinforced epoxy composite. It was found that the crack length in the self-healed composite
was reduced by 51% under compression after impact (CAI) test.
Although Grubbs’ catalyst is renowned for its high metathesis activity,13 there are always
issues such as low melting point (Tm D 1538C) of DCPD, high price and low versatility
which prevent it from being commercialized.37 Wilson et al.38 compared the chemical, ther-
mal, and catalytic properties of three different catalysts; first-generation Grubbs’ catalyst,
second-generation Grubbs’ catalyst, and Hoveyda-Grubbs’ second-generation catalyst.
Alternative catalysts such as tungsten (VI) chloride catalyst, WCl2,6,39 and Scandium (III)
Triflate catalyst40,41 were also investigated as these catalysts are more cost-effective as well as
higher thermal stability and availability.
Recently, Guadagno et al.42–44 showed great result in self-healing epoxy with 5-ethyli-
dene-2-norbornene (ENB) healing agent and Hoveyda-Grubbs’ first generation catalyst.
This catalyst showed great thermal stability as high as 1708C without being deactivated.44
They also compared the metathesis reaction of DCPD and ENB where ENB showed higher
yield even at low temperatures with a faster ROMP.42,45 A healing efficiency of more than
90% was achieved for this formulated material42–44 under fracture test. Table 1 shows the
summary of the capsule/catalyst self-healing system.

2.1.1.2 Dual capsule self-healing system. Instead of having polymer resin filled capsules and
catalyst, dual-microcapsule self-healing system encompasses monomer and polymerizer/
hardener which are being encapsulated separately and embedded into the self-healing
230 I. L. HIA ET AL.

polymer composite.46 As the crack forms and ruptures the capsules, the monomer will be
polymerized when it comes into contact with hardener and eventually heal the cracks.
Yuan et al.21 encapsulated epoxy and its hardener mercaptan and embedded within epoxy
matrix. This epoxy/hardener, diglycidyl tetrahydro-o-phthalate (DTHP)/ pentaerythritol tet-
rakis (3-mercaptopropionate) (PETMP) system showed a healing efficiency slightly more
than 100%. It was also shown that the high healing efficiency and rapid healing of this
epoxy/hardener system were governed by the strong alkalinity of the catalyst, high activity
of mercaptan, and low viscosity of the encapsulated polymer. Moreover, keeping the right
stoichiometric ratio or the homogeneity of both the components are crucial for the addition
polymerization.21
Subsequently, Yuan et al.47 also developed alternative epoxy/hardener healing system with
diglycidyl ether bisphenol A (DGEBA) and 2,4,6-tris(dimethylaminomethly)phenol (DMP-
30) being encapsulated within poly(melamine-formaldehyde) (PMF) capsules. This dual-
microcapsule self-healing composite was able to retain its autonomous healing capability
even at high temperature curing and thermal exposure due to the high thermal stability of
DGEBA and lower volatility of DMP-30. The healing efficiency of the specimens remained
above 95% under thermal exposure below 2008C. Then et al.48 introduced the urea-mela-
mine-formaldehyde (UMF) microcapsules filled with DCPD for self-healing dental restor-
ative materials. Nesterova et al.49 found that capsules with UMF shells were easier to
synthesize and were more robust, which increased the stability of the microcapsules.
Yin et al.50 synthesized dual-microcapsule self-healing epoxy composite by incorporating
encapsulated bisphenol-A epoxy healing agent into mixture of CuBr2(2-MeIm)4 latent hard-
ener and bisphenol-A composite matrix. This latent hardener will dissociate only at 1308C
to 1708C which is higher than the curing temperature of the composite matrix, therefore, it
can be homogeneously pre-dispersed into the composite matrix instead of being encapsu-
lated.50 This dual microcapsule system did not affect much on the composite fracture tough-
ness compared to virgin epoxy specimens. The healing efficiency achieved was 111% at 10
wt% epoxy microcapsules and 2 wt% latent hardener.
Xiao et al.51 overcame the limitations of stoichiometric ratio and healing at elevated tem-
perature as discussed previously by using boron trifluoride diethyl etherate ((C2H5)2O ¢ BF3)
as the hardener. The healing of the composite was dominated by cationic chain polymeriza-
tion of the ((C2H5)2O ¢ BF3) hardener and epoxy in which the reaction occurred rapidly at
ambient temperature. As the conventional UF encapsulation method was not applicable for
the highly active ((C2H5)2O ¢ BF3) hardener, instead it was infiltrated into polymeric hollow
microcapsules produced under UV irradiation. It was found that at 5 wt% epoxy and 1 wt%
((C2H5)2O ¢ BF3) hardener, the healing efficiency of 85% was achieved. One of the challenges
of this self-healing mechanism is the uncompleted curing of epoxy due to the high reaction
rate of healing agent.51
Jin et al.46 developed a dual-microcapsule self-healing epoxy composite by incorporating
modified aliphatic polyamine (EPIKURE 3274) and diluted epoxy monomer (EPON 815C)
microcapsules into epoxy matrix. Epoxy resin capsules are synthesized by UF encapsulation
whereas amine capsules were synthesized by vacuum infiltration of EPIKURE 3274 into
polymeric hollow microcapsules. Healing efficiency of 91% was obtained for room tempera-
ture cured epoxy and it was reduced to 40% for post-curing at 1218C for 8 h. Subsequently,
Jin et al.7 improved the epoxy/amine dual-microcapsule system by using DGEBA epoxy
resin diluted with reactive diluent, o-cresyl glycidyl ether, and polyoxypropylenetriamine
 POLYMER REVIEWS 231

(POPTA) amine curing agent. Epoxy resin DGEBA was encapsulated within double wall
PU/PUF double-walled (PU/PUF) microcapsules25 and amine curing agent POPTA was
encapsulated into hollow UF microcapsules.7 This epoxy/amine system had the advantage of
having the similar healing efficiency of 90% with epoxy cured at higher temperature (1218C,
6 h) than the previous system which was only 40%. Another dual-microcapsule epoxy/amine
self-healing composite proposed by Li et al.52 was incorporating the encapsulated epoxy
resin DGEBA and hardener polyetheramine within polymethyl methacrylate (PMMA) shell
in the epoxy matrix.
Recently, Zhang et al.53–55 developed a two part self-healing polymer through amine-
epoxy chemistry where amine was loaded within specially developed etched hollow glass
bubbles (HGB) whereas epoxy resin was encapsulated in UF shell.54 During the fracture test
of the tapered double cantilever beam (TDCB) specimens, healing efficiency up to 64% was
achieved. Subsequently, the same team loaded both amine and epoxy in dual HGB and the
highest healing efficiency achieved was 62% which was comparable to the previous study.55
Moreover, this study showed that the etched HGBs were much stronger and more brittle
than PU or PUF shell. Table 2 shows the summary of the dual capsule self-healing system.

2.1.1.3 Mono capsule self-healing system. The method of using solvents such as methanol
and ethanol in healing the cracks of thermoplastic polymers such as polymethyl methacry-
late at elevated temperatures has been reported by Lin et al.57 and Wang et al.,58 respectively.
Using the same healing concept, Caruso et al.59 incorporated only solvent filled capsules into
thermoset polymer matrix as self-healing polymer composites. The solvent worked as a wet-
ting agent on the polymer surface, causing the bulk polymer material to swell which led to
reptation and interlocking of the chains across the crack plane. Thus, the crack is healed and
the mechanical properties are recovered. Similar to previous capsule-based healing system,
this mono capsule self-healing system consists of embedded solvent capsules which are sus-
ceptible to rupture during the crack formation; liquid solvent will then fill up the cracks and
healing is achieved.
Using the similar approach, Caruso et al.59 had screened for various solvents particularly
for their healing abilities on the cracks formed in thermoset polymer matrix as well as the
ability to be encapsulated within UF capsules. Nitrobenzene was found to be successfully
encapsulated and at the same time showed great healing ability under in situ healing test.
Despite the simple, cost effective, and great healing abilities of nitrobenzene, its toxicity
prevents this self-healing mechanism to be commercialized.5 Thus, Caruso et al.5 further
improved the solvent self-healing mechanism by using phenylacetate (PA) and ethyl phenyl-
acetate (EPA) which were considered as low toxicity solvents. To further improve the healing
efficiency, the team co-encapsulated the mixture of both solvent and epoxy monomer
together and embedded into the polymer matrix as the solvent self-healing mechanism.
Healing efficiencies of 100% were obtained for epoxy-EPA microcapsule self-healing system.
Besides, this self-healing system also showed multiple healing events of three to five times. It
has been shown, however, that the performance of the epoxy-EPA microcapsule self-healing
system decrease over time for the reasons of water absorption and the premature release of
EPA solvent through the capsule barrier.60
Neuser et al.61 improved the EPA solvent self-healing system with SMA wires. Upon
crack formation, the EPA solvent diffuses into the cracks and at the same time the heated
SMA wires reduce the crack gap and foster epoxy residual cure. The study showed an
 232
I. L. HIA ET AL.

