INTRODUCTION

The ability of materials to self-heal from mechanical and thermally induced damage
is explored in this report and has signi?cance in the ?eld of fracture and fatigue.
The history and evolution of several self-repair systems is examined including
nano-beam healing elements, passive self-healing, autonomic self-healing and
ballistic self-repair. Self-healing mechanisms utilized in the design of these
unusual materials draw much information from the related ?eld of polymer-polymer
interfaces and crack healing. The relationship of material damage to material
healing is examined in a manner to provide an understanding of the kinetics and
damage reversal processes necessary to impart self-healing characteristics. In
self-healing systems, there are transitions from hard-to-soft matter in ballistic
impact and solvent bonding and conversely, soft-to-hard matter transitions in high
rate yielding materials and shear-thickening ?uids. These transitions are examined
in terms of a new theory of the glass transition and yielding, viz., the twinkling
fractal theory of the hard-to-soft matter transition. Success in the design of
self-healing materials has important consequences for material safety, product
performance and enhanced fatigue lifetime.

Self-healing materials are a class of smart materials

<http://en.wikipedia.org/wiki/Smart_material> that have the structurally
incorporated ability to repair damage caused by mechanical usage over time. The
inspiration comes from biological systems, which have the ability to heal after
being wounded. Initiation of cracks and other types of damage on a microscopic
level has been shown to change thermal <http://en.wikipedia.org/wiki/Thermal>,
electrical <http://en.wikipedia.org/wiki/Electrical>, and acoustical
<http://en.wikipedia.org/wiki/Acoustical> properties, and eventually lead to whole
scale failure of the material. Usually, cracks are mended by hand, which is
difficult because cracks are often hard to detect. A material (polymers
<http://en.wikipedia.org/wiki/Polymer>, ceramics, etc.) that can intrinsically
correct damage caused by normal usage could lower production costs of a number of
different industrial processes through longer part lifetime, reduction of
inefficiency over time caused by degradation, as well as prevent costs incurred by
material failure. For a material to be defined as self-healing, it is necessary
that the healing process occurs without human intervention.

Self-healing materials are polymers, metals, ceramics and their composites that
when damaged through thermal, mechanical ,ballistic or other means have the
ability to heal and restore the material to its original set of properties. Few
materials intrinsically possess this ability, and the main topic of this review is
the design for self-repair. This is a very valuable characteristic to design into a
material since it effectively expands the life time use of the product and has
desirable economic and human safety attributes.

In self-healing systems, there are transitions from hard-to-soft matter in

ballistic impact and solvent bonding and conversely, soft-to-hard matter
transitions in high rate yielding materials and shear-thickening ?uids used in
liquid armor. These transitions are examined in terms of a new theory of the glass
transition and yielding, viz., the twinkling fractal theory of the hard-to-soft
matter transition. It also gives an overview of the most recent advances in the
self-healing ?eld, including the biomimetic micro?uidic healing skins ,and provides
some prospective for the future design of self-healing materials. The biological
analogy of self-healing materials would be the modi?cation of living tissue and
organisms to promote immortality, and many would agree that partial success in the
form of expanded lifetime would be acceptable.
Observation of self-healing materials

Materials such as polymers and composites experience damage and fatigue during
their normal utilization and the concept of eliminating this damage through a self-
healing mechanism holds the promise of enhanced lifetimes and enduring strength.

This is especially important in materials that are intended to perform in a

designed manner for signi?cant times where repair is not possible. Our early
attention to self-healing materials in the1970sarose through the need to understand
the constitutive properties of ?lled elastomers ,such as those used in solid rocket
propellants for applications in space exploration (Apollo), Earth studies(Shuttle)
and more recently, ballistic missile interdiction. These materials consisted of
ammonium perchlorate -?lled hydroxyl terminated polybutadiene crosslinked with
diisocyanates. Itwas clear that mechanical action caused microscopic damage at the
nano scale, which could coalesce to form larger microscopic cracks, which in turn
could propagate as macroscopic cracks and cause catastrophic loss of the material
and pay load. However, it became readily apparent that much of this damage could
self-heal and measures of damage through modulus loss or mechanical stress-strain
hysteresis were developed to quantify the damage and healing processes
.

