Theo van de Ven and Armand Soldera (Eds.

)
Advanced Materials
Advanced
Materials

Edited by
Theo van de Ven and Armand Soldera
Editors
Prof. Theodorus van de Ven
Dept. of Chemistry
McGill University
Pulp & Paper Research Centre
3420 Rue University
Montreal, Québec H3A 2A7
Canada
[email protected]

Prof. Armand Soldera

Dept. of Chemistry
Faculty of Sciences
Université de Sherbrooke
2500 bld de l’université
Sherbrooke, Quebec, J1K 2R1
Canada
[email protected]

ISBN 978-3-11-053765-9
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List of Contributors
Cyril Aumaitre Anthony Jolly
Département de chimie and Centre de Département de chimie and Centre de
Recherche sur les Matériaux Avancés Recherche sur les Matériaux Avancés
(CERMA) (CERMA)
Université Laval Université Laval
1045 Ave de la Médecine 1045 Ave de la Médecine
Québec Québec
Canada G1V 0A6 Canada G1V 0A6

Serene S. Bayram Olivier Lebel

Department of Chemistry Department of Chemistry and Chemical
McGill University Engineering
Montreal, QC Canada Royal Military College of Canada
Kingston, ON, Canada
Amy Szuchmacher Blum [email protected]
Department of Chemistry
McGill University Janine Mauzeroll
Montreal, QC, Canada Department of Chemistry
[email protected] McGill University
801 Sherbrooke Street West, Room 21
Nadi Braidy Montreal, Québec
Chemical and Biotechnological Engineering Canada H3A 0B8
Canada Research Chair in Synthesis and [email protected]
Charaterization in Multifunctional
Nanomaterials Christopher Moraes
Université de Sherbrooke Department of Chemical Engineering
2500, boul. Université McGill University
Sherbrooke, Québec J1K 2R1 Montreal, QC, Canada
Canada [email protected]
[email protected]
Jean-François Morin
Danny Chhin Département de chimie and Centre de
Université du Québec à Montréal Recherchesur les Matériaux Avancés (CERMA)
Case postale 8888, succursale Centre-ville Université Laval
Montréal, Québec H3C 3P8 1045 Ave de la Médecine
Canada Québec
[email protected] Canada G1V 0A6
[email protected]
Corinne A. Hoesli
Department of Chemical Engineering Sooran Noroozi
McGill University Laboratory of Complex Fluids Research
Montreal, QC, Canada Department of Chemical Engineering
[email protected] Université Laval, Québec
QC G1V 0A6, Canada
[email protected]

https://doi.org/10.1515/9783110537734-204
XII List of Contributors

Michael U. Ocheje Steen B. Schougaard

Department of Chemistry and Biochemistry Université du Québec à Montréal
University of Windsor Case postale 8888, succursale Centre-ville
Windsor, ON Montréal, Québec H3C 3P8
Canada Canada
[email protected] [email protected]

William L. Odette Hanadi F. Sleiman

Department of Chemistry Quebec Centre for Advanced Materials
McGill University Department of Chemistry
801 Sherbrooke Street West, Room 21 McGill University
Montreal, Québec Montreal QC Canada
Canada H3A 0B8 [email protected]
[email protected]
Armand Soldera
Dmitrii F. Perepichka Département de Chimie
McGill University Université de Sherbrooke
Department of Chemistry Sherbrooke, QC, Canada
801 Sherbrooke St. [email protected]
West Montréal, Québec H3A 0B8
Canada Shuhui Sun
[email protected] Institut National de la Recherche
Scientifique-Énergie Matériaux et
Janane F. Rahbani Télécommunications
Quebec Centre for Advanced Materials Varennes
Department of Chemistry QC J3X 1S2, Canada
McGill University [email protected]
Montreal, QC, Canada
[email protected] Seyed Mohamad Taghavi
Laboratory of Complex Fluids Research
Simon Rondeau-Gagné Department of Chemical Engineering
Department of Chemistry and Biochemistry Université Laval, Québec
University of Windsor QC G1V 0A6, Canada
Windsor, ON, Canada [email protected]
[email protected]
M. Nazir Tahir
Md Sazzad Hossain Department of Chemistry and Biochemistry
Université du Québec à Montréal University of Windsor
Case postale 8888, succursale Centre-ville Windsor, ON
Montréal, Québec H3C 3P8 Canada
Canada
[email protected] Raymond Tran
Department of Chemical Engineering
Julia A. Schneider McGill University
Fordham University Montreal, QC, Canada
Department of Chemistry [email protected]
441 E Fordham Rd,
Bronx NY 10458
[email protected]
 List of Contributors XIII

Theo G.M. van de Ven Kacper Wojtkiewicz

Pulp and Paper Research Centre and Department of Chemistry and Biochemistry
Quebec Centre for Advanced Materials University of Windsor
Department of Chemistry Windsor, ON
McGill University Canada
Montreal QC Canada [email protected]
[email protected]
Bing Yu
M.A. (Tony) Whitehead Département de chimie
Pulp & Paper Research Centre and Université de Sherbrooke
Quebec Centre for Advanced Materials Sherbrooke, Québec
Department of Chemistry Canada J1K 2R1
McGill University [email protected]
Montreal QC Canada
[email protected] Gaixia Zhang
Institut National de la Recherche
Qiliang Wie Scientifique-Énergie Matériaux et
Institut National de la Recherche Télécommunications
Scientifique-Énergie Matériaux et Varennes
Télécommunications QC J3X 1S2, Canada
Varennes
QC J3X 1S2, Canada Yue Zhao
Département de chimie
Université de Sherbrooke
Sherbrooke, Québec
Canada J1K 2R1
Contents
Preface V

List of Contributors XI

Julia A. Schneider, Dmitrii F. Perepichka

1 Design Principles for Organic Semiconductors 1

Bing Yu, Yue Zhao

2 CO2-Controlled Polymer Self-Assembly and Application 51

M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz,

Simon Rondeau-Gagné
3 Self-Healing Materials: Design and Applications 87

William L. Odette, Janine Mauzeroll

4 Redox-Responsive Self-Assembled Amphiphilic Materials: Review and
Application to Biological Systems 113

Sooran Noroozi, Seyed Mohamad Taghavi

5 Ultrafine Nanofiber Formation by Centrifugal Spinning 143

Qiliang Wei, Gaixia Zhang, Shuhui Sun

6 Rational Design of Highly Efficient Non-precious Metal Catalysts for
Oxygen Reduction in Fuel Cells and Metal–Air Batteries 161

Janane F. Rahbani, Hanadi F. Sleiman

7 Toward the Assembly of Dynamic and Complex DNA Nanostructures 183

Theo G.M. van de Ven, M.A. (Tony) Whitehead

8 Alternating Copolymer Nanotubes 209

Olivier Lebel, Armand Soldera

9 Molecular Glasses: Emerging Materials for the Next Generation 239

Raymond Tran, Christopher Moraes, Corinne A. Hoesli

10 Production of Pluripotent Stem Cell-Derived Pancreatic Cells by
Manipulating Cell-Surface Interactions 261
X Contents

Nadi Braidy
11 Phase Diagram of an Au–Pt Solid Core–Liquid Shell Nanoparticle 285