Table 2. Summary of dual capsule self-healing system.

Matrix Curing Agent Components Healing Condition Evaluation Method Measured Max. Healing Ref.
Parameter Efficiency (%)
56
Epoxy-EPON 828 DETA Epoxy: Epoxy 711 (PMF) Hardener: 24 hr, 20 C Mode I, TDCB Fracture toughness 83
PMP (PMF) Catalyst: BDMA (disperse)
47
Epoxy-EPON 828 2-ethyl-4-methylimidazole Epoxy: DTP (PMF) Hardener: PMP (PMF) 24 hr, 200 C Mode I, TDCB Fatigue Fracture toughness 86
Catalyst: BDMA (disperse)
51
Epoxy-EPON 828 TETA Epoxy: EPON 828 Hardener: (C2H5)2O ¢ BF3 2 hr, 20 C Mode I, Impact test Impact strength 88
46
Epoxy-EPON 828 DETA Epoxy: EPON 815C (UF) Hardener: RT Mode I, TDCB Fracture toughness 91
EPIKURE 3274 (hollow capsule)
52
Epoxy- DGEBA Polyetheramine Epoxy: DGEBA (PMMA) Hardener: 24 hr, RT Mode I, TDCB Peak fracture load 84
Polyetheramine (PMMA)
54
Epoxy-Epolam 5015 DETA Epoxy: Epolam 5015 (UF) Hardener: 24 hr, 50 C Mode I, TDCB Peak fracture load 64
DETA (HGB)
 POLYMER REVIEWS 233

improvement in healing efficiency from 24% to 78% with the use of SMA wires. Subse-
quently, Jones et al.62 achieved almost a full recovery on interfacial bond strength during
fiber/matrix debonding test. Using the solvent based healing chemistry, the co-encapsulated
epoxy-EPA were functionalised on the surface of glass fiber. As the fiber/matrix interface
was debonded, the capsules ruptured, releasing the resin and solvent into the damage area.
Yuan et al.20,63 encapsulated epoxy resin and blend the microcapsules into cyanate ester resin
matrix with 4,40 -diaminodiphenylsulfone (DDS) as curing agent. This system with curing
temperature ( 1808C) and self-healing ability demonstrated an 11-43% increase in fracture
toughness compared to neat resin. Besides, the material showed a healing efficiency of 85%
under fracture test.
Few studies have been done using the monocapsule self-healing system into its possible
applications. Samadzadeh et al.64 successfully encapsulated Tung Oil into PUF shell and syn-
thesized into self-healing paint coatings. Apart from that, a self-heal packaging board was
developed by incorporating food grade healing capsules, showing the ability in reducing
crack formation and promoting healing upon ceasing of packaging board effectively. Subse-
quently, Vimalanandan et al.65 introduced self-healing coating with self-sensing corrosion
protection. This self-healed corrosion protection layer contains redox-triggered release heal-
ing agents of conducting polymer (CP) within a redox-sensitive polyaniline (PANI) shell.
The PANI shell shows reversible ability to switch from impermeable to permeable when
there is a change in potential concurrent, in order to release the active agents and vice versa.
Another self-healing anticorrosion coating was reported by incorporating nanocapsules with
benzotriazole (BTA) loaded polystyrene (PS) core domain and polyethylenimine (PEI) as
the shell material.66 Corrosion protection through self-healing polymer and hybrid multi-
layers formed via layer-by-layer (LbL) approach has been a resurgence of interest.67
Khun et al.68 improved the tribological properties of epoxy composite through incorpo-
ration of hexamethylene diisocyanate (HDI) filled polyurethane capsules. These capsules
served as lubricant and healing capsules which eventually improved the wear resistance of
epoxy composites. Using the mono capsule approach, Blaiszik et al.69 developed self-healing
conductors by embedded different types of microencapsulated healants which includes eutectic
gallium-indium (Ga-In) liquid metal, tetrathiafulvalene-tetracyanoquinodimethane) (TTF-
TCNQ) charge-transfer salt solution,70 conductive silver (Ag) ink,71 and functionalized carbon
black (FCB).72 The conductance restoration efficiency of using FCB is in the range of 95-100%.
Overall, the mono capsule self-healing system had great advantages due to the exclusion
of catalyst which can avoid the concerns on catalyst dissolution, deactivation and expensive
catalyst.37 However, the chain mobility within the undercured epoxy matrix is required
which is limited for low temperature curing systems.46 As reported earlier, studies have been
done on utilizing the mono capsule concept to improvize on the possible applications espe-
cially for tribological restoration coating, anticorrosion coating, conductivity restoration
coating, etc. Table 3 shows the summary of the mono capsule self-healing system.

2.1.2 Vascular network self-healing mechanism

2.1.2.1 One-dimensional vascular network self-healing system. One-dimensional vascular

network self-healing polymer composite is developed by embedding or creating one dimen-
sional pipelines within a polymer composite matrix and filled with either one-part healing
system, two-part resin and hardener system or a resin system with hardener as shown in
234 I. L. HIA ET AL.

Table 3. Summary of mono capsule self-healing system.

Curing Evaluation Measured Max. Healing
Matrix Agent Components Healing Condition Method Parameter Efficiency (%) Ref.
59
Epoxy-EPON 828 DETA Nitrobenzene 24 hr, RT Mode I, TDCB Peak fracture load 82
(UF)
5
Epoxy- EPON 828 DETA PA (UF) 24 hr, RT Mode I, TDCB Peak fracture load 84
73
Epoxy-EPON 828 DETA EPA (UF), 24 hr, RT Mode I, TDCB Crack gap 78
SMA wires 30-90 min
SMA activation
62
E-glass Epoxy DETA EPON 24 hr, RT Microbond test Peak applied load 86
composite 862CEPA
(UF)
20
Cyanate Epoxy DDS Epoxy resin 1 hr, 2208C Mode I, SENB Fracture toughness 85
(UF)

Fig. 2. When damage is triggered, the healing agent will flow into the damage area through
capillary action and polymerized, thus completing the healing process. This self-healing sys-
tem is preferred over the capsule-based self-healing systems as besides being a self-healant
container, the vascular network works as a reinforcement as well.12 Using the same principle
of self-repaired cement matrix,74,75 Dry76 then developed a self-heal thermoset polymer by
incorporating hollow 100 mm glass pipette tubes filled with two-part epoxy (monomer and
hardener) into epoxy matrix.
Hollow glass fibers (HGF) as small as 5 mm2 and as big as 30 mm15 were developed.
Although a low healing efficiency was shown for smaller diameter HGF and higher healing
efficiency of 93% was achieved for the bigger diameter HGF under impact test, fiber blockage