Cyclic stress-strain curves of a HPP ?ber with interveninghealing times from 10 to

1000 min at room temperature.

An explicit example of a self-healing material was demonstrated with hard elastic

polypropylene (HPP).HPP is a stress-crystallized PP which has a morphology
consisting of stacked lamella perpendicular to the extrusion direction of the ?bers
or ?lms. When stretched along the ?ber axis, the lamellae would splay apart
permitting large reversible strains up to 500%.

Why self healing ?

} Traditional repairs are expensive

No matter how carefully you use your accessories in day to day life , by your
fault or by some others mistake sometime these things get damaged . Sometime the
damage is at very large scale and you have to replace the whole accessory and some
time the damage is at lower scale which could be repaired.
This low scale damage may be in the form of scratches or dents to the motor
vehicles or some other form of small damages. But due to the lack of time and due
to working on the repair of a single portion of accessory the repairs becomes very
expansive.
Tradition repair process of leaving the car to garage and wait for the mechanic to
remove the dents is time consuming and expansive. Hence the concept of self healing
comes into picture for the small damages because it is fast and less expansive .
} To design (never two the same)
it is never possible to design the new replacement with the same level of accuracy
and surface finish . Even after spending the money and time we did' nt get the
exact original piece. But by self healing processes we need not to replace the
original , because by using self healing techniques we are providing the
materials the power of healing itself which minimizes the chances of replacement
and the original is kept original with same dimensional accuracy and quality.

} To implement (removal from service or in-situ repair)

in situ repairs are the repairs which are done to prevent the whole part to be
replaced. If this is not possible in the assembly then you have to replace the
whole .And also in situ repairs are very much expansive and also not that much
precise and perfect . This problem can be overcome by using self healing
techniques , as this techniques the facility of in situ repair by itself with very
high level of accuracy.

} To certify & monitor (additional inspection often required) throughout

remaining operational life.
Generally the repairs made to different materials requires expert monitoring and
certification .but by applying self healing techniques we need not to inspect or
monitor the repairs they are precisely done with self healing phenomenon.

} Sense and respond to damage,restore performance without affecting inherent

properties.
Self healing sense and respond to damage ,restore performance and does not affect
the inherent properties of material. Usually self healing materials are used to
repair the small cracks in material when the self healing component is exposed to
surroundings without affecting inherent properties of the materials.

} No human intervention required.

For self healing process no human intervention is required . It decreases the
chances of error during the repair. In this process self healing of material starts
without any human interference .

} Provide early means of detection of damage

It is like modeling and mimicking of the human body and other living systems which
have the ability to self heal. If the self healing inserts are used then the
detection of damage is very early and as soon as the damage is detected the healing
repair starts. It prevent the material from more damage .

Self healing polymers

Research in the last decade has led to the development of self-healing polymeric
materials that mimic some of these features found in biological systems .These
self-healing polymers offer promise in significantly extending the life of
polymeric components by autonomically healing microcracks whenever and wherever
they develop. Potential applications for such materials are broad and include
structural PMC for aerospace, prosthetics, civil infrastructure, and electronics.
Though the potential bene?ts are quite high, there are several practical
limitations (such as crack healing kinetics, stability of the healing functionality
to environmental conditions, material costs, and virgin property reduction) that
need to be overcome in order for the bene?ts to be realized.

There are several different strategies to impart self healing functionality that
have been developed to various levels. The strategies, which are discussed in
detail in the following headings, are broadly classi?ed into three categories:
healing with an embedded liquid phase repair agent, thermally activated solid phase
healing, and healing of projectile puncture. Most of the work has been related to
the liquid phase healing agent strategy, which will be described ?rst.

Polymer breakdown
From a molecular perspective, traditional polymers yield to mechanical stress
though cleavage of sigma bonds <http://en.wikipedia.org/wiki/Sigma_bond>. While
newer polymers can yield in other ways, traditional polymers typically yield
through homolytic <http://en.wikipedia.org/wiki/Homolytic> or heterolytic
<http://en.wikipedia.org/wiki/Heterolytic> bond cleavage. The factors that
determine how a polymer will yield include: type of stress, chemical properties
inherent to the polymer, level and type ofsolvation
<http://en.wikipedia.org/wiki/Solvation>, and temperature.