Serene S. Bayram, Amy Szuchmacher Blum

12 Directing the Self-Assembly of Nanoparticles for Advanced Materials 307

Cyril Aumaitre, Anthony Jolly, Jean-François Morin

13 Toward Well-Defined Carbon Nanotubes and Graphene Nanoribbons 327

Danny Chhin, Md Sazzad Hossain, Steen B. Schougaard

14 Modeling of Lithium-Ion Batteries 353

Index 389
Preface
In 2006, RAND published a report on the Global Technology Revolution 2020
(https://www.rand.org/pubs/technical_reports/TR303.html). Among the 56 tech-
nologies identified as having profound impacts by 2020, 16 are at the top of the list
for their better chance of becoming established and for their social relevance.
Among them, nine are directly related to advanced materials. A year before the ref-
erence year of this report, we show that research carried out in our Center is per-
fectly aligned with the expected trends. This Centre, Quebec Centre for Advanced
Materials/Centre Québécois sur les Matériaux Fonctionnels (QCAM/CQMF), funded
in 2017, arises from a merge between two recognized centers: Center for Self-Assem-
bled Chemical Structure (CSACS), whose director was Prof. Theo van de Ven, and
CQMF, whose director was Prof. Armand Soldera. Conceptually, it is divided into
three fundamental themes devoted to advanced materials: self-assembly, polymer
science, and nanoscience; and three applied themes dedicated to functional materi-
als: energy, sustainable development, and biomedical applications. This book high-
lights the importance of research in materials in Quebec.
An advanced material can be defined as a material for which some properties
have been greatly improved, comparatively to more conventional materials. This
book contains the main trends regarding this topic from basic research to industrial
applications. The topics of this book fall mainly under TRL (Technology Readiness
Level) 1 to 5. It is also aimed at exposing research in advanced materials developed
by members of CQMF/QCAM. Moreover, it represents a follow-up of our previous
book entitled Functional Materials published by de Gruyter, which mainly repre-
sents a pedagogical treatment of these materials.
The guiding principle underlying the large development of advanced materials
is certainly the way their design is performed. This rational design is at the heart of
all the chapters of this book. All the aspects related to the design of advanced mate-
rials going from fundamental to applied research, or touching biomaterials to elec-
tronic structures, are thus inspected.
A very original design strategy has been envisioned by Rahbani and Sleiman
(Chapter 7): the origami approach. It provides an ideal tool to specifically position
functional objects and study their interactions at the nanoscale level. This way to
fashion DNA leads to the development of nanomechanical devices for applications
ranging from biomedicine to material sciences. The approach in designing biomate-
rials advocated by Hoesli et al. (Chapter 10) follows a different strategy. They pro-
pose to develop tailored functional materials in differentiating pancreatic cells for
cellular therapy of diabetes. For this, an interdisciplinary approach is required to
(1) design platforms to mimic pancreas development and (2) study developmental
biology in vitro. From a different perspective, Odette and Mauzeroll (Chapter 4) pro-
pose to use redox-sensitive lipid-based materials for applications in biological

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VI Preface

systems. They find there a very new source for the development of clinically thera-
peutic systems.
Thanks to a fine-tuning of their constituting molecules, new and optimal prop-
erties emerge. Rondeau-Gagné (Chapter 3) proposes the development of self-healing
materials. This ability to regenerate spontaneously and autonomously has a strong
potential to revolutionize many areas such as advanced technologies or consumer
goods. The propensity of small molecules to form glass instead of the expected crys-
tals also leads to a great variety of applications, including pharmaceutical, pho-
tonic, and optoelectronic. Molecular glasses are also noteworthy materials that can
play an important role in such applications. However, their very understanding re-
mains a challenge. An overview of the progress made in the last 25 years, from their
design, synthesis, their characterization, and the simulation of their properties, is
described by Lebel and Soldera (Chapter 9).
To design new materials that will ultimately lead to interesting applications, self-
assembly remains a very stimulating avenue. van de Ven and Whitehead (Chapter 8)
propose alternate copolymers, where specific self-assembly driving monomers are in-
troduced to generate hollow nanotubes. Morphology transformation was triggered
differently by Yu and Zhao (Chapter 2). It is CO2 that plays this role, thanks to an ap-
propriate introduction of functional groups into polymers. Different CO2-responsive
functional groups are thus proposed. Control of solid-state assembly is exploited by
Schneider and Perepichka (Chapter 1) to regulate charge mobility in organic semicon-
ductors. Structure–property relationships are thus elaborated to better tackle charge
mobility. Achieving semiconducting properties from organic materials is actually
very challenging. To address this issue, Morin et al. (Chapter 13) review some of the
most important aspects regarding the synthesis, purification, and applications of two
highly praised carbon nanomaterials, namely carbon nanotubes and graphene nano-
ribbons. Nanoparticles are advanced materials where self-assembly can leverage
technological applications. Bayram and Blum (Chapter 12) present an overview of the
internal and external methods for directing this self-assembly of nanoparticles. Sta-
bility of such nanosystems, actually for nanoparticles as large as 100 nm, was shown
to greatly depend on the interface. The phase diagram of Au–Pt solid core–liquid
shells was thus revisited by Braidy (Chapter 11).
Designing is also uncovered in the way materials are prepared. The centrifugal
spinning is a novel efficient technique to prepare nanofiber. It consists in extruding
fibers through high speed, rotating polymer solution jets. The setup and the mathe-
matical model are discussed by Taghavi and Noroozi (Chapter 5).
Advanced materials have also a strong impact in designing fuel cells. Two stud-
ies reported in this book are concerned by improvement in this kind of application.
Sun et al. (Chapter 6) explore the chemistry of Fe/N/C electrocatalysts to replace
the rare and expensive platinum for the oxygen reduction reaction in polymer elec-
trolyte fuel cells. Outstanding nonprecious metal catalyst emerges from their lab.
Schougaard et al. (Chapter 14) survey researches on Li-ion batteries, revealing the
 Preface VII

importance in their modeling to incorporate such devices in numerous applications

like storage of renewable energy, electric vehicles, and energy recovery.
To foster the use of performing materials, chemists, physicists, biologists, engi-
neers, and numerical experimentalists must combine their skills to rationalize the
design of materials. This book reveals the powerful energy stemming from the re-
search in Quebec in the domain of materials in 2019. Great strides in this domain
are expected. This book, a follow-up of “Functional Materials” (de Gruyter), is cer-
tainly a concrete example.
M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz,
Simon Rondeau-Gagné
3 Self-Healing Materials: Design
and Applications
Objects and materials that can regenerate themselves spontaneously and autono-
mously, and restore their initial properties after suffering from damages (strain,
puncture, cracks, etc.) seem to be coming directly out of a Sci-Fi movie. With the
recent progress in soft materials, polymer chemistry, and materials chemistry, self-
healing materials are becoming a reality, bringing a multitude of exciting opportu-
nities and possibilities for various day-to-day life applications such as healthcare,
electronics, telecommunication, transport, infrastructure, and others. In this chap-
ter, we will cover important concepts for self-healing and describe some recent ex-
amples of highly efficient self-healing materials. A special emphasis will be put on
the chemistry of this class of materials by examining different strategies that can be
used to design more efficient and autonomously intrinsic self-healing materials. Fi-
nally, examples of applications of self-healing materials for organic electronics will
be described, highlighting some of the promises of self-healing materials for the
next generation of smart materials.