Figure 2. HGF self-healing system, (a) one-part resin being encapsulated within the HGF, (b) two-part
resin with resin and hardener being encapsulated separately in HGF and (c) resin being encapsulated with
catalyst being distributed evenly within polymer matrix.2
 POLYMER REVIEWS 235

was still present in both cases. This is due to the low volume filling into such tiny fibers as
well as rapid curing of one-part epoxy resin system.
Trask and Bond12,77 introduced epoxy filled HGF into glass fiber reinforced polymers
(GFRPs) and carbon fiber reinforced polymer (CFRP). Both self-healing composites showed
good healing efficiencies under four-point bending test but their initial strength were
reduced. Williams et al.78 proved that the embedded resin filled HGF within CFRP laminates
recovered without having much influences on the mechanical properties of host laminate.
The strength recovery showed by the self-healed specimens were exceeded 90% under quasi-
static impact damage.
Instead of using HGF, Huang et al.79 incorporated stainless steel wires to create vascules
within the fiber reinforced polymer (FRP) laminate. The vascules were formed by a polyte-
trafluoroethylene (PTFE) coated stainless steel wire with high rigidity and high melting tem-
perature. These wires were introduced at the mid-layer of the laminate and removed
manually after the laminate was cured. Coope et al.80 then further investigated the healing
performance of CFRP composite material containing embedded scandium (III) triflate cata-
lyst and microvascular channels which were manufactured using the method as discussed
above.79 The double cantilever beam (DCB) specimens were found to be healed up to five
times with healing efficiency up to 108%.
Trask et al.81 incorporated a low-pressure sensor within the fiber reinforced polymer
(FRP) composite laminate and once ply delamination is detected, the delivery of healing
agent to the damage zone is triggered. Two types of epoxy systems, a commercial epoxy sys-
tem (RTI5I) and an in-house developed epoxy-based system (DGEBA/DETA) were evalu-
ated in this study. Compression after impact (CAI) test was used to assess the self-healing
performance of the FRP laminate and healing efficiencies of 91% and 94% were showed for
RTI5I and DGEBA/DETA system, respectively. The vascule diameter and resin viscosity
were critical to the development of this self-healing system as they governed the fluid deliv-
ery and the cost to mechanical performance tightly. For instance, a smaller diameter vascular
network requires a higher pressure to deliver the healing agent to the damaged site due to
increasing frictional loss. On the other hand, a lower fluid viscosity will lead to higher infu-
sion potential which eventually increases the healing efficiency and would significantly
reduce the fluid delivery cost as well.
Patrick et al.82 developed a self-healing microvascular polymeric foam which was used as
core materials for sandwich structures. The advantage of this system is the volumetric
expansion of the healing chemistry which shows the ability to heal macro-scale damage. The
quick foaming reaction at room temperature also leads to rapid in situ healing. A two-part
healing chemistry was infiltrated into dual network vasculature within rigid polyurethane
(PUR) foam. An over 100% of fracture recovery with 4 healing cycles were obtained for the
vertical configuration of the vascule network.
A new aluminum hollow tube reinforced shape memory polymer (AHTR-SMP) was devel-
oped by Ji et al.83 During the low velocity impact test, the hollow metallic core acts as energy
absorbent which prevents the matrix from being damaged. In the future, this new polymer
composite could possibly be applied on critical structural applications due to its prominent
results in matrix recovering and cracks healing after multiple damage events. He et al.84 devel-
oped a self-healing electronic sensor by loading thermal-sensitive ionic liquid into the micro-
channel formed within the thermoplastic supporting matrix. The thermal sensing ability of the
broken specimens are able to recover repetitively when the broken parts are attached to each
236 I. L. HIA ET AL.

Table 4. Summary of one dimensional vascular network self-healing system.

Healing Evaluation Measured Max. Healing
Matrix Components Condition Method Parameter Efficiency (%) Ref.
15
E-glass/Epoxy HGF: MY750 24 hr, Ambient Mode I, Four Flexural strength 93
point bend
GFRP laminate HGF: Cycom 823 2 hr, 100 C Mode I, Four Flexural strength 100 12

point bend
CFRP laminate HGF: Cycom 823 45 min, 70 C then CAI test Compressive strength 90 78

75 min, 125 C
 80
Carbon/Epoxy Catalyst: Sc(OTf)3 24 hr, 80 C Mode I, DCB Strain energy 108
laminate Vascule: Epoxy 828 release rate
81
FRP laminate Vascule: EPON 828/DETA 7 days, RT CAI test Compressive strength 94
82
PUR foam Vascule: X-30 24 hr, RT Mode I, SENB Fracture toughness 160
system (foam) Fatigue

other. This study has showed the potential of self-healing in sensing applications. Table 4
shows the summary of the one-dimensional vascular network self-healing system.

2.1.2.2 Two- and three-dimensional network self-healing system. Self-healing composites

featuring microvascular networks have attracted immense attention in recent years. Com-
pared to the hollow fiber and microcapsule self-healing mechanism, this higher dimension
microvascular network self-healing mechanism has the ability to heal the same damage area
for more than once. Due to the interconnected microvascular network system, there will be
constant flow of healing agent within the microvascular structure, thus multiple healing
events can be achieved as shown in Fig. 3.
Williams et al.86 created 2D vascular network within self-healing sandwich panel by lay-
ing the PVC tubing in the middle of the panels and holes were drilled perpendicular to the
panel, through the core and into the tubes to create the 2D network. Premixed resin or two-
part epoxy resin/hardener system were infiltrated into the network separately and their self-
healing ability were assessed. Only the premixed resin specimens showed evidence of com-
plete healing. Williams et al.16 then study vascular self-healing on foam-cored sandwich
panel by alter the distribution of risers of the network. The pressurized autonomous speci-
mens (two-part healing chemistry) showed comparable healing efficiency with premixed sys-
tem as discussed previously. The high pressure environment facilitate the mixing of epoxy
resin and hardener to perform self-healing ability. Hong et al.87 developed a self-reporting
polymer composite with integrated conductive microwire networks. The conductive micro/
nanowires and hollow microtubes were fabricated using fiber drawing nanomanufacturing

Figure 3. Two-part epoxy resin and hardener are being filled separately within 2D and 3D vascular net-
work self-healing system.85
 POLYMER REVIEWS 237

(FDN) method. Besides having self-healing ability, this self-reported polymer composite is
able to report the location of damage event. Recently, a polyacrylonitrile (PAN) electrospun
nanofibers used as microchannels for carrying two-part epoxy systems are developed by
Vahedi et al.88 The reported self-healing system is able to heal up to 6 times. The average
healing efficiency is 75% at 50 C compared to 38% at room temperature.
Toohey et al.89,90 created a 3D microvascular network in epoxy resin substrate with epoxy
coating using direct-wire assembly of a fugitive organic ink method.91 The healing of epoxy
coating was completed when the supplied DCPD through the microvascular network in the
underlying substrate was in contact with Grubbs’ catalyst embedded in the coating. Under
four point bending test, the coating/substrate specimens showed an average healing effi-
ciency of 49% and up to seven healing cycles.90
Previous studies showed the limitation of low healing cycles due to catalyst depletion.89
Thus, in order to overcome the low healing cycles, Hansen et al.92 used similar method,
direct-write assembly but with dual ink deposition and vertical ink writing features to incor-
porate 3D microvascular network that can contain two-part epoxy resin and a hardener sys-
tem into autonomous self-heal coating/substrate. This interconnected dual 3D
microvascular network was able to infiltrate epoxy resin and hardener separately. After the
coating was fractured under four point bending test, it was subjected to cyclic flexure loading
to enhance mixing of the fluids in the crack plane prior healing. Healing efficiency as high as
100% was achieved and at least 50% of the fracture toughness was retained after 30 healing
cycles.
Park and Braun93 developed self-healing polymer coatings by electrospinning coaxial
healing agent onto a substrate. This method is able to encapsulate the healing agents into a
core-shell bead-on-string morphology. Few advantages were claimed on this self-healing sys-
tem. First, only physical forces are utilized to form core/sheath arrangement which overcome
the limitation of minimum emulsion stability for chemical reaction and hold the capsules
together. Second, it has the inherent flexibility to control the diameter from micro- to nano-
scale for the microcapsules and connecting ligaments. Finally, the self-healing functionality
through electrospinning can be applied on a large area of substrates.
A hybrid carbon-fiber/epoxy composite reinforced with self-healing core-shell nanofibers
at interfaces was developed by Wu et al.94 Such multifunctional nanofibers were fabricated
by coelectrospinning where the healing agent DCPD was encapsulated into polyacrylonitrile
(PAN) to form core-shell DCPD/PAN nanofibers. A healing efficiency of 103% was achieved
for the polymer matrix composite (PMC) under three-point bending test. This ultrathin
core-shell nanofiber is said to be cost effective due to the low cost of coelectrospinning fabri-
cation method, low weight penalty, low nanofiber content, and low impact to the mechanical
properties of the PMCs.
Patrick et al.9 developed another 3D microvascular network through vaporisation of sac-
rificial components (VaSC) process. This interconnected vascular network has the ability to
circulate the chemicals throughout the composite structure. Two-part healing chemistry,
DGEBA, and triethylenetetramine (TETA) were infiltrated into the microvascular network
within pristine composite laminate. Two types of network configurations, parallel and her-
ringbone were fabricated and the effect of fluid interspersion on in situ mixing was assessed.
Herringbone network showed three successive healing cycles and the healing efficiency
increased with each cycle. The maximum healing efficiency was up to 125%. Besides the effi-
cient and repetitive healing features, this microvascular architecture offers an increased
238 I. L. HIA ET AL.

