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Review
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 1 July 2015
Received in revised form
3 September 2015
Accepted 27 September 2015
Available online 31 October 2015
Self-healing materials are attracting increasing interest of the research community, over the last decades,
due to their efciency in detecting and autonomically healing damage. Numerous attempts are being
presented every year focusing on the development of different self-healing systems as well as their
integration to large scale production with the best possible propertyecost relationship. The current work
aims to present the most recent breakthroughs in these attempts from many different research groups
published during the last ve years. The current review focuses in polymeric systems and their composites. The reviewed literature is presented in three distinct categories, based on three different scopes
of interest. These categories are (i) the materials and systems employed, (ii) the experimental techniques
for the evaluation of materials properties and self-healing efciency of the materials/structures and (iii)
the characterization techniques utilized in order to evaluate (off-line) and monitor (on-line) the healing
efciency of the proposed systems. Published works are presented separately in all the different categories, thus the interested reader is advised to follow the structure of the review and refer to the chapter
of interest.
2015 Elsevier Ltd. All rights reserved.
Keywords:
Self-healing materials
A. Polymerematrix composites (PMCs)
B. Mechanical properties
C. Mechanical testing
1. Introduction
Self-healing materials are a relatively new class of smart materials that possess the ability to fully or partially recover a functionality that is mediated by operational use. Local functionality
loss can be dened as the situation when a section of a material or
structure exhibits degraded performance when compared with the
rest of the material/structure. Global functionality loss can be
dened as the situation when the material or structure exhibits
degraded performance when compared to its properties prior to
any exposure to operational loads.
This work focuses on self-healing polymers and their composites. The incorporation of healing agents in polymeric materials inadvertently leads in a new material with altered
properties when compared to the material that does not possess
the healing functionality. The performance and life-time of the
new composite in conjunction with the efciency of the selfhealing functionality are of primary importance as they are
often competing with each other.
* Corresponding author.
E-mail address: paipetis@cc.uoi.gr (A.S. Paipetis).
http://dx.doi.org/10.1016/j.compositesb.2015.09.057
1359-8368/ 2015 Elsevier Ltd. All rights reserved.
The scope of the rst section of this work is to describe the three
primary self-healing approaches (intrinsic, capsule based and
vascular) as well as the critical issues and challenges associated
with each approach. A review of the literature on the materials that
have been used as healing agents over the last ve years is
presented.
The aim of the second section of this review is to present the
most frequently used testing procedures and specimen geometries
found in research publications during the last ve years. Special
consideration is given to the ones that provide, either qualitatively
or quantitatively, insight on the self-healing performance of the
composites. Associated ASTM standards are also presented.
Finally, in order to gain an overall insight into the behavior of
self-healing materials, their structure, performance and selfhealing effectiveness is evaluated via the use of various characterization and monitoring techniques. The combination of mechanical
testing and materials characterization techniques can exploit the
actual capabilities as well as restraints associated with these materials. The ongoing development of the microscopic, spectroscopic
and other characterization methods during the last decades, renders them invaluable tools, which can provide knowledge about the
structure of materials, their chemical composition, as well as the
way the react. In the last section of the current review, an extensive
93
Fig. 1. Schematic depiction of the DielseAlder based shape memory assisted selfhealing process in a polyurethane material based on PCL and furan-maleimide
chemistry [12].
Reprinted with permission from Rivero G, Nguyen L-TT, Hillewaere XKD, Du Prez FE.
One-Pot Thermo-Remendable Shape Memory Polyurethanes. Macromolecules.
47(6):2010e8. Copyright (2014) American Chemical Society.
94
95
Fig. 2. Thermal-switching of the vesicle-based gel. Photographs of a sample in aqueous solution: (a) before and (b) after heating. (c) Schematic illustration of the solegel transition
[16].