3.1 Introduction
The human body is an incredible source of innovation and technological advance-
ments. Our body is not only functioning in a precise and perfectly regulated man-
ner, but also has incredible properties and characteristics. Among these, the ability
of the body to heal and regenerate itself after an injury is particularly remarkable
from a scientific point of view. Regardless of the type of damage suffered, different
components of our immune system are activated immediately to repair and rebuild
the damaged parts spontaneously and autonomously; everything is done automati-
cally in a relatively short time. The best example is wounds that autonomously stop
bleeding, or broken bones that heal after some time. Throughout the ages, nature
(especially the human body) has inspired generations of scientists to try and repro-
duce these incredible self-healing characteristics. This poses a thought: Would it be
possible to have materials capable of regenerating themselves spontaneously after
being damaged like the human body does? If so, by having such healing abilities,
these types of materials could drastically impact and revolutionize many facets of

M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné, Department of

Chemistry and Biochemistry, University of Windsor, Canada

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88 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

our world, beginning from the way we design consumer products, all the way to the
manufacturing process and conception of new advanced technologies. This may
sound like fiction, but the concept of self-healing is currently under the spotlight of
material scientists, and new materials with self-healing and improved mechanical
properties are continuously being developed and prepared [1–3]. This chapter is in-
tended to present the basic concepts of self-healing and to put into perspective the
different strategies of self-healing as well as the recent technological advances in
this field of materials chemistry.

3.1.1 A Brief History

Self-healing materials have peaked curiosity since the times of antiquity. For a very
long time, humans tried to improve the mechanical robustness and durability of ma-
terials. As architectural achievements have grown, new solutions have made their
presence to slow down, and even prevent, the degradation of materials utilized for
construction. A good example of primitive self-healing comes from the Roman era. As
we know, the Romans have been at the forefront of important architectural achieve-
ments which, even today, remain in very good condition. This preservation through
the ages comes especially from the use of mortar. This mortar, used to bind and stick
the bricks together, was made from volcanic ash and lime, and represents one of the
first examples of self-healing materials [4]. When this material is exposed to rain, a
certain amount of the lime becomes soluble and can move through the brick network.
Thus, lime can fill any crack that has formed over time. Upon water evaporation, the
lime filling the cracks becomes solid, which reinforces the construction and sponta-
neously repairs damages. This phenomenon allowed the Roman construction to self-
regenerate upon damages, which greatly increased the structure’s durability even if
mortar is not a highly resistant material. Based on this ancient concept, several con-
temporary constructions, particularly in Europe and Asia, also relied on the same
principle of a self-healing “glue” to increase their durability.

3.2 Concepts in Self-Healing

Self-healing materials are attracting a lot of attention in modern material sciences
as exemplified by the growing number of scientific publications in the area, which
went from less than 10 in 2007 to almost 500 in 2017 (source: Web of Science). As a
result, a lot of different materials with different self-healing properties have been
reported using a wide variety of approaches. Before describing these approaches
and materials, it is important to understand the basics of self-healing and the con-
cepts that best describe this phenomenon.
 3 Self-Healing Materials: Design and Applications 89

3.2.1 Types of Self-Healing

Self-healing is best described as the property of a material to recover, fully or par-

tially, a certain function or property lost upon damage or stress. Self-healing is di-
vided in two categories: (1) autonomous healing and (2) nonautonomous healing
[5]. As the name suggests, autonomous self-healing occurs without any external
trigger and intervention. Healing of a human skin injury generally occurs spontane-
ously which is a good example of autonomous self-healing. In contrast, nonautono-
mous self-healing requires external interventions, which can be of several types.
For example, if the damaged material requires heat treatment or irradiation in order
to regenerate, this behavior is known as nonautonomous self-healing.
Another way to describe and classify self-healing is regarding the intrinsic ca-
pacity of the materials to regenerate themselves after being damaged, identified as
intrinsic or extrinsic self-healing. In intrinsic self-healing, materials already have
all the components necessary for the activation of self-healing. On the contrary, ex-
trinsic self-healing requires the addition of the required healing agents to trigger
the healing process. These two types of self-healing are directly related to the ap-
proach used and can be modified and tuned directly through the design of the ma-
terials. In general, intrinsic self-healing is preferred as it reduces the energy costs
and decreases the number of steps required for the material to exhibit self-healing
properties.

3.2.2 Self-Healing Mechanism and Efficiency

To get a better understanding of self-healing, it is important to know the different

stages of the process. In the case of the self-healing of bulk mechanical properties,
healing mechanisms proceed through successive steps, as depicted in Figure 3.1 [6].
First, when materials are strained or stretched, the applied tensile energy will dissi-
pate by the system through the formation of macroscopic, microscopic, and/or nano-
scale cracks. This process is known as tensile strain dissipation. Self-healing will be
triggered by the formation of a mobile phase in the materials, which can be formed

(a) (b) (c) (d) (e)

Figure 3.1: Basic mechanism for crack healing in damaged materials: (a) The bulk self-healing ma-
terial before being damaged; (b) crack formation through tensile strain dissipation; (c) formation of
a mobile phase at the surface of the crack; (d) mass transport of the mobile phase to completely fill
the crack; and (e) solidification of the material to restore its initial morphology.
90 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

spontaneously or via an external intervention. This mobile phase is important and

will directly affect the rate and efficiency of the healing. Once the mobile phase is
formed at the surface of the cracks, it can migrate into the crack, thus initiating the
healing process. This mass transport will allow the reconnection of the damaged parts
either chemically or physically. At the final stage, the mobile phase solidifies and be-
comes an integral part of the material, which is completely (or partially) restored.
Since self-healing applies to a specific property of the material, quantifying the
effectiveness of this process can be challenging. To facilitate and quantify self-heal-
ing efficiency, the relationship between the properties investigated before and after
self-healing must be established. Therefore, the self-healing efficiency (η) is defined
by the percent recovery of the property or function f, evaluated for the native and
healed materials (Figure 3.2).

Native material → Damaged material → Healed material → Damaged material

Δf native Δf healed

Δf healed
η =
Δf native

Figure 3.2: Self-healing efficiency calculation and quantification.