resistance to delamination, initiation and propagation. Later, they introduced a vascular net-
work by using conventional PLA sacrificial fiber with tin (II) oxalate (SnOx) catalyst par-
ticles through melt spinning. The addition of SnOx catalyst particle into PLA increases the
options of thermal processing techniques for sacrificial microvascular template where the
possible applications can be used to fabricate self-healing vascular network.95
Nji and Li96 developed a 3D woven fabric reinforced shape memory polymer composite
equipped with self-healing ability. This polymer composite is able to heal for 15 times before
it perforates under impact test. The emerging of shape memory polymers (SMP) is getting
more attention as it is cheap, light weight and easy to process.97 Table 5 shows the summary
of the two- and three-dimensional vascular network self-healing system.

2.2 Intrinsic self-healing mechanism

Intrinsic self-healing of thermoplastic materials are designed with inherent repeatable
reform abilities after damages where the presence of healing agent and catalyst are not requi-
site. The intrinsic healing of thermoplastic structure is achieved at the molecular level due to
the low Tg of thermoplastic polymers where the heating and cooling process will lead to
molecular interdiffusion, randomisation, recombination of chain ends, etc.98 Unlike extrinsic
self-healing, this simpler concept of self-healing mechanism can be more competitive in
terms of end products manufacturing and applications. Although no monomer or catalyst is
required, different external stimuli to trigger the self-healing are essential, depending on the
types of self-healing mechanism which are going to be discussed in subsequent sections.

2.2.1 Thermally reversible Diels-alder self-healing system

Thermal remendable crosslinked polymer through Diels-Alder (DA) an retro-DA (rDA)
reactions was introduced by Chen et al.17 The material is rigid at room temperature which is
similar to commercial polymer resins, whereas the physical properties deteriorate at high
temperatures due to “intermonomer” disconnection but the properties revert back to their
original form upon cooling. This thermally reversible polymer is synthesized through DA
cycloaddition of 4 furan (4F) and 3 maleimide (3M) monomers (Fig. 4a), showing recovery
of 57% in fracture toughness and 3 consecutive healing cycles under heating/cooling proce-
dure. Healing efficiency of re-mendable polymer is strictly governed by the accuracy of
realigning the two broken parts together, healing temperature, as well as the pressure
applied.
Subsequently, Chen et al.99 developed a new re-mendable polymer, 2MEP4F in which sol-
vent was not required for polymerization. The specimens showed an average healing effi-
ciency of 80% and 78% for 2 consecutive healing cycles. For the same crosslinked polymer
2MEP4F, Plaisted and Nemat-Nasser100 found an alternative method to evaluate the healing
properties quantitatively using double cleavage drilled compression (DCDC) specimen
geometry (Fig. 4b). This DCDC geometry specimen had the feature of being in one-piece
after the test, facilitating the realign of fracture surfaces prior to healing. The specimens
were healed at a lower temperature compared to previous study99 due to creeping at high
temperature. A full recovery and 5 healing cycles were shown from the specimens under
fracture test. Ghezzo et al.101 introduced CFRP laminates and remendable crosslinked poly-
mer 2MEP4F hybrid. Due to the fast kinetics rate of the monomers 2MEP and 4F, the proc-
essing time for the hybrid polymer is short. Subsequently, another advanced composite
Table 5. Summary of two and three-dimensional vascular network self-healing system.
Matrix Components Healing Condition Evaluation Method Measured Parameter Max. Healing Max. Healing Cycle Ref.
Efficiency (%)
16
E-glass/913 Epoxy & foam Silicone tube: RT310 resin 24 hr, RT Edgewise CAI test Compressive strength 115 1
sandwich panel
90
Epoxy coating-substrate 3D microvascular: DCPD 12 hr, 25 C Mode I, Four point bend Fracture toughness 80 7
Coating: Grubbs
92
Epoxy coating-substrate Dual 3D microvascular: 48 hr, 30 C Mode I, Four point bend Fracture toughness 100 30
EPON 8132 & EPIKURE 3046
94
CFRP laminate DCPD/PAN nanofiber 2 hr, RT Mode I, Three point bend Flexural stiffness 103 1
9
Pristine composite laminate Dual 3D microvascular: 48 hr, 30 C Mode I, DCB Strain energy release rate 125 3
EPON 8132 & EPIKURE 3046
88
Epikote 828 PAN nanofiber: Araldite 506 & DETA 72 hr, 50 C TDCB Fracture toughness 75 6
96
Veriflex shape memory Q-cell 6014 glass microballoons 30 min, 110 C Low velocity impact test Damaged area - 15
polystyrene
POLYMER REVIEWS
239
240 I. L. HIA ET AL.

Figure 4. (a) Schematic representation of DA and rDA reactions between 3M and 4F moieties.17 (b) Sche-
matic of DCDC geometry where the dotted lines represent the location of pre-crack and its crack exten-
sion. Diagram (A) to (C) represents the healing sequence of a DCDC specimen. (A) Virgin specimen with
hole and pre-crack in the middle. (B) Damaged specimen after first fracture. (C) Healed specimen after first
healing. (D) Damaged specimen after second fracture.100 (a) © AAAS. Reproduced by permission of AAAS.
(b) © Elsevier. Reproduced by permission of Elsevier. Permission to reuse must be obtained from the
rightsholders.

possessed self-healing ability and shape memory effect using bis-maleimide tetrafuran
(2MEP4F) and electrical resistive heating via carbon fibers was introduced by Park et al.102
using the injection molding method. This composite showed multiple healing events with
strength recovery up to 90%.
Apart from integrating furan and maleimide monomers, Murphy et al.103 developed two
new thermally remendable polymers with a single component which contained dicyclopen-
tadiene core and acts as both diene and dienophile in the rDA reaction. Two types of speci-
mens were produced from two new monomeric units, monomer 400 and 401. Three-point
bending tests showed that polymer 401 was tougher and brittle than polymer 400. On the
other hand, fracture tests showed polymer 400 had better healing ability than polymer 401
with average healing efficiency of 46% over 23% for polymer 401. Polymer 400 can be healed
up to three times whereas it was only one time for polymer 401.
Tian et al.10 introduced an epoxy functionalized with both furan and maleimide groups.
Such a newly synthesized thermoset exhibits the inherited excellent properties of epoxy
along with thermal reversible functionality. Peterson et al.104 developed a thermal remend-
able fiber reinforced composite by integrating a maleimide-functionalized glass fiber within
a furan-functionalized epoxy-amine thermosetting matrix. An overall healing efficiency of
41% was shown under the single fiber microdroplet pullout test with five successful healing
cycles. Another approach such as incorporating both furan and maleimide into polymetha-
crylate copolymer was introduced by Bose et al.105 A full recovery in scratch healing was
achieved at a temperature of 1208C to 1608C in less than 1 hour.
Du et al.106 introduced a new self-healing linear polyurethane via DA reaction between
polyurethane end-capped with furan groups and bismaleimide (Fig. 5a). This newly synthe-
sized polyurethane exhibited better mechanical property, thermal stability, and thermal
reversibility along with self-healing properties. In the subsequent year, two types of shape
memory self-healing polyurethanes through rDA reaction between furan and maleimide
moieties were developed by Heo and Sodano.107 These polymers were able to close the crack
 POLYMER REVIEWS 241