Reprinted from Colloid and Polymer Science, Vol. 291(7), 2013, pp. 1749e58, Thermal-responsive self-healing hydrogel based on hydrophobically modied chitosan and vesicle. Hao
X, Liu H, Xie Y, Fang C, Yang H., Figure 2, Original caption: Thermal-switching of the vesicle-based gel. Photographs of a sample of hm-chitosan (0.4%) and DTAB/5 mS (16 mM/
20 mM) in aqueous solution: a before and b after heating. Before heating, the sample is strongly viscoelastic and holds its weight in the inverted vial. After heating at 55 C for
10 min, the sample is transformed into a low viscosity uid that ows easily. c Schematic illustration of the solegel transition., Copyright Springer-Verlag Berlin Heidelberg 2013,
with kind permission from Springer Science and Business Media.
capsules size were also examined. Results indicated that the critical
resin-solvent ratio in order to obtain submicron capsules (0.6 lm
diameter) was 30:70 in which a total 83% recovery of IFSS was reported. Fig. 3 depicts SEM images of bers with varying capsule
coverage that have been used for the IFSS experiment.
Dual-component microcapsules also drew the attention of the
research community. The approach lies in fabricating a self-healing
epoxy composite by embedding a healing agent consisting of epoxy
and its hardener inside separate capsules. He Zhang and co-worker
[36] created two types of healing agent carriers, i.e. microcapsules
containing epoxy solution (Epolam 5015 and hardener 5015) and
etched hollow glass bubbles (HGBs) loaded with amine solution
(diethylenetriamine and ethyl phenylacetate) which they incorporated in self-healing epoxy system (Epolam 5015 and hardener
5015). Using TGA, SEM and optical microscopy they managed to
characterize both capsules and bubbles. The results indicate that
the amine in the etched HGBs shows high thermal stability during
the curing stage. A mathematical model has been also formulated
in order to calculate the available healants and the diffusion distance on the crack plane of a two-part epoxy-amine. Based on the
simple cubic array model, the diffusion distance of the released
healing agent was calculated to be inversely proportional to the
cubic root of the concentration of the healing agent carrier. In a
more recent study [37], Jin and his team focused on the encapsulation of epoxy and amine reactants in separate polymeric microcapsules. In the case of the epoxy resin, a polyurethane (PU)poly(urea-formaldehyde) (PUF) double shell wall was used. The
core consisted of disphenol-A epoxy resin diluted with a low viscosity reactive diluent (o-cresyl glycidyl ether). As for the amine
capsules, they were produced following a method of vacuum
inltration of polyoxypropylenetriamine (POPTA) into polymeric
hollow (PUF walled) microcapsules, demonstrating thus a simple
approach for the encapsulation of a highly reactive core material.
Both epoxy and amine microcapsules can be seen in Fig. 4.
96
Fig. 4. (a) Epoxy capsules consist of a polyurethane e poly(UF) double shell wall and a DGEBA/o-CGE core. (b) Amine capsules contain a poly(UF) shell wall and a POPTA core [37].
Reprinted from Jin H, Mangun CL, Grifn AS, Moore JS, Sottos NR, White SR. Thermally stable autonomic healing in epoxy using a dual-microcapsule system. Advanced Materials.
26(2):282e7, Copyright (2013) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
97
Fig. 5. A representative TEM image of a microtomed cross-section of a silica coated DCPD-lled capsule. The DCPD core is removed during the microtoming process [38].
Reprinted from Aaron C. Jackson, Jonathan A. Bartelt, Kamil Marczewski, Nancy R. Sottos, Paul V. Braun. Silica Protected Micron and Sub-Micron Capsules and Particles for SelfHealing at the Microscale. Macromolecular Rapid Communications. Copyright (2010), Wiley Periodicals. Inc.
98
Fig. 7. Life-cycle of a self-healing microvascular ber-composite. Pristine woven composite laminate showing stacked textile reinforcement with dual-channel (red/blue), liquid
lled vascular network [48]. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
Reprinted from Patrick JF, Hart KR, Krull BP, Diesendruck CE, Moore JS, White SR, et al. Continuous self-healing life cycle in vascularized structural composites. Advanced materials.
26(25):4302e8, Copyright (2014) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fig. 8. (aec) Schematics of the unit cell of the preforms. Optical micrographs show surfaces (def) normal to the warp direction and surfaces (gei) normal to the weft direction. Scale
bars represent 1 mm [49].