Self-healing only applies to a specific property or function, so it is important to con-

sider that not all initial properties of the material are regenerated. The self-healing
efficiency must therefore always be considered in relation to the specific property
studied. In addition, the properties or functions of the materials are rarely fully re-
stored following self-healing. An example of materials’ properties versus time is de-
picted in Figure 3.3 [7]. A traditional material can be stretched up to its breaking
point without a significant loss of performance (green curve). Through several strat-
egies, one might improve the material’s performance and tolerance to tensile strain,
which pushes back the breaking point. However, the material will suffer from a sig-
nificant loss of performance once it reaches its failure point (blue curve). In a self-
healing material or system, a partial loss of performance will occur upon tensile
strain. The performance will then be regenerated upon self-healing, but the initial
performance of the materials will not be fully recovered (red curve). Following sev-
eral self-healing cycles, this hysteresis in the material’s maximum performance will
ultimately lead to complete degradation. In an ideal self-healing phenomenon, no
such hysteresis is observed, which implies fully restored mechanical properties of
the materials after failure and self-healing. However, for most of self-healing strate-
gies, full recovery of the material’s initial properties is very challenging and is
never entirely achieved.
 3 Self-Healing Materials: Design and Applications 91

Performance
Towards ideal self healing

Traditional Improved
material traditional
material
material failure

Time

Figure 3.3: Material’s performance versus time. After an extended period of use or the addition of
stimuli, traditional materials exhibit property failures. For classically improved traditional materi-
als, the mechanisms remain the same. With respect to self-healing materials, they are able to re-
cover their performance and undergo many cycles of stress without exhibiting total mechanical
failure. However, the hysteresis in materials performance before and after self-healing ultimately
leads to material’s degradation.

3.3 Approaches for Self-Healing

Research on the development of new self-healing materials and new concepts has
intensified during the last decade, which led to the establishment of various strate-
gies for self-regeneration. Strongly dependent on the types of materials used and
their properties (elastic modulus, thermal transitions, surface energy, solubility,
etc.), each approach presents important advantages and drawbacks when com-
pared to one another. The following section will present the key approaches for
self-healing and an overview of the most recent developments in their utilization.

3.3.1 Encapsulation of Repairing Agents

Polymers are one of the most studied and investigated type of materials for self-
healing because of several factors such as the ease of chemical functionalization,
an amorphous morphology which allows high mobility of molecules (and polymer
chains) at low temperature and good solubility which facilitate their processing in
different sizes and shapes. For these reasons, encapsulation of regenerating agents
inside a polymer matrix has become a major approach for the development of self-
healing polymers, especially for industries and manufacturers. This type of extrin-
sic self-healing is based on the incorporation of heterogeneities into a polymer ma-
trix, which are composed of active agents (compounds) [8]. Upon damages, these
active chemicals are “spilled” from the damaged areas, thus triggering the healing
reaction. These heterogeneities can be introduced under different shapes and sizes,
92 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

but are generally introduced in the matrix as nanoparticles or hollow fibrous

structures.
As depicted in Figure 3.4a, the self-healing material is designed and processed to
contain heterogeneous pockets of monomers or reagents. Catalytic species are also dis-
persed in the polymeric matrix uniformly. Upon cracks (or damage), the microcapsules
are broken, which liberates reactive agents through the polymer matrix (Figure 3.4b).
Upon exposure to the catalyst embedded in the matrix, polymerization occurs, which
cross-links the reactive monomers and forms an internal glue. The solid phase then
fills the damaged area, regenerating the initial polymer matrix.

(a)

(b)

(c)

Figure 3.4: Self-healing via encapsulation of healing agent. Adapted with permission from Ref. [8].
Copyright 2001 Nature Publishing Group.

Even though this approach can be straightforward and easily applicable to a multi-
tude of different types of polymers, several parameters must be controlled to maxi-
mize self-healing efficiency and allow optimal regeneration of damaged materials.
First, the heterogeneities must be stable in the polymer matrix and deliver enough
materials to allow for complete healing. This important parameter is particularly
challenging to control: large capsules contain more healing agents but can drastically
 3 Self-Healing Materials: Design and Applications 93

affect the bulk properties of the polymeric matrix by modifying the roughness of the
materials and induce crack propagation. In contrast, smaller capsules typically have
a limited amount of healing agents available for delivery upon damage but do not
modify the bulk properties of the polymer. The heterogeneities also need a membrane
fragile enough to rupture when damaged. Therefore, the interface between the poly-
mer and the membrane is important to control and investigate to optimize the release
of the healing agent. Similar to the capsules, the incorporation of the catalyst in the
polymer matrix must not affect the material’s bulk properties. In addition, the healing
agent (monomer) must have a low viscosity (mass transport), a good stability, and be
immiscible with the native polymer. Finally, to enable an optimal self-healing, the
cross-linking reaction must be fast and efficient at room temperature.
One of the most efficient and early demonstrations of the microencapsulation
approach for self-healing has been achieved by embedding encapsulated dicyclo-
pentadiene (DCPD) monomers inside an epoxy matrix (Figure 3.5a) [8]. Grubb’s cat-
alyst (bis(tricyclohexylphosphine) benzylidene ruthenium (IV) dichloride) was used
to trigger a ring-opening metathesis polymerization (ROMP). In this example, DCPD
was used because of its low viscosity, which promoted the dispersion of the healing

(a)

x y

(b)

Figure 3.5: (a) Cross-linking reaction of DCPD with Grubb’s catalyst and (b) scanning electron mi-
croscopy image (SEM) of a fractured capsule containing urea-based healing agents. Adapted with
permission from Ref. [8]. Copyright 2001 Nature Publishing Group.
 94 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

agent in the epoxy matrix. Interestingly, the ROMP reaction successfully repaired
the damaged epoxy polymers, which recovered 75% of its initial fracture toughness
after self-healing. This example clearly demonstrates that the microencapsulation,
when carefully designed and controlled, is a very efficient approach for self-heal-
ing. The utilization of several cross-linking reactions has also been reported since
the last decade. Among others, the polymerization of poly(dimethylsiloxane)
(PDMS) triggered by Pt catalyst, the reaction of epoxide with CuBr2/2-methylimida-
zole complex (CuBr2(2-MeIM)4) and the polymerization of isocyanate in the pres-
ence of water (Figure 3.5b) [9], showed great promise for the extrinsic healing of
polymeric matrices through microencapsulation.

3.3.2 Dynamic Cross-Linking

Based on the rational chemical design of materials, dynamic cross-linking is one of the
most promising approaches in developing intrinsic self-healing materials. Recent de-
velopments in the fields of coordination and supramolecular chemistry have given rise
to motifs capable of forming intermolecular covalent and noncovalent bonds possess-
ing a dynamic characteristic [10, 11]. Furthermore, these interactions can spontane-
ously and autonomously break and reform. This means that the incorporation of such
dynamic bonds into materials through rational chemical design, which can allow ma-
terials to regenerate spontaneously via bond reformation after being damaged, is now
feasible. The following pages will cover several types of dynamic bonds used for the
design of intrinsically self-healing materials. Each of these interactions possesses sev-
eral advantages and disadvantages, which will also be highlighted. Figure 3.6 presents
the most important noncovalent interactions along with their typical range of binding
strength. The comparison between noncovalent and covalent bonds will also be

500
Binding Energy (kcal/mol)

400

300

200

100

0
Metal–Ligand Hydrogen π–π van der Ion–ion Ion dipole Covalent
bonding Waals Bond

Figure 3.6: Binding energies of different types of covalent and noncovalent bonds.
 3 Self-Healing Materials: Design and Applications 95

considered. Because of the wide variety of motifs and binding energies, the choice of
dynamic bonding used for self-healing depends on the desired bulk properties and
chemical design of the materials. The most common methods of producing dynamic
bonds that undergo self-healing are covalent bonding, hydrogen bonding, and metal–
ligand coordination, principally because of the wide range of energy covered and syn-
thetic ease (Figure 3.7).