Figure 5. (a) Schematic of DA and rDA reactions of linear polyurethane with DA bonds. (b) Schematic
showing damaged polyurethane being healed at 120 C for 60 s and 300 s consecutively.106 © The Royal
Society of Chemistry. Reproduced by permission of The Royal Society of Chemistry. Permission to reuse
must be obtained from the rightsholder.

autonomously through the shape memory effect without the aid of external forces. An effi-
ciency as high as 84% was achieved under compact tension test. A self-healing coating based
on thermal reversible crosslinking by DA cycloaddition was developed by K€otteritzsch et
al.108 This polymer was formed from a methacrylate-furan backbone and maleimide units in
the side chain. The self-healing ability of this polymer film was assessed by observing the
healed scratch film after heat treatment under scanning electron microscope (SEM). The
scratches showed complete healing in a short time under high temperature.
A thermally self-healing thermoset polyketones (PK-furan) was synthesized by function-
alising with bis-maleimide through DA reaction.109,110 This newly introduced thermoset is
reworkable at 120-1508C and able to recycle up to seven times.109 Zeng et al.111 introduced a
bio-based self-healing furan polymer through DA reaction. This material has greater ability
in bringing a more eco-friendly and safe products to the society as this material can be

Table 6. Summary of thermal reversible DA self-healing system.

Evaluation Measured Max. Healing
Matrix Healing Condition Method Parameter Efficiency (%) Max. Healing Cycle Ref.
99
2MEP4F 1158C, 30 min Mode I, Compact Peak fracture 83 2
408C, 6 hr tension load
100
2MEP4F 858C, pressure DCDC Fracture 106 5
958C, without toughness
pressure
102
2MEP4F 1008C, 3 hr Mode I, Three Strain 90 4
point bend energy ratio
103
Polymer 400 & 401 1208C, 20 hr, Mode I, Three Fracture 60 3
Argon point bend toughness
104
Furan 908C, 1 hr Microdroplet Max. load 41 5
Polymer-Maleimide 228C, 12 hr single
E-glass pull out test
106
PU-furan-bismaleimide 1208C, 5 min Tensile test Tensile strength 80 2
608C, 24 hr
110
PK-furan 1208C, 20 min Mode I, Three Peak fracture 100 7
point bend load
111
PFS-M2 RT, pressure, Tensile test Tensile 74 1
1-10 Days strength
242 I. L. HIA ET AL.

produced by biomass. Such thermal re-mendable polymer system by utilizing DA and rDA
reactions to obtain healing at high temperature has the potential for anti-scratch coating
applications. Table 6 shows the summary of the thermal reversible DA self-healing system.

2.2.2 Thermoplastic/thermoset blend self-healing system

This self-healing mechanism incorporates a weak thermoplastic solid-state healing agent into a
thermosetting matrix system. The weak chemical bonds of thermoplastic within the composite
will break and reform upon heating which enable the matrix to be repaired after damage.
There are three critical properties that make thermoplastic as healing agent in terms of crack
healing. First, low melting point and viscosity to enable it to flow into the cracks and perform
healing while the thermoset matrix remains in solid state at elevated temperatures. Second, the
functional groups of thermoplastics must be chemically reactive with amine groups in epoxy.
Lastly, the thermoplastic must have good adhesive properties as well in order to have strong
bonding such as hydrogen bond with the matrix during crack healing.112
Hayes et al.113,114 developed a new self-healing composite by blending the poly(bisphenol-
A-co-epichlorohydrin) thermoplastic material with DGEBA based resins. The blend matrix
showed that increasing healing temperature will improve the degree of recovery under com-
pact tension tests.113 Besides, the incorporation of thermoplastic healing agent into glass
fiber composite also showed good healing ability for delamination and matrix cracking. Luo
et al.22 developed another thermally remendable polymer by blending phase-separated poly
(e-caprolactone) (PCL) with epoxy resin. Upon heating, the specimen showed crack healing
with full recovery on mechanical integrity when moderate force was applied. The healing
was attributed by thermal expansion of PCL to fill the cracks. Rodriguez et al.115 reported a
self-healing polymer that combines shape memory and thermoplastic diffusion with crack
closure and rebonding capabilities through the blend of linear and network poly(e-caprolac-
tone) (Figs. 6a and 6b). Subsequently, shape memory assisted self-healing (SMASH) polymer
composites were reported with the incorporation of electrospun PCL fibers116 (Fig. 6c) and
dual-electrospun of poly(vinyl acetate) (PVAc) and PCL interwoven fibers.117 This system
has the potential to apply on self-healing coating as well as packaging materials due to its
simplicity of fabrication. 117
Wang et al.118 incorporated two types of thermoplastics, poly(ethylene-co-methyl acry-
late) (EMA) and poly(ethylene-co-methacrylic acid) (EMAA) patches into carbon fiber com-
posite. The incorporation of EMA and EMAA patches improved composite fracture
toughness but reduced their interlaminar strength. Under the interlaminate fracture tough-
ness test, the composites showed healing efficiency of 88% for EMAA and 46% for EMA
compared to un-modified specimens without healing patches. Subsequently, Dell’Olio et
al.18 incorporated modified thermoplastic healing agent EMAA into epoxy/amine (DGEBA/
TETA) polymer network. The specimens showed a great fracture load recovery and multiple
cycles of healing especially for the high molecular weight epoxy additive specimens. The
healing mechanism of this system occurred through a pressure delivery mechanism of
EMAA into the crack plane during thermal activation.119 Table 7 shows the summary of the
thermoplastic/thermoset blend self-healing system.

2.2.3 Ionomers in ballistic self-healing system

Ionomers in ballistic self-healing mechanism can be described as an instantaneous healing of
a polymeric structure followed by a ballistic impact.8,120 EMAA ionomers and copolymers
Figure 6. (a) Preparation of shape memory thermoplastic polymer by blending n-PCL and 1-PCL by UV-initiated Thio-ene polymerisation, in the presence of non-reac-
tive 1-PCL.115 (b) Schematic showing crack closure and crack rebonding of the shape memory thermoplastic blend specimens under different healing temperature, the
higher temperature showed better crack healing.115 © The American Chemical Society. Reproduced by permission of The American Chemical Society. Permission to
reuse must be obtained from the rightsholder. c) Schematic diagram of SMASH polymer composite coating concept embedded with electropspun PCL fibers.116
© The American Chemical Society. Reproduced by permission of The American Chemical Society. Permission to reuse must be obtained from the rightsholder.
POLYMER REVIEWS
243
244 I. L. HIA ET AL.

Table 7. Summary of thermoplastic/thermoset blend self-healing system.