Reprinted from Composites Part A: Applied Science and Manufacturing, Vol. 59, Coppola AM, Thakre PR, Sottos NR, White SR. Tensile properties and damage evolution in vascular
3D woven glass/epoxy composites. pp. 9e17, Copyright (2014), with permission from Elsevier.
99
100
101
SRR %
102
Fig. 13. Adhesion recovery as function of the healing temperature and cross-linker type at 65 C using (a) 4-SH or (b) 3-SH [73].
Reprinted from Lafont U, van Zeijl H, van der Zwaag S. Inuence of cross-linkers on the cohesive and adhesive self-healing ability of polysulde-based thermosets. ACS applied
materials & interfaces. 4(11):6280e8. Copyright (2012) American Chemical Society.
Fig. 14. (a) Three-point bending test set up, (b) three-point bending specimens [77].
Reprinted from Wu X-F, Rahman A, Zhou Z, Pelot DD, Sinha-Ray S, Chen B, et al. Electrospinning Core-Shell Nanobers for Interfacial Toughening and Self-Healing of Carbon-Fiber/
Epoxy Composites. Journal of Applied Polymer Science. Copyright (2012), Wiley Periodicals. Inc.
An alternative geometry to the TDCB geometry is the widthtapered double cantilever beam (WTDCB) (Fig. 16). The WTDCB
provides a crack length independent measurement of mode I
fracture toughness like the TDCB geometry. Jin et al. [27] uses the
103
Fig. 16. (a) Geometry of WTDCB specimen consisting of adhesively bonded A36 steel
adherents. (b) Optical microscopy of cross section of a self-healing adhesive incorporated with Grubbs' catalyst and DCPD microcapsules [27].
Reprinted from Polymer, Vol. 52(7), Jin H, Miller GM, Sottos NR, White SR. Fracture and
fatigue response of a self-healing epoxy adhesive. pp. 1628e34, Copyright (2011), with
permission from Elsevier.
Fig. 17. Schematic showing the interplay locations of the EMAA bers and the
delamination fracture plane in the carbon bereepoxy laminates [92].
Reprinted from Composites Part A: Applied Science and Manufacturing, Vol. 43(8),
Pingkarawat K, Wang CH, Varley RJ, Mouritz AP. Self-healing of delamination cracks in
mendable epoxy matrix laminates using poly[ethylene-co-(methacrylic acid)] thermoplastic. pp. 1301e7, Copyright (2012), with permission from Elsevier.
104
healing functionality. In order to explore if a system shows selfhealing functionalities the creation of an articial defect in the
coating system, and evaluation of the ability of the system to suppress or decrease corrosion to desired levels and restore the protective functionality has been broadly used. A detailed review
regarding the employed self-healing corrosion protection methodologies can be found in Ref. [103].
One of the most used techniques in corrosion science to
monitor local corrosion damage is the Electrochemical Impedance Spectroscopy (EIS) via bod plots (Fig. 22) [104e106]. In order to access the charge transfer resistance or polarization
resistance that is proportional to the corrosion rate at the
monitored interface, EIS results have to be interpreted with the
help of a model of the interface. An important advantage of EIS
over other laboratory techniques is the possibility of using very
small amplitude signals without signicantly disturbing the
properties being measured. To make an EIS measurement, a small
amplitude signal is applied to a specimen over a range of frequencies. The EIS instrument records the real (resistance) and
imaginary (capacitance) components of the impedance response
of the system. Depending upon the shape of the EIS spectrum, a
circuit model or circuit description code and initial circuit parameters are assumed and input by the operator. EIS can provide
quantitative information about the electrochemical state of a
coating. The EIS set up is used by Garcia et al. [29] in order to
assess the healing performance of their proposed self-healing
anticorrosive organic coating. Scanning Vibrating Electrode
Technique (SVET) is also employed in order to provide further
verication on the EIS results.
Corrosion activity maps can be obtained by using the SVE
Technique [107]. SVET uses a single wire to measure the voltage
drop in a solution. This voltage drop is a result of local current at
the surface of a sample. Measuring this voltage in the solution,
Fig. 19. End notched exure specimen geometry as adopted by Ref. [94].