From a macromolecular <http://en.wikipedia.org/wiki/Macromolecular> perspective,

stress induced damage at the molecular level leads to larger scale damage called
micro cracks. <http://en.wikipedia.org/wiki/Self-healing_material> A micro crack is
formed where neighboring polymer chains have been damaged in close proximity,
ultimately leading to the weakening of the fiber as a whole.

Different types of polymer breakdown are -

� Homolytic bond cleavage

� Heterolytic bond cleavage

� Reversible bond cleavage

� Supramolecular breakdown

Homolytic bond cleavage

<http://en.wikipedia.org/wiki/File:HomolyticcleavageofPMMA.gif>

Homolytic cleavage of poly(methyl methacrylate)

<http://en.wikipedia.org/wiki/Poly(methyl_methacrylate)> (PMMA).
Polymers have been observed to undergo homolytic bond cleavage through the use of
radical <http://en.wikipedia.org/wiki/Radical_(chemistry)> reporters such as DPPH
<http://en.wikipedia.org/wiki/DPPH> (2,2-diphenyl-1-picrylhydrazyl) and PMNB
(pentamethylnitrosobenzene.) When a bond is cleaved homolytically, two radical
species are formed which can recombine to repair damage or can initiate other
homolytic cleavages which can in turn lead to more damage.

Heterolytic bond cleavage

<http://en.wikipedia.org/wiki/File:HeterolyticcleavageofPEG.gif>

Heterolytic cleavage of polyethylene glycol

<http://en.wikipedia.org/wiki/Polyethylene_glycol>

Polymers have also been observed to undergo heterolytic bond cleavage through
isotope labeling experiments. When a bond is cleaved heterolytically, cationic
<http://en.wikipedia.org/wiki/Cationic> and anionic
<http://en.wikipedia.org/wiki/Anionic> species are formed which can in turn
recombine to repair damage, can be quenched <http://en.wikipedia.org/wiki/Quenched>
by solvent, or can react destructively with nearby polymers.

Reversible bond cleavage

Certain polymers yield to mechanical stress in an atypical, reversible manner.

Diels-Alder <http://en.wikipedia.org/wiki/Diels-Alder>-based polymers undergo a
reversible cycloaddition <http://en.wikipedia.org/wiki/Cycloaddition>, where
mechanical stress cleaves two sigma bonds <http://en.wikipedia.org/wiki/Sigma_bond>
in a retro Diels-Alder <http://en.wikipedia.org/wiki/Diels-Alder> reaction. This
stress results in additional pi-bonded electrons as opposed to radical or charged
moieties.

Supramolecular breakdown
Supramolecular <http://en.wikipedia.org/wiki/Supramolecular> polymers
<http://en.wikipedia.org/wiki/Polymer> are composed of monomers that interact non-
covalently <http://en.wikipedia.org/wiki/Non-covalent>.
<http://en.wikipedia.org/wiki/Self-healing_material> Common interactions include
hydrogen bonds <http://en.wikipedia.org/wiki/Hydrogen_bond>, metal coordination
<http://en.wikipedia.org/wiki/Coordination>], and van der Waals forces
<http://en.wikipedia.org/wiki/Van_der_Waals_forces>. Mechanical stress in
supramolecular polymers causes the disruption of these specific non-covalent
interactions, leading to monomer separation and polymer breakdown.

Reversible healing polymers

Reversible systems are polymeric systems that can revert to the initial state
whether it is monomeric <http://en.wikipedia.org/wiki/Monomeric>, oligomeric
<http://en.wikipedia.org/wiki/Oligomeric>, or non-cross-linked. Since the polymer
<http://en.wikipedia.org/wiki/Polymer> is stable under normal condition, the
reversible process usually requires an external stimulus for it to occur. For a
reversible healing polymer, if the material is damaged by means such as heating and
reverted to its constituents, it can be repaired or "healed" to its polymer
<http://en.wikipedia.org/wiki/Polymer> form by applying the original condition used
to polymerize it.