Composite Healing Evaluation Measured Max. Healing Max. Ref.
Condition Method Parameter Efficiency (%) Healing Cycle
113
Poly(bisphenol-A- 1308C, 1hr Mode I, Peak fracture 75 1
co-epichlorohydrin) Compact tension load
Epoxy blend
118
EMA & EMAA Carbon 1508C, 30 min Mode I, DCB Fracture 88 1
Epoxy Composite toughness
18
EMAA-Epoxy/Amine 1508C, 30 min Model 1, SENB Peak 45 4
fracture load

that possess this unique instantaneous self-healing ability on ballistic puncture with velocity
up to 500 ms¡1 which is different from other self-healing mechanisms.8,120,121 This self-heal-
ing mechanism does not require any chemicals or thermal energy to be triggered which leads
to a wide range of possible applications including military vehicle fuel tanks, protective wall
of oil tankers, spacecraft protective barrier, and other means of containment applica-
tion.121,122 This mechanism was proposed to follow a two-stage process.8 First, the elastic
rebounds of molten polymer close the hole upon release of projectile. Second, the closed
hole is then sealed through melt interdiffusion of EMAA polymer chains (Fig. 7).
Kalista and Ward120 studied EMAA self-healing response at different temperatures and
showed that most of the EMAA specimens were healed even at -308C except for non-ionic
copolymer. This proved that the puncture process was able to raise the film temperature to
viscoelastic state even at low temperature. An earlier study by the same team showed that
the self-healing behavior of EMAA materials were not dependent on the ionic groups within
the polymer.8 However, recent study had established a self-healing “phase diagram” where
the ionomer self-healing mechanism had great relationship with ionic content and impact
temperature.122
Varley and van der Zwaag123 investigated on the elastic and viscous response of ionomer,
Surlyn 8940 (DuPont) under ballistic impact. Different behaviors were exhibited at different
regions of the impact area. It was found that ductile/elastic behavior was exhibited on outer
impact regions whereas elastomeric and viscous behavior was observed closer to the impact

Figure 7. Schematic showing the instantaneous healing process in which the polymer is being penetrated
by high velocity bullet. It shows the process of being impact, deformed, elastic rebound, and hole closure
through melt interdiffusion of polymer chains.8
 POLYMER REVIEWS 245

area. This material showed multiple healing events and the healing events were found to be
dependent on the presence of ionic clusters. Another new method to quantify the healing
efficiency of ionomer was established by measuring the volume/area ratio of specimens
recovered under a scratch test.124 The study showed that the maximum scratch healing effi-
ciency of 65% was achieved which was independent to the cluster state. In order to exploit
the inherent self-healing capability of ionomers, Rahman et al.125,126 blended ionomers with
epoxidised natural rubber (ENR). The thermal and mechanical properties of the blend can
be tuned by altering the composition of the blend and at the same time without significant
losing the self-healing properties. Unlike the previous discussed self-healing mechanisms,
there are no established assessment methods in evaluating ionomer self-healing system to
date due to the challenges faced in measuring healing corresponds to the impact and thermal
change that occurred in split seconds.

2.2.4 Photochemical self-healing system

Chung et al.127 was the first to introduce photochemical self-healing polymer that only
require light stimuli. In his work, the self-healing polymer was introduced through photo-
chemical [2C2] cycloaddition of cinnamoyl groups. In order to assess the self-healing ability
of 1,1,1-tris-(cinnamoyloxymethyl)ethane (TCE) film, the specimens were cracked and then
healed under UV light of λ > 180 nm for 10 min. The flexural strength recovery of the speci-
mens was up to 19% and a higher efficiency was obtained at higher temperature. Oya et al.128

Figure 8. Schematic showing the self-healing mechanism of PBAC2/C4.128 © Nature. Reproduced by per-
mission of Nature. Permission to reuse must be obtained from the rightsholder.
246 I. L. HIA ET AL.

developed another photo-remendable polymer from a cinnamoyl-telechelic poly(butylene

adipate) (PBAC2) and a tetracinnamoyl linker (C4) through photodimerisation process of
the cinnamoyl groups (Fig. 8). As the polymer structure was damaged, it led to the dissocia-
tion of cinnamate dimers along the crack surfaces into cinnamate monomers. The cinnamate
monomers and network polymer were re-dimerized upon exposure to UV irradiation and
healing occurred consequently.
Ghosh et al.129,130 introduced self-healing polyurethane networks upon exposure to the
UV light. The polyurethane network was crosslinked with oxetane-substituted chitosan pre-
cursor to form oxetane-substituted-chitosan-polyurethane (OXE-CHI-PUR) where the
OXE-CHI precursor was the main factor for network remendability (Fig. 9).130 The self-
healing ability of the specimens was evaluated by creating a scratch on the surface and exam-
ine the damaged area optically upon healing under UV light of 302 nm wavelength for
30 min. The healing of the scratch was found to be improved with increasing UV light inten-
sity. The same team also found that at higher acidity, healing was inhibited and the scratch
will expand instead.131 On the other hand, decreasing of OXE content within OXE-CHI-
PUR networks will reduce the healing time as well. The inherent self-healing polyurethane
can be used in a wide range of coating applications as polyurethane itself is a good scratch
resistant material.
Subsequently, Ling et al.19 crosslinked polyurethane network with coumarin as a side
chain. The photosensitive and improved mobility features of coumarin made the polymer

Figure 9. Schematic showing the synthesis of OXE-CHI, (1) forming of OXE-CHI precursor and (2) formation
of remendable OXE-CHI-PUR polymer network.130 © The AAAS Publishing Group. Reproduced by permis-
sion of The AAAS Publishing Group. Permission to reuse must be obtained from the rightsholder.
 POLYMER REVIEWS 247

structure reversible under UV irradiation. This coumarin crosslinked polyurethane had sim-
ilar properties as conventional polyurethane such as transparency and mechanical perform-
ances but with photo-remendability. It can be healed multiple times under UV light at
ambient temperature with first healing efficiency at 70%. Amamoto et al.131 incorporated
reactive thiuram disulphide (TDS) units with re-shuffling capability into low Tg polyure-
thane main chains. A cylindrical specimen of this crosslinked polymer was cut and placed
into the two broken pieces in contact under visible light at room temperature. The specimen
was completely healed after 24 hr to initial integrity and shape.
Dong et al.132 developed a novel class of A2-B3 supramolecular hyperbranched polymers
(SHP) which was photoreversible. This was formed by host-guest complexation of azoben-
zene dimer (Diazo) and b-cyclodextrin trimer (b-CD3). This polymer structure has the abil-
ity to switch reversibly by ultraviolet/visible (UV/Vis) light irradiation and vice versa. To
date, no study has been done to assess the healing ability of this A2-B3 SHP. Another photo-
chemical self-healing supramolecular polymer was developed by Burnworth et al.133 This
supramolecular polymer was formed by combining a rubbery, amorphous poly(ethylene-co-
butylene) core with 2,6-bis(10 -methylbenzimidazoyl)pyridine (Mebip) ligands at the termini
and metal ions (Zn2C or La3C). Upon UV light exposure, the metal-ligand motifs were
excited and as the excited states returned to the ground states, the absorbed energy was con-
verted to heat, thus allowing the structure to depolymerize, liquefy, and heal the dam-
age.133,134 Under stress-strain experiments, the specimens showed a full recovery upon UV
irradiation.

2.2.5 Dynamic bond self-healing system

Generally, dynamic bond self-healing can be defined as any type of bonds that are able to
undergo breaking and reformation repetitively under an equilibrium state.135 Dynamic bond
self-healing can be segregated into two divisions—supramolecular and dynamic covalent
self-healing. The healing of supramolecular polymer systems is normally under equilibrium,
while dynamic covalent systems require extra intervention (heat, salt, etc.) for healing.
Supramolecular self-healing system does not relies solely on covalent bonding, but a more
complex strategy is involved which includes the use of non-covalent and transient bonds
such as p-p stacking, hydrogen bonds, and coordination of ligands to metal ions to generate
networks in order to execute multiple healing events.136-138 Cordier et al.139 first developed
supramolecular self-healing material which behaves like rubber, showing recoverable exten-
sibility of several hundred percent and low creep formation under load. Furthermore, it was
able to self-heal repetitively when the fracture surfaces were brought together at room tem-
perature. Another self-healing elastic nanocomposite was introduced by Wang et al.140 by
integrating hydrogen-bonded polymer with graphene oxide (GO) crosslinker. The small
amount of GO for dramatic improvement in mechanical properties resulted in the high den-
sity of available hydrogen sites was still maintained. A 90% of tensile strength was recovered
at room temperature.
Hentschel et al.141 reported a self-healing material with the concept of supramolecular
block copolymer in bulk solid state. This multiphase supramolecular block copolymer was
able to retain both the stiffness and toughness of thermoplastic elastomers with healing abil-
ity of supramolecular structures. A 75% recovery of tensile strength was shown after healing
at 458C for 18 hr. Tee et al.142 then introduced a self-healing composite with pressure- and
flexion-sensitive properties which can be applied in electronic skin. It is a composite material
248 I. L. HIA ET AL.