– Upon physical stress, – Chain ends come in

Native polymer network chains are cleaved contact (segmental
– Reactive chain ends mobility and
generated conformation changes)
– Bond reformation
– Self-healing

Figure 3.7: Schematic illustration of ideal self-healing mechanism in polymers incorporating dynamic
bonding moieties. Upon physical damage, reactive end groups are generated. Upon conformational
changes and segmental mobility of the polymer chains, the dynamic moieties get in contact with
each other, enabling bond reformation and regeneration of the initial polymer network.

Hydrogen Bonding
Hydrogen bonds (H-bonds) are by far the most common and widely studied type of
noncovalent interactions. These supramolecular bonds come from the dipolar interac-
tion of a hydrogen attached to an electron-withdrawing group interacting with a neigh-
boring electronegative atom. These newly formed bonds may not be the most robust
nor as strong as noncovalent bonds, but their dynamic behavior can enable remarkable
mechanical and chemical resistance in materials. In addition, the presence of various
moieties forming H-bonds in natural compounds inspired chemists to develop several
synthetic motifs capable of forming such bonds with different orientation and with dif-
ferent strengths. The complementarity of H-bonds, guided by the design of the donor-
acceptor (D–A) pairs, also brings an additional level of possibility in terms of design by
rationally tuning the bonding strength, and, thus, the mechanical properties of the ma-
terials. Various self-healing polymers have been reported to use this type of dynamic
bonding, making H-bonds one of the most promising supramolecular interactions for
the design of spontaneous self-healing materials [12–14]. Figure 3.8 shows some exam-
ple of self-healing materials based on H-Bonds, enabled by urea and amide groups.
(a) (b)
96

(c)

Figure 3.8: Self-healing materials based on hydrogen bonding motifs: (a) complimentary copolymers incorporating urea functionalities, (b) urea
isopyrimidone (Upy), and c) polyamides. Adapted with permission from Ref. [12] to [14].
M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné
 3 Self-Healing Materials: Design and Applications 97

“Molecular velcro”

Figure 3.9: A self-healing hybrid polymer based on dynamic hydrogen bonding and phase separa-
tion. Adapted with permission from [12]. Copyright 2012 Nature Publishing Group.

Self-healing polymers that rely on H-bonding have the dynamic interactions

directly embedded in a polymer matrix. Therefore, various effects can additionally
influence the efficiency of self-healing, that is, fiber formation, stacking interac-
tions, phase separation, and crystallization of the polymer chains. Moreover, sec-
ondary effects such as dipole–dipole interactions or secondary hydrogen bonding
can also be enabled. Because of these additional effects, the molecular design
and the choice of hydrogen bonding moieties are crucial parameters to control. A
good example of highly efficient self-healing materials based on H-bonds and en-
hanced by phase separation has been recently reported by Guan and coworkers
(Figure 3.9) [12]. In their design, the authors utilized a high glass transition tem-
perature (Tg) polystyrene-based backbone, on to which soft polar H-bonding
brushes were grafted with a low Tg, based on polyacrylate amide. This unique de-
sign allowed for a phase separation in the bulk state, which enabled an entirely
controlled self-healing process. Specifically, when the hybrid polymer was dam-
aged, the weak supramolecular bonds, contained in the polar phase, were prefer-
entially ruptured. Because of the low glass transition of the polyacrylate amide
98 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

matrix, the polymer network can easily rearrange and reform the dynamic amide
H-bonds. This unique design and approach allowed for very efficient self-healing
(92% recovery of the initial mechanical properties) after 24 h and represents an im-
portant example of the versatility of self-healing via dynamic hydrogen bonding.
As mentioned previously, hydrogen bonding offers great versatility for design-
ing self-healing materials. However, in bulk and large-area applications, they are
limited due to the fact that this method is sensitive to moisture and other environ-
mental parameters. Additionally, when compared to different types of dynamic su-
pramolecular interactions, H-bonds are relatively weak.

Metal–Ligand Interactions
Although this method has been extensively studied for different application purposes,
coordination chemistry is another particularly attractive approach to implement self-
healing to a polymer matrix. Based on the affinity of different coordinating motifs to
metal centers, this approach offers multiple design possibilities and great control over
the dynamic interaction strength and orientation. By carefully adjusting for the type
of metal ion and ligand interaction, it is possible to design a cross-linking network
that exhibits appropriate bond strengths with highly stretchable and self-healing
properties [15–18]. It is, therefore, not surprising if metal coordination is found in na-
ture in stretchable and self-healable systems, such as the mussels’ byssus thread,
which utilizes coordination of Fe(III) by pendant catechol units (Figure 3.10) [19].

HO OH O O O O
Fe Fe HO Fe O
HO O
O O O
O HO O HO O

Figure 3.10: Dynamic coordination of Fe(III) by catechol moieties.

Similar to other types of dynamic bonding, the self-healing capabilities of metal–ligand

interactions are because of their dynamic behavior and the ability to dissipate energy
upon strain through bond breakage/reformation. Furthermore, the wide variety of
binding strengths in coordination chemistry enhances the stimuli responsiveness of
the materials, changing the ligand and metal centers, allowing for fine tuning of the
 3 Self-Healing Materials: Design and Applications 99

self-healing process upon different external stimulus, for example, light, heat, and pH.
Also, interestingly, this phenomenon can also be tuned by the different approaches
used in the preparation of the self-healing metallopolymers. In fact, as depicted in Fig-
ure 3.11, depending on the manner that the ligand and metals are inserted in the poly-
mer matrix, different directionality and bonding strength will be achieved.

n– n+
X M Metal ions attached by electrostatic attraction

L L Metal ions attached by coordination on the side chains

L L
M Metal ions as part of the polymer backbone
L L

M
M Metal ions interacting physically with the polymer chain

Figure 3.11: Chemical design approaches to prepare self-healing materials by metal coordination
and incorporation to polymers.

3.3.3 Dynamic Covalent Bonds

While the two approaches that were previously discussed to achieve self-healing in
materials rely on the use of supramolecular bonds, the use of dynamic chemical reac-
tions to generate new covalent bonds is also becoming a popular approach to enable
self-regeneration. Unlike supramolecular interactions, covalent bonds have the ad-
vantage of being more robust and more stable to external conditions such as temper-
ature, moisture, and solvents. It is therefore not surprising to see an increasing
number of reported examples of self-healing materials based on this approach
[11, 20, 21]. The type of dynamic reaction incorporated into the material greatly de-
pends on the final application. Among the parameters to carefully control, the energy
barrier of the equilibrium (direct reaction vs. inverse reaction), the number of mole-
cules involved and the need for external triggers or reagents, are particularly important
factors to consider when designing a technique using dynamic covalent bonding.
100 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