Covalently bonded system

Diels-Alder and retro-Diels-Alder

Among the examples of reversible healing polymers, the Diels-Alder

<http://en.wikipedia.org/wiki/Diels-Alder> (DA) reaction and its retro-Diels-Alder
<http://en.wikipedia.org/wiki/Diels-Alder> (RDA) analogue seems to be very
promising due to its thermal reversibility. In general, the monomer
<http://en.wikipedia.org/wiki/Monomer> containing the functional groups such as
furan <http://en.wikipedia.org/wiki/Furan> or maleimide
<http://en.wikipedia.org/wiki/Maleimide> form two carbon-carbon bonds in a specific
manner and construct the polymer through DA reaction. This polymer, upon heating,
breaks down to its original monomeric units via RDA reaction and then reforms the
polymer <http://en.wikipedia.org/wiki/Polymer> upon cooling or through any other
conditions that were initially used to make the polymer. During the last few
decades, two types of reversible polymers <http://en.wikipedia.org/wiki/Polymer>
have been studied: (i) polymers where the pendant groups, such as furan
<http://en.wikipedia.org/wiki/Furan> or maleimide
<http://en.wikipedia.org/wiki/Maleimide> groups, cross-link through successive DA
coupling reactions; (ii) polymers where the multifunctional monomers link to each
other through successive DA coupling reactions.

Cross-linked polymers

In this type of polymer <http://en.wikipedia.org/wiki/Polymer>, the polymer forms

through the cross linking of the pendant groups from the linear thermoplastics
<http://en.wikipedia.org/wiki/Thermoplastics>. For example, figure have shown the
reversible cross-linking of modified poly(N-acetylethyleneimine)s containing either
maleimide <http://en.wikipedia.org/wiki/Maleimide> or furancarbonyl pendant
moideties. The reaction is shown in Scheme 3. They mixed the two complementary
polymers <http://en.wikipedia.org/wiki/Polymer> to make a highly cross-linked
<http://en.wikipedia.org/wiki/Cross-linked> material through DA reaction of furan
and maleimide units at room temperature, as the cross-linked
<http://en.wikipedia.org/wiki/Cross-linked> polymer
<http://en.wikipedia.org/wiki/Polymer> is more thermodynamically stable than the
individual starting materials. However, upon heating the polymer to 80 �C for two
hours in a polar <http://en.wikipedia.org/wiki/Chemical_polarity> solvent
<http://en.wikipedia.org/wiki/Solvent>, two monomers
<http://en.wikipedia.org/wiki/Monomer> were regenerated via RDA reaction,
indicating the breaking of polymers <http://en.wikipedia.org/wiki/Polymer>.[6]
<http://en.wikipedia.org/wiki/Self-healing_material> This was possible because the
heating energy provided enough energy to go over the energy barrier and results in
the two monomers <http://en.wikipedia.org/wiki/Monomer>. Cooling the two starting
monomers <http://en.wikipedia.org/wiki/Monomer>, or damaged polymer
<http://en.wikipedia.org/wiki/Polymer>, to room temperature for 7 days healed and
reformed the polymer.

<http://en.wikipedia.org/wiki/File:Cross-linking_DA.png>

Scheme 3. Reversible polymer cross-linking via Diels-Alder

<http://en.wikipedia.org/wiki/Diels-Alder> cycloaddition
<http://en.wikipedia.org/wiki/Cycloaddition> reaction between furan and maleimide.

The reversible DA/RDA reaction is not limited to furan-meleimides based polymers

<http://en.wikipedia.org/wiki/Polymer> as it is shown by the work of Schiraldi et
al. They have shown the reversible cross-linking of polymers bearing pendent
anthracene <http://en.wikipedia.org/wiki/Anthracene> group with maleimides.
However, the reversible reaction occurred only partially upon heating to 250 �C due
to the competing decomposition <http://en.wikipedia.org/wiki/Decomposition>
reaction.
Polymerization of multifunctional monomers