formed by a supramolecular organic polymer with embedded nickel nanostructured micro-

particles. At ambient temperature, this material showed about 90% of initial conductivity
restoration and full restoration of mechanical properties within a short time.
Bode et al.143 crosslinked iron (III) sulphate onto terpyridine containing copolymers
to obtain a material that can have a compromise between mechanical properties and
self-healing features. At 808C, the lauryl methacrylate copolymer crosslinked with iron
(III) sulphate specimen showed highest healing ability on scratches. Zeng et al.144 devel-
oped a copolymer containing dibenzylammonium (DBA). It possesses multi-stimuli
responsiveness properties with self-healing capability of at least three times (Fig. 10). In
future, focus will be towards improving the mechanical strength and structural stability
of supramolecular polymer system.139
On the other hand, dynamic covalent self-healing system attracts equal attention due
to the repetitive self-healing properties with mechanically stable structures.145 Such
polymer systems utilize reversible covalent bonds in response to external stimuli to
achieve healing. Canadell et al.146 developed a covalently disulfide crosslinked rubber
where the healing is carried out through exchange of the disulfide groups. This polymer
is able to heal repetitively at moderate temperature and is ideal for coating applications.

Figure 10. Supramolecular gel that responsive to multi-stimuli. (a) Guest- (b) thermo- (c) chemical- (d) KC-
and (e) acid/base-induced gel-sol transition.144 © Elsevier. Reproduced by permission of Elsevier. Permis-
sion to reuse must be obtained from the rightsholder.
 POLYMER REVIEWS 249

Figure 11. Images show the healing of hydrogel thin film from damages captured by digital camera (a, d,
g), brightfield optical microscopy (b, e, h) and atomic force microscopy (c, f, i) virgin hydrogel (a-c), dam-
aged hydrogel (d-f) and after healing by rehydration (g-i).147© John Wiley and Sons. Reproduced by per-
mission of John Wiley and Sons. Permission to reuse must be obtained from the rightsholder.

A self-healing hydrogel film was introduced that has the ability to heal instantly and
repetitively when solvated by water (Fig. 11).147 This hydrogel film is fabricated by (LbL)
polyelectrolyte assembly. With the increasing interests on polyelectrolyte multilayers due to
its attractive properties for biomedical applications, a new self-heal compact polyelectrolyte
complexes (CoPECs) was developed.148 This material, poly(acrylic acid) (PAA)/poly(allyl-
amine hydrochloride) (PAH) CoPECs has the inherent mending properties. The cut PAA/
PAC CoPECs film is able to adhere together in the presence of salt. Amamoto et al.145 dem-
onstrated another polymer gel that undergoes repetitive self-healing through dynamic cova-
lent reshuffling of trithiocarbonate (TTC) units responsive to UV irradiation in the presence
of solvent. As the trend was shifting to autonomic self-healing, Imato et al.149 developed a
covalent cross-linked polymer film that can be healed under mild conditions without any
external stimuli (Fig. 12).
Recently, Cromwell et al.150 developed a polymer with its malleability and self-healing
properties that are tunable by crosslinking 1,2-diol-containing polymer backbones with tele-
chelic divalent diboronic esters. Likewise, another self-healing polymer system with its Tg
being tunable was introduced by Kuhl et al.151 This polymer film is able to heal deep
scratches up to 1 cm in length with 10 mol% of crosslinker at 125 C (Fig. 13).

3. Comparison study for different self-healing mechanisms

This review aims to provide an overview of the recent developments for self-healing polymer
composite especially in the past five years. Two types of self-healing mechanisms are being
focused on which includes extrinsic and intrinsic self-healing mechanisms. Each self-healing
mechanism are being discussed and compared on their healing efficiencies, limitations, and
250 I. L. HIA ET AL.

Figure 12. Images show self-healing behavior of two different polymer gel (gel 2 and control specimen)
under air at room temperature; cut, mended, and stretched state after 24 hr. Polymer gel 2 shows
remendability/healing after 24 hr whereas the control specimen remains into two separate gels.149 ©
John Wiley and Sons. Reproduced by permission of John Wiley and Sons. Permission to reuse must be
obtained from the rightsholder.

assessment method. This section aims to provide a summary and comparison for both the
extrinsic and intrinsic self-healing mechanisms by presenting the advantages, disadvantages
and their possible or existed applications respectively as shown in Table 8.

4. Conclusions and future perspectives

Over the past decade, development of self-healing materials has been subjected to extensive
research and significant progress was made in producing high performance polymers and
composites with self-repairing ability either extrinsically or intrinsically. A large variety of
self-healing concepts and approaches were introduced to suit the real time applications.
However, great research efforts are required to address several technical challenges in order
to transform laboratory samples into practical applications.
For both extrinsic and intrinsic self-healing systems, finding high throughput, scalable
and cost-effective methods in mass producing these materials require highly focused
research efforts. However, recent studies by researchers focused more on the design and fab-
rication of self-healing composites for specific purposes and cases rather than

Figure 13. Self-healing of crosslinked polymer (acylhydrazone monomer with TEGMEMA and HEMA como-
nomer): (a) annealed polymer film (b) scratch before heating and (c) healed scratched after heating for 64
hr at 100 C.151 © John Wiley and Sons. Reproduced by permission of John Wiley and Sons. Permission to
reuse must be obtained from the rightsholder.
Table 8. Comparison table for different self-healing mechanisms.
Self-healing system Category Advantages
Capsule-based Capsule/Catalyst – simple healing concept with the incorpo-
system ration of catalyst and epoxy-loaded cap-
sules only.
– the epoxy-loaded capsules can be pro-
duced easily without the need of an
advanced device.
Dual Capsule – no catalyst is needed, thus cheaper com-
pared to capsule/catalyst healing system.
– the capsules can be easily dispersed
within the matrix without having any
concern of formed clusters.
Mono capsule – it is the simplest among the capsule-
based healing system, only require one
type of capsule for healing.
– can be easily dispersed into matrix
homogeneously.
– not require other functionalities to trig-
ger healing.
– can be easily encapsulate through con-
ventional UF encapsulation method.
Vascular-based One dimensional – multiple healing cycles can be achieved
system – healing agent is evenly distributed in one
direction.
Disadvantages
– limited to one time healing cycle, poor
dispersion of catalyst substantially pre-
vent the healing agent being cured and
thus incomplete healing.
– catalyst deactivation by curing agent but
wax protected catalyst has been used to
improve this issue.
– to date, Grubbs’ catalyst provides the
best results though it is not cost effective,
and its sensitive to moisture and oxygen.
– limited to one time healing cycle.
– stoichiometric ratio of monomer and
hardener as well as dispersion homoge-
neity are crucial for complete healing.
– reactive nature of hardeners makes it dif-
ficult to be encapsulated.
– healing microcapsules must be rigid to
withstand mechanical stress during the
fabrication and brittle at the same time
to facilitate capsule rupture upon crack
formation.
– this healing system requires chain
mobility of the under-cured epoxy
matrix which is only limited to the low
temperature curing system.52
– most of the solvents are toxic and this
prevent it from being commercialised.
– blockage of core fiber may occur during
filling and releasing of healing agents,
depending on the viscosity and diame-
ter of the vascule.
– the implementation of vascules reduces
laminate composite strength.
Possible/Existed applications
aircraft, aerospace and automotive industries
– the increasing usage of thermoset com-
posite in aerospace and automotive
industries thirst for advanced engineer-
ing materials.
– ionomers can be applied for aerospace,
military transport and etc. to withstand
the high impact damages.
coatings, paintings, adhesives
– tribological coatings or self-lubricating
coatings for wear resistance and friction
reductions.
– the use of SMP in self-heal coating for
packaging to prevent cracking and heal
the cracks during ceasing.
– anti-scratch painting for automobile, per-
sonal goods, electronics and etc.
– anti-corrosion coating for automobile,
aerospace, marine, oil and gas engineer-
ing and etc.
medical devices
– any prosthetic implant body parts where
repair and maintenance are not possible
such as pacemaker, limbs, joints or
fittings.
– with the self-healing features, it prolongs
the service time of the prosthetic
implants and sports equipment.
– the durability and quality of sports equip-
ment are always prioritised as apart from
prolong the service time, it also enhances
the safety of the users such as badminton
racquet, golf clubs, tyres and etc.
electrical & electronic Device
POLYMER REVIEWS
– self-healing electrical circuit that able to
heal and restore the electrical conductiv-
ity after damage.
251
(continued on next page)