Reprinted from International Journal of Solids and Structures, Vol. 46(13), Ouyang Z, Li
G. Nonlinear interface shear fracture of end notched exure specimens. pp. 2659e68,
Copyright (2009), with permission from Elsevier.
Fig. 20. Energy vs. time curves for microcapsules contained glass ber reinforced
composites [98].
Reprinted from Chowdhury RA, Hosur MV, Nuruddin M, Tcherbi-Narteh A, Kumar A,
Boddu V, et al. Self-healing epoxy composites: preparation, characterization and
healing performance. Journal of Materials Research and Technology. 2015;4(1):33e43.
Copyright (2015), with permission from Elsevier.
105
The self-healing concept has also been implemented and achieved for materials with electrical functionality. Such materials are
able to recover conduction paths at different scales and most investigations of conductivity recovery in the literature deal with the
healing of such conductive paths.
A qualitative way to monitor the recovery of conductivity in
self-healing materials can be found in the works of Palleau et al.
[109]. Here a simple electronic circuit consisting of a LED, a voltage
source and a self-healing stretchable (SHS) wire in series is
monitored and captured in video (Fig. 26). The SHS wires are a
combination of a self-healing polymer structured with microchannels lled with EGaIn. Scissors are used to cut the wire so
that the circuit continuity is lost. When the wires are aligned, the
liquid metal components merge together forming a continuous
and conductive wire.
For studies where a very small change in resistivity is to be
monitored, a Wheatstone bridge set-up is preferred. This technique
measures an unknown resistance by using an electrical circuit. The
Fig. 22. (a, b) Bode plot and phase angle, (c) of specimens coated with nanocapsules loaded with various types of corrosion inhibitors [106].
Reprinted from Progress in Organic Coatings, Vol. 76(10), Choi H, Kim KY, Park JM. Encapsulation of aliphatic amines into nanoparticles for self-healing corrosion protection of steel
sheets. pp. 1316e24, Copyright (2013), with permission from Elsevier.
106
Fig. 23. (A) SVET current density map and (inset) visual appearance of the scratched control sample. (B) SVET current density map and (inset) appearance of the scratched NPs_BTAa sample [30].
Reprinted from Hollamby MJ, Fix D, Donch I, Borisova D, Mohwald H, Shchukin D. Hybrid polyester coating incorporating functionalized mesoporous carriers for the holistic
protection of steel surfaces. Advanced materials. 23(11):1361e5, Copyright (2011) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Vnorm Vh V =Vo V ;
where Vo is the bridge voltage before damage, V is the bridge
voltage measured for a fully broken circuit, and Vh is the instantaneous bridge voltage of the circuit. The value of Vnorm ranges
from zero for a specimen with no electrical conductance to one for
Fig. 24. (A) Scheme depicting the model-coating system and the experimental set-up used to evaluate the self-healing performance of the coating system. (B) Corrosion potential
monitored by SKP in the defect. (C) Delamination proles recorded by SKP [108].
Reprinted from Vimalanandan A, Lv LP, Tran TH, Landfester K, Crespy D, Rohwerder M. Redox-responsive self-healing for corrosion protection. Advanced materials. 25(48):6980e4,
Copyright (2013) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
107
Fig. 25. (a) Optical micrograph of AA2024-T3 sample with bare and silyl-treated surface. (b) SECM image of the transition area on (a) using the electroreduction of oxygen. (c)
Approaching-curves performed on the bare metal (black line) and on the silyl-covered area (red line). (d) Overlapped approaching-curves corresponding to measurements using
electrochemical mediator (red-dashed line) and oxygen reduction (black-solid line) [28]. (For interpretation of the references to color in this gure legend, the reader is referred to
the web version of this article.)
lez-Garca Y, Garca SJ, Hughes AE, Mol JMC. A combined redox-competition and negative-feedback SECM
Reprinted from Electrochemistry Communications, Vol. 13(10), Gonza
study of self-healing anticorrosive coatings. pp. 1094e7, Copyright (2011), with permission from Elsevier.
tension and both EIS and in situ tensile loading and electrical
conductivity test revealed a 24 h restoration of this coating
analogous to pure ECNT.