In this type of polymer, the DA reaction takes place in the backbone itself to
construct the polymer, not as a link. For polymerization and healing processes of a
DA-step-growth furan <http://en.wikipedia.org/wiki/Furan>-maleimide
<http://en.wikipedia.org/wiki/Maleimide>based polymer (3M4F) were demonstrated by
subjecting it to heating/cooling cycles. Tris-maleimide (3M) and tetra-furan (4F)
formed a polymer through DA reaction and, when heated to 120 �C, de-polymerized
through RDA reaction, resulting in the starting materials. Subsequent heating to
90-120 �C and cooling to room temperature healed the polymer, partially restoring
its mechanical properties through intervention. The reaction is shown in Scheme 4.
<http://en.wikipedia.org/wiki/File:DAstepgrowthpolymer.png>

Scheme 4. Reversible highly cross-linked furan-maleimide based polymer network.

Thiol-based polymers

The thiol-based polymers have disulfide bonds

<http://en.wikipedia.org/wiki/Disulfide_bonds> that can be reversibly cross-linked
through oxidation <http://en.wikipedia.org/wiki/Oxidation> and reduction
<http://en.wikipedia.org/wiki/Redox>. Under reducing condition, the disulfide
<http://en.wikipedia.org/wiki/Disulfide> (SS) bridges in the polymer breaks and
results in monomers, however, under oxidizing condition, the thiols
<http://en.wikipedia.org/wiki/Thiols> (SH) of each monomer forms the disulfide bond
<http://en.wikipedia.org/wiki/Disulfide_bond>, cross-linking the starting materials
to form the polymer. Chujo et al. have shown the thiol
<http://en.wikipedia.org/wiki/Thiol>-based reversible cross-linked polymer using
poly(N-acetylethyleneimine).

<http://en.wikipedia.org/wiki/File:Disulfidebridge.png>

Scheme 5. Reversible polymer cross-linking by disulfide bridges

Autonomic polymer healing

Self-healing polymers <http://en.wikipedia.org/wiki/Polymer> follow a three-step

process very similar to that of a biological response. In the event of damage, the
first response is triggering or actuation, which happens almost immediately after
damage is sustained. The second response is transport of materials
<http://en.wikipedia.org/wiki/Material> to the effected area, which also happens
very quickly. The third response is the chemical repair process. This process
differs depending on the type of healing mechanism that is in place. (e.g.,
polymerization <http://en.wikipedia.org/wiki/Polymerization>, entanglement,
reversible cross-linking). These self-healing materials can be classified in three
different ways: capsule based, vascular, and intrinsic (which is listed as
�Reversible healing polymers� above). While similar in some ways, these three ways
differ in the ways that response is hidden or prevented until actual damage is
sustained. Capsule based polymers sequester the healing agents in little capsules
that only release the agents if they are ruptured. Vascular self-healing materials
sequester the healing agent in capillary type hollow channels which can be
interconnected one dimensionally, two dimensionally, or three dimensionally. After
one of these capillaries is damaged, the network can be refilled by an outside
source or another channel that was not damaged. Intrinsic self-healing materials,
as you can see from above, do not have a sequestered healing agent but instead have
a latent self-healing functionality that is triggered by damage or by an outside
stimulus.

Thus far, all of the examples on this page require an external stimulus to initiate
polymer <http://en.wikipedia.org/wiki/Polymer> healing (such as heat or light).
Energy is introduced into the system to allow repolymerization to take place. This
is not possible for all materials. Thermosetting polymers
<http://en.wikipedia.org/wiki/Thermosetting_polymer>, for example, are not
remoldable. Once they are polymerized (cured <http://en.wikipedia.org/wiki/Cured>),
decomposition <http://en.wikipedia.org/wiki/Decomposition> occurs before the melt
temperature is reached. Thus, adding heat to initiate healing in the polymer is not
possible. Additionally, thermosetting polymers
<http://en.wikipedia.org/wiki/Thermosetting_polymer> cannot be recycled, so it is
even more important to extend the lifetime ofmaterials
<http://en.wikipedia.org/wiki/Material> of this nature.