Several types of reactions have already been proven to be effective for self-
healing. Among others, [4+2] cycloaddition reactions (Diels–Alder), are interest-
ing because of their reversibility, by generating retro Diels–Alder adducts. How-
ever, in cases where a high activation energy is required, their compatibility with
low Tg polymeric matrixes will be limited. Exchange reactions, such as the forma-
tion of imine bonds, generated from the condensation of an aldehyde and an
amine, have also been shown to be an effective approach for self-healing. This
acid-catalyzed spontaneous reaction has been recently used to obtain self-healing
materials based on polyethylene glycol (PEG) chains [22]. In addition, another ap-
proach that is quickly gaining attention when producing self-healing materials is
the reaction that spontaneously allows for the exchange between thiol and disul-
fide bonds, given the spontaneity of the reaction and the low energy barrier re-
quired to influence the chemical equilibrium (Figure 3.12) [23, 24]. Finally, the
generation of radicals, resulting from the breakage of a covalent bond under a me-
chanical force, can also be used to repair materials. In general, the lifetime of rad-
icals is much shorter than the time required for self-healing. However, by
carefully developing a method, it is possible to extend the lifetime of the radicals
for a period long enough to regenerate the broken covalent bonds, following self-
healing steps of rearrangement, diffusion, and randomization, discussed earlier
in this chapter. Thiocarbonate, thiuram disulfide derivatives, or alkoxyamines are
some examples of motifs that can be used for this type of dynamic cross-linking
[25, 26]. The breakdown of NO–C bonds, well known to occur for TEMPO deriva-
tives, is also known to generate self-healing material.

Figure 3.12: Self-healing of materials based on the thiol–disulfide exchange.

 3 Self-Healing Materials: Design and Applications 101

3.3.4 Other Approaches to Self-Healing

Shape-Memory Effect
Reactive groups and the type of dynamic bonding, as demonstrated previously, are
very important to consider for the efficiency of self-healing. Another important as-
pect to consider is the ability of the physical network to be remodeled. Upon physi-
cal damage, the ability of a polymeric network to “remember” its initial shape is a
particularly attractive parameter for self-healing, on which the development of
shape-memory polymer is based on [27]. This last family of polymers, in most cases,
relies on the ability of the materials to react to external stimuli and recover their
initial shape and morphology from a temporarily altered physical state. As it is for
most self-healing strategies, the shape-memory effect is highly dependent on the
material’s Tg. At high temperature (above the Tg), the polymer chains are highly
mobile and can flow through the materials. At lower temperature, polymer chains
are fixed and rigid. Therefore, these competing effects can be used to modulate the
segmental mobility of the polymer chains and control the morphology of the materi-
als and self-healing process. It is important to mention that properties other than Tg
can be used to enable a shape-memory effect such as cross-linking density (light-
triggered) and melting point (temperature-triggered). When used in combination
with other self-healing strategies, such as dynamic cross-linking or self-repairing
agents, the shape-memory effect is a powerful technique to enhance the efficiency
of self-healing by enabling an additional opportunity to drive crack closure. A good
example of an efficient, light-triggered, and self-healing shape-memory polymer
has been reported by Langer and coworkers [28]. First, a light responsible polymer
is stretched and irradiated at a specific wavelength (λ) above 260 nm to fix the poly-
mer network through cross-linking. Upon stress release, the polymer remains in its
elongated shape. Interestingly, upon irradiation with λ < 260 nm, the new cross-
linking bonds are cleaved, allowing for the network to recover its memorized, initial
shape. As a result, the damages caused by stretching are entirely healed, allowing
for the material to endure further strain cycles. This light-triggered shape-memory
self-healing is depicted in Figure 3.13.

Migration of Nanoparticles
Another very interesting approach to develop and regenerate a polymer matrix is
based on the migration of nanoparticles. Unlike previous approaches based on the
mobility of polymer chains and on the linkage of various covalent and dynamic
bonds, this approach relies on the incorporation of particles randomly dispersed in a
polymer phase and which, depending on the appearance of cracks or deformations,
can move and concentrate at the damaged interface, causing self-healing within the
material. Based on recent molecular dynamics experiments and confirmed experi-
mentally with CdSe/ZnS nanoparticles embedded in polymethylmethacrylate
102 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

Figure 3.13: Shape-memory effect of a photo-responsive polymer as reported by Langer and

coworkers. Adapted with permission from Ref. [28]. Copyright 2005 Nature Publishing Group.

(PMMA), it has been shown that nanoparticles tend to be attracted toward the dam-
aged area in a polymer matrix, at a higher temperature. As soon as one particle be-
gins to move toward the damaged area, another area becomes depleted of
nanoparticles, which results in the movement of other localized particles to attain
equilibrium again. Upon cooling of the materials, a new and healed morphology can
be generated. Interestingly, it has been shown that larger particles are more effective
than smaller ones, especially at shorter timescales.
Despite being naturally attracted into the depleted regions of a damaged poly-
mer matrix, material chemists creatively designed a new autonomous system to en-
hance the migration of functional particles, which as a result will bolster the self-
healing ability and stimuli response. One of the most inventive approaches has
been reported by Wang and coworkers, using self-propelled nanomotors to autono-
mously seek and repair cracks in electrical systems [29]. More specifically, Au/Pt
Janus spherical nanomotors have been prepared and characterized. These nanomo-
tors can be powered when hydrogen peroxide is introduced in solution as “fuel,”
which reacts with the Pt surface. Therefore, when a crack is formed on the gold
electrode, preventing electrical conductivity, the nanomotors can swim to the dam-
aged area and restore contact. This way, the nanomotors act as conductive
“patches” in the broken circuit and can restore the electrical current. This concept
of self-healing through self-propelled nanoparticles is illustrated in Figure 3.14..
 3 Self-Healing Materials: Design and Applications 103

(a) (b) (c)

Figure 3.14: Schematic illustration of autonomous self-healing of damaged gold electrodes through
migration of self-propelled Janus particles: (a) structure of the Janus Au/Pt nanoparticles, (b) upon
damage, the gold circuit is cracked, thus preventing electrical conductivity, and (c) upon adding H2O2
fuel, the nanomotors move across the system and concentrate at the crack site, thus restoring a con-
ductive pathway. Adapted with permission from Ref. [29]. Copyright 2015 American Chemical Society.

3.4 Some Applications of Self-Healing Materials

As previously demonstrated, there are multiple design possibilities toward self-
healing materials. Therefore, by using the different synthetic tools available, mate-
rial chemists can now design more efficient self-healing materials for various appli-
cations, including regenerative medicine, wearable and stretchable electronics,
consumer goods, advance manufacturing, and so on. In order to give a glimpse of
these applications, the next pages will cover some new and exciting applications of
self-healing materials.