4. Characterization of self-healing systems and monitoring of
their healing efciency
Next to the technical challenge of realizing a self-healing system, there is an inevitable need both for characterizing the functional components that constitute it and monitor the whole process
of self-healing. A variety of characterization techniques can be
found in the literature. However, the methods for monitoring the
self-healing process are limited.
More specically, in the area of characterization the most
common techniques are Fourier Transform Infrared Spectroscopy
(FTIR), Nuclear Magnetic Resonance Spectroscopy, Optical and
Scanning Electron Microscopy (OM and SEM), Transmission electron microscopy (TEM), Atomic Force Microscopy (AFM), X-ray
108
Fig. 26. a) Schematics illustrating the disconnection and reconnection of a simple electronic circuit using a self-healing wire. b) Variation of the resistance of SHS wires during
connection/disconnection/reconnection experiments [109].
Reprinted from Palleau E, Reece S, Desai SC, Smith ME, Dickey MD. Self-healing stretchable wires for recongurable circuit wiring and 3D microuidics. Advanced materials.
25(11):1589e92, Copyright (2013) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
diffraction analysis and rheological studies. In the eld of monitoring, the reported techniques include Raman spectroscopy,
acoustic emission and ultrasonics.
The following section presents an overview of the research
conducted by several groups, with specic examples for each
technique.
4.1. Characterization techniques
4.1.1. Fourier transform infrared spectroscopy (FTIR)
FTIR is a well-established technique based on molecular interactions. In the eld of self-healing materials, this technique is
by far the mostly employed methodology in order to conrm
the healing functionality, compare the virgin and healed materials, as well as to monitor the process of self-healing reactions.
It has been employed both for the characterization of microcapsules [26,39,113e115] and intrinsic self-healing systems
based on DielseAlder cycloadditions [11,116e118]. FTIR has also
been used in other self-healing systems such as self-healing
gels [118], intrinsic reversible crosslinked networks healed via
photocyclization or on disulde links [119], mendable epoxy
networks and 3D braided composites with vascular channels, or
polyurethane/graphene self-healable nanocomposites [120].
An interesting example of the use of FTIR can be found in the
work of Araya-Hermosilla et al. [7] who presented a novel reversible thermoset with tunable Tg based on chemical modication of
aliphatic polyketones and furan and/or amine groups. In this material system they monitored the cycloaddition through the spectral band of CeO stretching around 1000e1300 cm1. As the molar
ratio between furan and maleimide groups increased, the intensity
of the band centered around 1180 cm1 (corresponding to CeOeC
ether peak) also increased, thus testifying the occurrence of the
DielseAlder reaction.
109
Fig. 27. Evolution of the normalized bridge voltage and force during four-point bend tests of a self-healing specimen (a) and a control specimen (b). (c) The percentage of samples
where healing was observed [111].
Reprinted from Blaiszik BJ, Kramer SL, Grady ME, McIlroy DA, Moore JS, Sottos NR, et al. Autonomic restoration of electrical conductivity. Advanced materials. 24(3):398e401,
Copyright (2012) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
110
Fig. 28. Stress and normalized electrical resistance of an ECNT coating (a) without capsules, with (b) hexyl acetate capsules, (c) EPA:EPON microcapsules, and (d) EPA:ECNT [112].
Reprinted with permission from Bailey BM, Leterrier Y, Garcia SJ, van der Zwaag S, Michaud V. Electrically conductive self-healing polymer composite coatings. Progress in Organic
Coatings. 2015;85:189e98, Copyright (2015), with permission from Elsevier.
Fig. 29. Fourier transform infrared spectra of poly(phenylene oxide) (PPO) and the
uncured and cured cyanate ester (CE)/poly(phenylene oxide) systems [122].
Reprinted from Yuan L, Huang S, Hu Y, Zhang Y, Gu A, Liang G, et al. Poly(phenylene
oxide) modied cyanate resin for self-healing. Polymers for Advanced Technologies.
Copyright (2014) John Wiley & Sons Ltd.