Hollow tube approach

For the first method, fragile glass capillaries or fibers are imbedded within a
composite material <http://en.wikipedia.org/wiki/Composite_material>. The resulting
porous network is filled with monomer <http://en.wikipedia.org/wiki/Monomer>. When
damage occurs in the material from regular use, the tubes also crack and the
monomer is released into the cracks. Other tubes containing a hardening agent also
crack and mix with the monomer <http://en.wikipedia.org/wiki/Monomer>, causing the
crack to be healed. There are many things to take into account when introducing
hollow tubes into a crystalline structure
<http://en.wikipedia.org/wiki/Crystalline_structure>. First to consider is that the
created channels may compromise the load bearing ability of the material due to the
removal of load bearing material. Also, the channel diameter, degree of branching,
location of branch points, and channel orientation are some of the main things to
consider when building up microchannels within a material
<http://en.wikipedia.org/wiki/Material>. Materials that don't need to withstand
much mechanical strain <http://en.wikipedia.org/wiki/Strain>, but want self-healing
properties, can introduce more microchannels than materials
<http://en.wikipedia.org/wiki/Material> that are meant to be load bearing.
<http://en.wikipedia.org/wiki/Self-healing_material> There are two types of hollow
tubes: discrete channels, and interconnected channels.
<http://en.wikipedia.org/wiki/Self-healing_material>

Discrete channels

Discrete channels can be built independently of building the material

<http://en.wikipedia.org/wiki/Material> and are placed in an array throughout the
material. When creating these micro channels, one major factor to take into account
is that the closer the tubes are together, the lower the strength will be, but the
more efficient the recovery will be. A sandwich structure is a type of discrete
channels that consists of tubes in the center of the material
<http://en.wikipedia.org/wiki/Material>, and heals outwards from the middle.
<http://en.wikipedia.org/wiki/Self-healing_material> The stiffness of sandwich
structures is high, making it an attractive option for pressurized
<http://en.wikipedia.org/wiki/Pressurized> chambers. For the most part in sandwich
structures, the strength of the material <http://en.wikipedia.org/wiki/Material> is
maintained as compared to vascular networks. Also, material shows almost full
recovery from damage.

<http://en.wikipedia.org/wiki/Self-healing_material>
Interconnected networks

Interconnected networks are more efficient <http://en.wikipedia.org/wiki/Efficient>

than discrete channels, but are harder and more expensive to createThe most basic
way to create these channels is to apply basic machining principles to create micro
scale channel grooves. These techniques yield channels from 600-700 micrometers.
This technique works great on the two-dimensional plane, but when trying to create
a three-dimensional network, they are limited.

Direct Ink Writing

The Direct Ink Writing (DIW) technique is a controlled extrusion of viscoelastic

inks to create three-dimensional interconnected
<http://en.wikipedia.org/wiki/Interconnected> networks. It works by first setting
organic <http://en.wikipedia.org/wiki/Organic> ink in a defined pattern. Then the
structure is infiltrated with a material <http://en.wikipedia.org/wiki/Material>
like an epoxy <http://en.wikipedia.org/wiki/Epoxy>. This epoxy is then solidified
<http://en.wikipedia.org/wiki/Solidified>, and the ink can be sucked out with a
modest vacuum, creating the hollow tubes.

Microcapsule healing

This method is similar in design to the hollow tube approach. Monomer is

encapsulated and embedded within the thermosetting polymer
<http://en.wikipedia.org/wiki/Thermosetting_polymer>. When the crack reaches the
microcapsule, the capsule breaks and the monomer bleeds into the crack, where it
can polymerize and mend the crack
<http://en.wikipedia.org/wiki/File:Polymerization_in_situ.jpg>

Figure 1. Depiction of crack propagation through microcapsule-imbedded material.