3.4.1 Field-Effect Transistors

Since the last decade, research is being performed to develop new electronic tech-
nology, such as wearable/stretchable devices, intelligent robotics, and body-con-
formable devices [30, 31]. In fact, the demand for such devices has been
significantly increasing in the past years with the rise of new portable and compact
devices. However, current silicon-based electronics, despite their outstanding effi-
ciency, sometimes suffer from limitations of mechanical compliance and robust-
ness. Therefore, different types of conjugated polymer-based materials have been
developed for numerous utilizations in electronics, mainly because of their inherent
characteristics including lightweight, flexibility, easy processing, and structural
versatility [32, 33]. Furthermore, self-healing properties have been recently imple-
mented to these systems toward electronics that can not only be stretched, but also
capable of regenerating themselves after being damaged.
The core units of modern electronic circuits and hardware are field-effect
transistors (FET). FETs are small devices that utilize an electric field to control the
104 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

electrical behavior of the electronic device. FETs are, thus, an integral logic compo-
nent [34]. In current technology, FETs are based on silicon. However, to develop new
stretchable and flexible devices, these devices also need to possess a good mechanical
compliance. Generally, fabricated through the combination of multiple functional ma-
terials (layered device), FETs incorporating self-healing materials have recently been
reported and demonstrated with very interesting properties. First, self-healable dielec-
trics (insulating materials) have been reported via the utilization of metal–ligand dy-
namic cross-linking. Based on polydimethylsiloxane (PDMS), a very stretchable
polymer, the new dielectric materials contain bipyridine moieties, which are capable
of spontaneously coordinating to metal centers, including Fe2+ and Zn2+ (Figure
3.15a–c) [35]. The resulting polymers showed very good electronic properties, crucial
for the fabrication of field-effect transistors including an increased dielectric constant
and good scapacitance. Moreover, the different coordinated bipyridine-containing
PDMS howed a very high stretchability (up 300% strain) and efficient spontaneous
self-healing. Even after a decrease in the stretchability because of the surface aging
for 24 h and then self-healing, the materials were still able to exhibit a strain tolerance
greater than 200% after healing. Interestingly, the new dielectric materials not only
showed good electric and mechanical properties, but also have been used in the fabri-
cation of entirely stretchable FETs. The resulting devices maintained the favorable me-
chanical properties of a dielectric metal-coordinated self-healing polymer, which
opens the door for the development of new electronic materials with autonomous
self-healing via dynamic cross-linking with metal–ligand interactions.
Simultaneously reported by Kim et al., a similar strategy, based on metal-coor-
dination, toward self-healing dielectric materials has been utilized (Figure 3.15d–f)
[36]. The authors reported the incorporation of catechol units to a stretchable soft
polymer based on PMMA. Previously utilized in other self-healing systems, catechol
moieties can form highly dynamic complexes with Fe3+ and are also easily accessi-
ble synthetically. The resulting elastomeric materials demonstrated good electronic
properties (dielectric constant and capacitance) and excellent mechanical compli-
ance, crucial for applications in stretchable electronics. Moreover, after a mild heal-
ing treatment (55 °C for 33 min.), the healed materials showed almost complete
restoration of their initial properties. Despite being nonautonomous, this report
highlights the recent efforts toward self-healable dielectrics and fabrication of fully
stretchable/self-healing FETs.
FETs not only need highly efficient dielectric materials, but more importantly,
require semiconductors with high charge mobility. Therefore, development of self-
healing semiconductors is crucial toward self-healing FETs. Conjugated polymers, a
specific class of organic macromolecules, are the most promising candidates to
achieve these characteristics because they possess all the qualities necessary for the
use as the semiconducting layer in stretchable/self-healing FETs, which include high-
charge carrier mobility, processability via solution deposition, and potential low cost
[32]. However, because of the intrinsic rigidity of conjugated polymeric backbone, the
(a) (b) (c)

(e) (f)
(d)

Figure 3.15: (a) Bipyridine-based cross-linked PDMS polymers (polymer chains and counterion have been omitted for clarity); (b) capacitance
versus frequency measured for various bipyridine-functionalized PDMS; (c) self-healing test for PDMS–bipyridine polymer cross-linked by coor-
dination to Zn2+. Self-healing has been performed under ambient conditions without any intervention; (d) schematic illustration of catechol-
3 Self-Healing Materials: Design and Applications

containing PMMA-based elastomers; (e) capacitance value of the catechol-containing dielectric before and after healing from mechanical break-
down; and (f) transfer characteristics of the FET devices built from catechol-containing PMMA-based elastomers after self-healing. Adapted with
permission from Ref. [35] and [36]. Copyright 2016 American Chemical Society.
105
106 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

development of self-healing conjugated polymers is still challenging. One of the only

examples of a self-healing semiconducting polymer has been reported in 2016 by Bao
et al. [37]. To enable stretchability and self-healing in a highly π-conjugated system,
the authors incorporated pyridine dicarboxamide (PDCA) units into diketopyrrolopyr-
role-based polymers, a unit known to lead to high-charge mobility (Figure 3.16). Inter-
estingly, the PDCA units were used because of their capacity of forming
intermolecular H-bonds via the amide moieties and also because of the fact that they
can act as ligands for various metal centers, including Fe3+ [38]. The resulting conju-
gated polymers, with intermolecular hydrogen bonding, showed an impressive en-
hancement in molecular stretchability and were shown to maintain their charge
transport properties, even at 120% strain. More important, after being damaged, mild
thermal and solvent treatments led to a complete restoration of the polymer morphol-
ogy, which demonstrates the efficiency of dynamic hydrogen bonding to heal the
polymer network. Finally, the new semiconducting polymers were used to fabricate
fully stretchable FET devices. Interestingly, the devices incorporating the healable
conjugated polymers were also able to demonstrate their healing abilities undergoing
similar solvent and thermal treatments. Despite being nonautonomous, the healing
properties of conjugated polymers and related FETs opened the door to the develop-
ment of novel electronic devices that can be both stretchable and healable.

(a) (c)

(b)

Figure 3.16: (a) Healable semiconducting conjugated polymers based on PDCA-containing DPP-
based polymers; (b) treatments used for healing the conjugated polymer thin films after being dam-
aged by strain and (c) charge mobility of the polymers after the different healing treatments.
Adapted with permission from Ref. [38]. Copyright 2016 Nature Publishing Group.

Finally, other stretchable FET components have been shown to possess autono-
mous self-healing ability. For example, conductive carbon nanotube (CNTs) net-
works have been used as electrodes for the fabrication of fully stretchable FETs
[39]. The self-healing ability of CNTs comes from the strong van der Waals interac-
tions between the tubes. Therefore, as soon as the strain is released, adjacent nano-
tubes will automatically come back into contact with each other restoring an
 3 Self-Healing Materials: Design and Applications 107

optimal morphology for electric conductivity. Moreover, this carbon-rich material is

particularly interesting for large-scale fabrication, given the possibility of perform-
ing solution deposition of the CNTs by a method known as spray coating.
In addition to electronics and related areas, the utilization of self-healing materi-
als attracted attention in other areas of application. Among others, new applications
for these materials include resistant fabrics, resealing tires, and long-life batteries
[40]. In order to give an overview of some new exciting applications for self-healing
materials, the following section highlights and describes some selected examples.

3.4.2 Advanced Manufacturing and Technologies

One of the first applications in which self-healing materials are now being investi-
gated is in advanced transportation technologies, especially in jet plane conception
and production. In that context, self-healing materials showed great potential for re-
placing conventional ceramic composites, widely used in current jet engines. Given
the fact that these ceramic composites are sensitive to failure and a variety of different
types of mechanical impacts, existing ceramic composites in combustion chambers
have been replaced by self-healing boron-containing composites [41]. The self-healing
properties of these boron composites are attributed to the formation of boron oxide
(B2O3) that can seal the matrix cracks. The self-healing properties of these materials
have been investigated at high temperatures (around 1,350 °C), temperatures typically
found in an aircraft engine combustion chamber. Even though this new approach has
not yet been optimized, these new self-healing materials showed great potential to
enhance the robustness of jet planes and transport technologies in general.