(OM), scanning electron microscopy (SEM) or transmittance electron microscopy (TEM) are employed depending on the size of the
studied morphology.
Numerous researchers employed SEM to study various features
including epoxy/hardener containing microcapsules [23,33], fracture surfaces of microcapsules [114], mendable epoxy resins [125],
unhealed and healed CFRPs [126], polyurethane/graphene selfhealing nanocomposites [95], solvent-lled microcapsules incorporated into a polyurethane layer which is deposited atop a silver
ink line for restoring electrical conductivity of the ink [88], shape
memory polymers [104] as well as healing agent containing micro/
nanocapsules embedded in anticorrosive coatings [105].
A very interesting analytical study using SEM in order to view a
three-dimensional image of both the inner and outer surface and
morphology of various capsules ranging from several tens of microns to below 100 nm in size, has been published by Hodoroaba
et al. [127]. In this study SEM was used in the Transmission Mode
and the samples were prepared on thin supporting foils (on TEM
grids). Fig. 30 shows SEM micrographs with corresponding EDX
analyses presented in their study.
Li et al. [128] produced a cement based system containing selfhealing microcapsules. Then, they studied those microcapsules
111
Fig. 30. Upper (a) and in-transmission (b) SEM observation of SiO2 submicrocapsules prepared on lacey carbon foil on TEM grids. (c) EDX analysis conrming compositional
differences of the two particles [127].
Reprinted from Hodoroaba VD, Akcakayiran D, Grigoriev DO, Shchukin DG. Characterization of micro- and nanocapsules for self-healing anti-corrosion coatings by high-resolution
SEM with coupled transmission mode and EDX. The Analyst. 2014;139(8):2004e10. Published by The Royal Society of Chemistry.
112
Fig. 31. Typical topographical AFM images of surface patterns associated with the detachment of two self-healing lms (thickness ~100 nm) from adhesive contact in contact
mechanics tests: a) more viscous state, bed) more elastic state, T 40 C [130].
Reprinted from Faghihnejad A, Feldman KE, Yu J, Tirrell MV, Israelachvili JN, Hawker CJ, et al. Adhesion and Surface Interactions of a Self-Healing Polymer with Multiple HydrogenBonding Groups. Advanced Functional Materials. 24(16):2322e33, Copyright (2014) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
range, chemical state and electronic state of the elements that exist
within a material.
Nowak et al. [104] prepared a self-healing polymer coating
which contained the organic corrosion inhibitors encapsulated
inside the polyelectrolyte nanocapsules. This coating was painted
onto the surface of AA2024 T3 alloy. They utilized XPS in order to
conrm the release of the inhibitor from a scratched coating and
thus the healing reaction of the produced coating. Fig. 32 shows
the acquired spectra from an unscratched surface, a dry scratched
surface and a wetted scratched surface of this self-healing organic
coating. The peak which appears at a binding energy of 163.5 eV
on the spectrum of the dry scratched surface was ascribed to the
inhibitor liberation from the destroyed capsules. The shift of this
peak to the lower value of 162.4 eV of binding energy in the
wetted sample conrms the formation of a sulfurealuminum
bond.
113
114
Fig. 33. Dynamic rheological study. (a) Storage modulus (G0 ) and loss modulus (G00 ) as a function of frequency for 0.4 wt% solution of hm-chitosan with different concentration of
5 mS at 25 C. (b) Relaxation of the concentration of 5 mS at 25 C [16].
Reprinted from Colloid and Polymer Science, Vol. 291(7), 2013, pp. 1749e58, Thermal-responsive self-healing hydrogel based on hydrophobically modied chitosan and vesicle. Hao
X, Liu H, Xie Y, Fang C, Yang H., Figure 5, Original Caption: Dynamic rheological study. (a) Storage modulus G0 (lled symbols) and loss modulus G00 (open symbols) as a function of
frequency for 0.4 wt% solution of hm-chitosan with different concentration of 5 mS (DTAB 16 mM) at 25 C. (b) The relaxation time as a function of the concentration of 5 mS at
25 C, the DTAB concentration is 16 mM., Copyright Springer-Verlag Berlin Heidelberg 2013, with kind permission from Springer Science and Business Media.