Monomer microcapsules are represented by pink circles and catalyst is shown by
purple dots.
A good way to enable multiple healing events is to use living (or unterminated
chain-ends) polymerization catalysts. If the walls of the capsule are created too
thick, they may not fracture when the crack approaches, but if they are too thin,
they may rupture prematurely.
In order for this process to happen at room temperature
<http://en.wikipedia.org/wiki/Temperature>, and for the reactants to remain in a
monomeric state within the capsule, a catalyst
<http://en.wikipedia.org/wiki/Catalyst> is also imbedded into the thermoset. The
catalyst lowers the energy barrier <http://en.wikipedia.org/wiki/Energy_barrier> of
the reaction <http://en.wikipedia.org/wiki/Reaction> and allows the monomer to
polymerize without the addition of heat. The capsules (often made of wax
<http://en.wikipedia.org/wiki/Wax>) around the monomer and the catalyst are
important maintain separation until the crack facilitates the reaction.
There are many challenges in designing this type of material
<http://en.wikipedia.org/wiki/Material>. First, the reactivity of the catalyst
<http://en.wikipedia.org/wiki/Catalyst> must be maintained even after it is
enclosed in wax. Additionally, the monomer must flow at a sufficient rate (have low
enough viscosity <http://en.wikipedia.org/wiki/Viscosity>) to cover the entire
crack before it is polymerized, or full healing capacity will not be reached.
Finally, the catalyst must quickly dissolve into monomer in order to react
efficiently and prevent the crack from spreading further.

<http://en.wikipedia.org/wiki/File:Reaction_for_wiki_page.png>

Scheme 6. ROMP of DCPD via Grubbs' catalyst <http://en.wikipedia.org/wiki/Grubbs

%27_catalyst>

This process has been demonstrated with dicyclopentadiene

<http://en.wikipedia.org/wiki/Dicyclopentadiene> (DCPD) and Grubbs' catalyst
<http://en.wikipedia.org/wiki/Grubbs%27_catalyst> (benzylidene-
bis(tricyclohexylphosphine)dichlororuthenium). Both DCPD and Grubbs' catalyst
<http://en.wikipedia.org/wiki/Grubbs%27_catalyst> are imbedded in an epoxy
<http://en.wikipedia.org/wiki/Epoxy> resin <http://en.wikipedia.org/wiki/Resin>.
The monomer <http://en.wikipedia.org/wiki/Monomer> on its own is relatively
unreactive and polymerization <http://en.wikipedia.org/wiki/Polymerization> does
not take place. When a microcrack reaches both the capsule containing DCPD and the
catalyst <http://en.wikipedia.org/wiki/Catalyst>, the monomer
<http://en.wikipedia.org/wiki/Monomer> is released from the core-shell microcapsule
and comes in contact with exposed catalyst, upon which the monomer undergoes ring
opening metathesis polymerization
<http://en.wikipedia.org/wiki/Ring_opening_metathesis_polymerization> (ROMP). The
metathesis <http://en.wikipedia.org/wiki/Metathesis_reaction> reaction
<http://en.wikipedia.org/wiki/Reaction> of the monomer
<http://en.wikipedia.org/wiki/Monomer> involves the severance of the two double
bonds in favor of new bonds. The presence of the catalyst
<http://en.wikipedia.org/wiki/Catalyst> allows for the energy barrier
<http://en.wikipedia.org/wiki/Energy_barrier> (energy of activation) to be lowered,
and the polymerization reaction <http://en.wikipedia.org/wiki/Reaction> can proceed
at room temperature. The resulting polymer <http://en.wikipedia.org/wiki/Polymer>
allows the epoxy <http://en.wikipedia.org/wiki/Epoxy> composite material
<http://en.wikipedia.org/wiki/Composite_material> to regain 67% of its former
strength.
Grubbs' catalyst <http://en.wikipedia.org/wiki/Grubbs%27_catalyst> is a good choice
for this type of system because it is insensitive to air and water, thus robust
enough to maintain reactivity within the material. Utilizing a live catalyst is
important to promote multiple healing actions. The major drawback is the cost. It
was shown that using more of the catalyst corresponded directly to higher degree of
healing. Ruthenium <http://en.wikipedia.org/wiki/Ruthenium> is quite costly, which
makes it impractical for commercial applications