3.4.3 Functional Coatings and Adhesives

Closer to our life, self-healing composites are also promising candidates toward self-
healing paints and coatings, capable of spontaneously recovering their function and
surface homogeneity after being damaged. The self-healing coatings also showed
some promising results for the protection of large structures from corrosion and
minor impacts. In order to achieve production such as self-healing coating materials,
Yang et al. recently synthesized an epoxy resin composite coating for steel alloys
with embedded urea formaldehyde microcapsules [42]. As described in previous sec-
tions, microcapsules are highly efficient healing agents and are particularly interest-
ing toward intrinsic and spontaneous self-healing. Therefore, this strategy has been
proved to be suitable for paint application. A key factor in their role as epoxy resin
composites is that in preparation and application, they did not break apart during
the coating step. In addition, the coated steel samples were successfully protected
against corrosion even after the coating was damaged and healed. It is important to
108 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

mention that protection against corrosion is particularly critical for many industries
as metallic alloys, including aluminum, titanium, and magnesium, are very impor-
tant components of many products and if they begin to corrode, the integrity of the
structure may be in jeopardy [43]. Another example is the use of self-healing vanadia
coatings for aerospace-grade aluminum and magnesium alloys that have been re-
ported recently, opening new opportunities for producing functional self-healing
coatings in aerospace and other advanced technology industries [44, 45].
Conductive polymer coatings, based on polyaniline and polypyrrole, also at-
tracted great interest for the design of protective coatings, especially because of
their ability to actively store ions. This intrinsic property confers with intrinsic self-
healing coatings through a specific process attributed to the reduction and healing
of the conductive polymers by releasing anions into the system when they are dam-
aged. This self-healing ability, combined with an eco-friendly nature, make self-
healing conductive polymer coatings promising candidates to replace traditional
hexavalent chromium coating, which are well known to be toxic and easily dam-
aged. Interestingly, self-healing conductive materials can also be used as adhesives
and metal fillers, which act as a channel for charge transport while also mechani-
cally strengthening the solid substrate. These new materials are considered as one
of the most promising replacements for Pb-based solders in electronic assembly ap-
plications. In a recent report, polystyrene was utilized to generate microcapsules,
which were filled with silver nanowires and dimethylbenzylamine. Upon external
stimuli and/or damage, the microcapsules are broken, thus releasing a healing
agent capable of repairing cracks. In addition to the mechanical healing, the con-
ductive silver nanowires can restore the conductivity, improving the self-healing ef-
ficiency and completely restoring the initial functionality of the adhesive.

3.4.4 Biomedical Engineering

Hydrogels are three-dimensional networks composed of hydrophilic polymers,

which possess the ability to absorb a large amount of water (up to thousands of
times their dry weight), thus generating a mimic of in vivo conditions. Hydrogels
with the ability to achieve autonomous self-healing of its initial properties after
being damaged are defined as “self-healing hydrogels.” In contrast to conventional
hydrogels, self-healing hydrogels exhibit greater potential for application, espe-
cially in the biomedical and bioengineering field. These applications include cell
therapy, tissue engineering, and drug delivery systems. For example, in the field of
cartilage and bone tissue engineering, self-healing hydrogels have shown great
promise as hydrogels are considered as good scaffolds for cartilage tissues. When
implanted in vivo, classic hydrogels generally suffer from poor integration to the
surrounding cartilage tissue, thus increasing the risks of fracture. However, when a
dynamic reversible acylhydrazone bond is incorporated into the rational design of
 3 Self-Healing Materials: Design and Applications 109

the hydrogel, autonomous self-healing is enabled, resulting in an enhanced adhe-

sion to tissues and cartilages. Such adhesion is resulting directly from the dynamic
Schiff-base reaction between surface aldehyde moieties of the hydrogel and the
amide moieties located at the surface of the cartilaginous tissue. Such dynamic in-
teractions drastically enhance the adhesive strength, capable of reaching a maxi-
mum pressure resistance of 10 kPa [44].

3.4.5 Petroleum Extraction

Sealing of wellbores in geothermal and tight oil/gas reservoirs by filling the annu-
lus with cement is a well-established practice during the petroleum extraction pro-
cess. However, failure of the cement, as a result of physical and/or chemical stress,
is a common problem with serious environmental and financial consequences. To
address this challenge, a self-healing polymer-cement composite was prepared by
combining self-healable thermoset disulfide containing epoxy resins with class H
wellbore cement. The thermal stability and mechanical strength of the resulting
self-healing polymer–cement composites were drastically improved, which was at-
tributed to the formation of numerous chemical interactions between the polymer
and cement matrix, including covalent bonds, hydrogen bonding, and van der
Waals interactions. Self-healing properties were demonstrated by sealing fractures
with 0.3−0.5 mm apertures, two orders of magnitude larger than typical wellbore
fractures. This polymer–cement composite represents a major advance in wellbore
cementing that could improve the environmental safety and economics of enhanced
geothermal energy and tight oil/gas production [45].

3.5 Conclusion and Perspectives

As discussed in this chapter, self-healing materials are promising candidates for the
development of new applications, including the development of new functional devi-
ces with robust conformations and long lifetimes, new ultra-durable coatings and
also for aerospace technologies. Although the research on self-healing composites
and polymers is still in its infancy, over the past decade, this research field of mate-
rial sciences highly intensified and achieved significant progress. Specifically, vari-
ous new strategies toward efficient self-healing has been developed and designed.
Among others, the incorporation of microcapsules containing repairing agents
showed great promise for efficient self-healing in the polymer matrices. In addition,
intrinsic spontaneous self-healing can also now be implemented in various materials
directly by rational chemical design and, in fact, synthetic chemistry allowed for the
incorporation of dynamic cross-linking moieties into materials. These dynamic
110 M. Nazir Tahir, Michael U. Ocheje, Kacper Wojtkiewicz, Simon Rondeau-Gagné

interactions, for example, hydrogen bonding, dynamic covalent bonds, thiol–disul-

fide exchange, and metal–ligand interactions, can spontaneously break and reform
upon being damaged, which opens the door to the preparation of a whole new library
of self-healable materials that can be fine-tuned through rational design.
Despite the accelerating development of self-healing materials with enhanced
efficiency, many challenges still remain to be addressed before using these materi-
als in our day-to-day lives. In fact, for both extrinsic and intrinsic self-healing sys-
tems, finding high throughput, scalable, and cost-effective methods for mass
production and manufacturing still requires highly focused research efforts. More-
over, many self-healing materials currently used and developed require harsh con-
ditions to trigger self-healing properties including high temperatures, light
exposure, physical contact, and so on. Therefore, to overcome such problems, ma-
terials that promote spontaneous self-healing or self-healing under milder condi-
tions must be developed.
Self-healing materials are a new and important class of materials that will un-
doubtedly revolutionize many areas, including consumer goods, advanced technol-
ogies, and manufacturing. Moreover, as described and exemplified in this chapter,
this field of materials chemistry and polymer science opens new and incredible op-
portunities of applications for chemists, materials scientists, and engineers.

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