Table 8. (Continued )
Self-healing system Category Advantages
Two & three – multiple healing events can be achieved
dimensional especially the ability of healing the same
damage area for more than once.
– healing agent is evenly distributed in all
direction.
Intrinsic self-healing – healing ability is inherent within the
material itself.
– do not require any catalysts or healing
agents to trigger healing.
– in principle, it can heal for infinite cycles
as there is no restriction of insufficient
healing agents.
– the strength of ionomers is much stron-
ger than other types of thermoplastic
materials. Tensile strength of 33 MPa.152
252
Disadvantages Possible/Existed applications
– addition of solvent for the purpose of – self-healing sensing devices, with the
reducing the viscosity of healing agent ability to restore the sensitivity of
will affect polymerisation process and sensors.
healing efficiency as well. packaging
I. L. HIA ET AL.
– blockage of core fiber may occur during – a good packaging is important to protect
filling and releasing of healing agents. the goods from being damaged. Thus, a
– for two part epoxy system, mixing and self-healed with shape memory packag-
breaking both carrier networks is a ing is preferred especially in food
challenge. packaging.
– the vascular network carrying healing
fluid within the matrix reduces composite
strength.
– complicated factors between vascular
network diameter, resin viscosity, fluid
delivery and cost to mechanical
properties.
– external stimuli is needed to trigger
healing activity such as light, heat and
etc.
– most of the intrinsic healing system is
limited to thermoplastic materials which
constrain the applications due to the low
strength and weaker bonds of thermo-
plastic materials
– at high temperature, the materials will
creep due to low Tg. Thus, not suitable
for high temperature applications.
 POLYMER REVIEWS 253

commercialization and mass production. Improving the properties of virgin self-healing

materials is essential, as self-healing materials usually have lower performance compared to
their conventional versions. It is still a challenge to apply the self-healing concept into practi-
cal
applications at different conditions (temperature, pressure, humidity, light, vacuum, etc.)
and this has to be considered carefully during design phase of a self-healing material in order
to achieve not only to long term but also high healing performance throughout the service
life. The vast majority of on-going research on self-healing materials will and should
undoubtedly overcome these challenges and lead to the development of tailor-made self-
healing materials for various applications.
Certainly, capsule based self-healing system has shown great improvements over time in
terms of capsule robustness, capsule types, and different healing mechanism approaches but
the main well-known issue of single healing event is still present. This is the main concern
when taking into consideration real practical applications. Thus, future studies have to focus
in tackling this issue either using different capsule structures or incorporating the shape
memory concept together with self-healing capsules to produce a self-healing material with
multiple healing cycles.
While the main focus of extrinsic self-healing studies has been on the recovery of
mechanical properties, this concept has been applied to impart other functionalities and to
prepare interesting smart materials such as self-healing anti-corrosion coating,66 self-healing
electrical conductive coating,70 thermosensitive composites,84 sensors,142 as well as self-lubri-
cating and wear resistant coatings.68 This strategy may be used by incorporating capsules
with chemicals such as biocides, antimicrobial, or anti-foaling agents for different types of
functional coatings. For instance, self-healing asphalts and concretes might be produced by
embedding capsules containing asphalt rejuvenator or binder which will provide a great
future in civil and construction industry especially in those countries which are constantly at
high risk and exposure to extreme events due to long-term climate change and natural disas-
ters. Meanwhile, the combination of self-healing approach with other methodologies like
self-sensing and shape memory might provide solutions for automatic healing of structural
composites in remote parts.
For the past decade, the self-healing microvascular structure has developed from 2D
pipette to a 3D interconnected network through different fabrication methods.
Improvements have been made to enhance the self-healing agent flowability and
increase mechanical properties of the composite. Recent breakthrough of 3D SnOx/PLA
printed networks has diversified the future possible applications into thermal manage-
ment and electroconfigurability.95 However, there are still studies which have to be
done in this area in order to increase the fundamental understanding of the self-healing
composites such as microfluidic behavior of healing agents, viscosity, and surface fric-
tion of the sacrificial vascular networks, the effect of vascule sizing, shape, gap size
between subsequent vascules, wall thickness, as well as the direction and speed of 3d
printing of vascules.
The burgeoning progression of intrinsic self-healing through DA and rDA reaction, ther-
moplastic/thermoset blends, ionomers, photochemical as well as dynamic bonding are
reported. The majority of the reported studies in this context are limited to thermoplastic
materials which also limited the possible applications especially heavy duty applications due
to the weaker strength, stiffness and low Tg properties. Nevertheless, ionomers show
254 I. L. HIA ET AL.

promising results in instantaneous crack closure and possible containment applications

under high impact risks.
As the trend is towards autonomic healing, the future intrinsic self-healing system has to
focus on healing either without relying on stimuli or just solely rely on easily available stim-
uli. For instance, healing at room temperature or in the presence of UV light that is available
from sunlight. In extrinsic self-healing system, it is common to use TDCB specimen to assess
the healing, but this is not the case for intrinsic self-healing system as there is still lack of a
universal testing method to assess or measure the respective healing. This is important espe-
cially for comparison study between different materials for the self-healing ability
respectively. Therefore, future studies have to look into developing a testing criteria for it.

Abbreviations
2,4,6-tris(dimethylaminomethly)phenol DMP-30

4,40 -diaminodiphenylsulfone DDS

5-ethylidene-2-norbornene ENB
b-cyclodextrin trimer b-CD3
Azobenzene dimer Diazo
Carbon fiber reinforced polymer CFRP
Compact polyelectrolyte complexes CoPECs
Compression after impact CAI
Dicyclopentadiene DCPD
Diels-Alder DA
Diethylenetriamine DETA
Diglycidyl ether bisphenol A DGEBA
Diglycidyl tetrahydro-o-phthalate DTHP
Double cantilever beam DCB
Double cleavage drilled compression DCDC
Epoxidised natural rubber ENR
Ethyl phenylacetate EPA
Ethylene-co-methacrylic acid EMAA
Ethylene-co-methyl acrylate EMA
Fiber drawing nanomanufacturing FDN
Fiber reinforced polymer FRP
Functionalised carbon black FCB
Glass fiber reinforced polymer GFRP
Graphene oxide GO
Hexamethylene diisocyanate HDI
Hollow glass fiber HGF
Layer-by-layer LbL
Pentaerythritol tetrakis (3-mercaptopropionate) PETMP
Phenylacetate PA
Poly(e-caprolactone) PCL
Poly(acrylic acid) PAA
Poly(allylamine hydrochloride) PAH
Poly(melamine-formaldehyde) PMF
Polyacrylonitrile PAN
Polyaniline PANI
Poly(butylene adipate) PBAC2
Polyketone PK
Polymer matrix composite PMC
Polymethyl methacrylate PMMA
Polyoxypropylenetriamine POPTA
Polytetrafluoroethylene PTFE
Polyurethane PU
Ring-opening metathesis polymerization ROMP
retro-Diels-Alder rDA
(continued on next page)
 POLYMER REVIEWS 255

Scanning electron microscope SEM

Single edge notch bend SENB
Supramolecular hyperbranched polymers SHP
Shape-memory alloy SMA
Shape memory assisted self-healing SMASH
Tin (II) oxalate SnOx
Tapered-double-cantilever-beam TDCB
1,1,1-tris-(cinnamoyloxymethyl)ethane TCE
Triethylenetetramine TETA
Urea-formaldehyde UF
Width-tapered-double-cantilever-beam WTDCB

Funding
This project was funded by a grant FRGS/2/2013/TK04/MUSM/03/1 from the Ministry of Higher
Education, Malaysia.

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