Fig. 34. ATME and diffusivity plot with tension crack over exposure time for (a) 100% cement material, (b) 60% cement mass:35% slag:5% Metakaolin [132].
Reprinted from NDT & E International, Vol. 57, In C-W, Holland RB, Kim J-Y, Kurtis KE, Kahn LF, Jacobs LJ. Monitoring and evaluation of self-healing in concrete using diffuse ultrasound. pp. 36e44, Copyright (2013), with permission from Elsevier.
Fig. 35. A sample plot of stress and cumulative acoustic emissions (AEcum) versus
strain. Locations used to record ultimate tensile stress (su), Young's modulus (E), and
strain at damage initiation (AEi) [49].
Reprinted from Composites Part A: Applied Science and Manufacturing, Vol. 59, Coppola AM, Thakre PR, Sottos NR, White SR. Tensile properties and damage evolution in
vascular 3D woven glass/epoxy composites. pp. 9e17, Copyright (2014), with permission from Elsevier.
The group of Zhu et al. [40], who synthesized multilayered microcapsules in a production sequence of four steps, used Raman
spectroscopy for the characterization of the produced structures.
These multi-layered microcapsules are comprised of distinct layers
of glycidyl methacrylate (GMA) e loaded poly(melamine-formaldehyde) (PMF) microcapsules as the core, living PMMA as the
second layer, cuprous bromide/N,N,N0 ,N0 ,N00 -pentamethyldiethylenetriamine catalyst system (CuBr/PMDETA) as the third layer and
a wax coat as the outer shell to protect the air sensitive Cu(I) in the
second layer.
The chemical structure of the microcapsules was veried via
Raman microscopy depth proling, depicted in Fig. 36. The prole
not only described the composition feature of the entire multilayered microcapsule, but also facilitated for a rough measurement of
the thickness of each layer.
Patrick et al. [135] probed the chemical composition of the
healed fracture interfaces of their 3D vascular composites. They
115
Fig. 36. (a e left) Raman spectra of the substances used for composing the multilayered microcapsules. (b e right) Typical Raman spectra of a multilayered microcapsule z120 mm
in diameter collected at the scanning depths from top to bottom [40].
Reprinted from Polymer, Vol. 54(16), Zhu DY, Rong MZ, Zhang MQ. Preparation and characterization of multilayered microcapsule-like microreactor for self-healing polymers. pp.
4227e36. Copyright (2013), with permission from Elsevier.
116
Fig. 37. In situ healing reaction characterization (single cycle, Da 70 mm) via uorescent images in combination with Raman spectroscopy [135].
Reprinted from Patrick JF, Hart KR, Krull BP, Diesendruck CE, Moore JS, White SR, et al. Continuous Self-Healing Life Cycle in Vascularized Structural Composites. Advanced materials.
Copyright (2014) Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
5. Concluding remarks
A wide variety of novel chemistries regarding both extrinsic and
intrinsic self-healing approaches have been developed by the
research community over the last years. As has been shown, signicant effort has been made towards developing an ideal fully
autonomous intrinsic self-healing system capable of regaining its
initial properties rapidly at ambient temperature.
Reversible reactions and especially DielseAlder mechanism are
very promising for the synthesis of processible, remendable and
highly oriented polymers. This class of materials is capable of
regaining its initial properties at the molecular level, theoretically
for an innite number of repetitions without any further addition
of chemicals. However, only small volumes of damage can be
healed because material contact is required for healing, and cyclic
reactions reduce the healing efciency after repeated healing
cycles.
117
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under visible light. Adv Mater 2012;24(29):3975e80.
[11] Toncelli C, De Reus DC, Picchioni F, Broekhuis AA. Properties of reversible
DielseAlder furan/maleimide polymer networks as function of crosslink
density. Macromol Chem Phys 2012;213(2):157e65.
[12] Rivero G, Nguyen L-TT, Hillewaere XKD, Du Prez FE. One-pot thermoremendable shape memory polyurethanes. Macromolecules 2014;47(6):
2010e8.
[13] Sch
afer S, Kickelbick G. Self-healing polymer nanocomposites based on
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