Liquid-based healing agents

Completely autonomous synthetic self-healing material was reported in 2001 on

example of an epoxy <http://en.wikipedia.org/wiki/Epoxy> system containing
microcapsules <http://en.wikipedia.org/wiki/Micro-encapsulation>.[21]
<http://en.wikipedia.org/wiki/Self-healing_material> These microcapsules were
filled with a (liquid)monomer <http://en.wikipedia.org/wiki/Monomer>. If a
microcrack <http://en.wikipedia.org/w/index.php?
title=Microcrack&action=edit&redlink=1> occurs in this system, the microcapsule
will rupture and the monomer will fill the crack. Subsequently it will polymerise
<http://en.wikipedia.org/wiki/Polymerization>, initiated by catalyst
<http://en.wikipedia.org/wiki/Catalyst> particles (Grubbs
<http://en.wikipedia.org/wiki/Robert_H._Grubbs> catalyst) that are also dispersed
through the system. This model system of a self healing particle proved to work
very well in pure polymers and polymer coatings.
A hollow glass fibre approach may be more appropriate for self-healing impact
damage in fibre-reinforced polymer composite materials. Impact damage can cause a
significant reduction in compressive strength with little damage obvious to the
naked eye. Hollow glass fibres containing liquid healing agents (some fibres
carrying a liquid epoxy monomer and some the corresponding liquid hardener) are
embedded within a composite laminate. Studies have shown significant potential.

Solid-state healing agents

In addition to the sequestered healing agent strategies described above, research

into "intrinsically" self-healing materials is also being performed. For example,
supramolecular polymers <http://en.wikipedia.org/wiki/Supramolecular_polymer> are
materials formed by reversibly connected non-covalent bonds
<http://en.wikipedia.org/wiki/Covalent_bond> (i.e. hydrogen bond
<http://en.wikipedia.org/wiki/Hydrogen_bond>), which will disassociate at elevated
temperatures. Healing of these supramolecullary based materials is accomplished by
heating them and allowing the non-covalent bonds to break. Upon cooling, new bonds
will be formed and the material will potentially heal any damage. An advantage of
this method is that no reactive chemicals or (toxic) catalysts are needed. However,
these materials are not "autonomic" as they require the intervention of an outside
agent to initiate a healing response.

Biomimetic design approaches

Self-healing materials are widely encountered in natural systems, and inspiration

can be drawn from these systems for design. There is evidence in the academic
literature of these biomimetic <http://en.wikipedia.org/wiki/Biomimicry> design
approaches being used in the development of self-healing systems for polymer
composites. In biology, for the minimum power to pump fluid through vessels
Murray's law <http://en.wikipedia.org/wiki/Murray%27s_law> applies. Deviation from
Murray's law is small however, increasing the diameter 10% only leads to an
additional power requirement of 3%-5%. Murray's law is followed in some mechanical
vessels, and using Murray's law can reduce the hydraulic resistance throughout the
vessels. <http://en.wikipedia.org/wiki/Self-healing_material> The DIW structure
from above can be used to essentially mimic the structure of skin. Toohey et al.
did this with an epoxy <http://en.wikipedia.org/wiki/Epoxy> substrate containing a
grid of microchannels containing dicyclopentadiene
<http://en.wikipedia.org/wiki/Dicyclopentadiene> (DCPD), and incorporated Grubbs'
catalyst <http://en.wikipedia.org/wiki/Grubbs%27_catalyst> to the surface. This
showed partial recovery of toughness after fracture, and could be repeated several
times because of the ability to replenish the channels after use. The process is
not repeatable forever, because the polymer <http://en.wikipedia.org/wiki/Polymer>
in the crack plane from previous healings would build up over time.

Potential Applications of Self Healing Materials

? Scientists have recently developed a polyurethane coating that heals its own
scratches when exposed to sunlight.
? The self-healing coating uses chitosan which is derived from chitin, the main
component of the exoskeleton of crustaceans .
? When a scratch occurs on the outer coating, the chemical structure is damaged
and the chitosan responds to the UV component of sunlight.
? Chemical chains are then formed with other materials in the coating,
eventually filling the scratch.
? Anything that cannot be reached for repair at the moment of damage!
? Civil Structures (Engineered cementitious composite)

? Tools (Nitinol)

? Space applications

? Self healing coatings for steel structure

? Composite materials for:

? Aerospace applications
? High quality sporting equipment
? Microelectronics
? Medical uses:
? To detect a breach in a glove, gown, etc., using electrohydrodynamic
technology