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Self-healing materials: A review

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DOI: 10.1039/B711716G

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REVIEW www.rsc.org/softmatter | Soft Matter

Self-healing materials: a review


Richard P. Wool
Received 31st July 2007, Accepted 30th November 2007
First published as an Advance Article on the web 10th January 2008
DOI: 10.1039/b711716g

The ability of materials to self-heal from mechanical and thermally induced damage is explored in this
paper and has significance in the field 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 field 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 fluids. 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.

1.0 Introduction and overview evolution of several self-repair systems including nanobeam-
healing elements, passive self-healing, autonomic self-healing
Self-healing materials are polymers, metals, ceramics and their and ballistic self-repair. Section 2 examines self-healing mecha-
composites that when damaged through thermal, mechanical, nisms, which could be deployed in the design of these unusual
ballistic or other means have the ability to heal and restore the materials and draws much information from the related field
material to its original set of properties. Few materials intrinsi- of polymer–polymer interfaces and crack healing. The relation-
cally possess this ability, and the main topic of this review is ship of material damage to material healing is examined in
the design for self-repair. This is a very valuable characteristic Section 3 in a manner to provide an understanding of the kinetics
to design into a material since it effectively expands the lifetime and damage-reversal processes necessary to impart self-healing
use of the product and has desirable economic and human safety characteristics. In self-healing systems, there are transitions
attributes. In this review, the current status of self-healing mate- from hard-to-soft matter in ballistic impact and solvent bonding
rials is examined in Section 1, which explores the history and and conversely, soft-to-hard matter transitions in high rate
yielding materials and shear-thickening fluids used in liquid
armor. These transitions are examined in Section 4 in terms of
Department of Chemical Engineering, University of Delaware, Newark DE
a new theory of the glass transition and yielding, viz., the twin-
19716-3144, USA. E-mail: wool@udel.edu
kling fractal theory of the hard-to-soft matter transition. Section
5 gives an overview of the most recent advances in the self-heal-
ing field, including the biomimetic microfluidic healing skins,
Dr Richard Wool is a Professor and provides some prospective for the future design of self-heal-
of Chemical Engineering and ing materials. The biological analogy of self-healing materials
Director of the Affordable would be the modification of living tissue and organisms to
Composites from Renewable promote immortality, and many would agree that partial success
Resources (ACRES) Program in the form of expanded lifetime would be acceptable. Hopefully,
in the Center for Composite the reader of this review is left with a sense of what-to-do and
Materials at the University of what-not-to-do when designing self-healing materials, perhaps
Delaware. He is author of the not always as this author intended.
books ‘‘Bio-Based Polymers
and Composites’’ and ‘‘Polymer
1.1 Observation of self-healing materials
Interfaces: Structure and
Strength’’. His research inter- Materials such as polymers and composites experience damage
ests are in the fields of bio-based and fatigue during their normal utilization and the concept of
Richard P: Wool polymers and composites, crack eliminating this damage through a self-healing mechanism holds
healing, fracture, interfaces, the promise of enhanced lifetimes and enduring strength.1 This is
glassy state, polymer entangle- especially important in materials that are intended to perform in
ments and dynamics. a designed manner for significant times where repair is not

400 | Soft Matter, 2008, 4, 400–418 This journal is ª The Royal Society of Chemistry 2008
possible. Our early attention to self-healing materials in the 1970s expanded to near-exfoliation by the elastomer and could open or
arose through the need to understand the constitutive properties close with mechanical action thereby producing a mechanical
of filled elastomers,2–4 such as those used in solid rocket propel- self-healing process similar to the nanobeams in Fig. 1.
lants for applications in space exploration (Apollo), Earth studies An explicit example of a self-healing material was demon-
(Shuttle) and more recently, ballistic missile interdiction. These strated with hard elastic polypropylene (HPP).8,9 HPP is a
materials consisted of ammonium perchlorate-filled hydroxyl- stress-crystallized PP which has a morphology consisting of
terminated polybutadiene cross-linked with diisocyanates. It stacked lamella perpendicular to the extrusion direction of the
was clear that mechanical action caused microscopic damage at fibers or films. When stretched along the fiber axis, the lamellae
the nanoscale, which could coalesce to form larger microscopic would splay apart permitting large reversible strains up to 500%,
cracks, which in turn could propagate as macroscopic cracks as shown in Fig. 2 and 3.
and cause catastrophic loss of the material and payload. The initial high modulus of this polymer and its subsequent
However, it became readily apparent that much of this damage elastomeric behavior earned it the name of hard-elastic polymers,
could self-heal and measures of damage through modulus loss which are quite unique to row-nucleated semicrystalline poly-
or mechanical stress–strain hysteresis were developed to quantify mers. The resulting network fracture morphology was often
the damage and healing processes.1 The first self-healing mechan- compared to a ‘‘Christmas paper bell’’. The mechanical proper-
ical element is shown in Fig. 14. ties shown in Fig. 3 show that the HPP when allowed to rest
This reversible self-healing crack element was used to examine at room temperature could completely recover its high elasticity
some of basic phenomena of an idealized self-healing element, as the interlamellar microvoids healed. In detailed studies, we
which could be used in series or parallel with elementary springs found that the interlamellar fracture damage could be
and dashpots, similar to the Maxwell or Voigt models. It completely healed at room temperature and accelerated with
consisted of two surfaces with an anharmonic potential function higher temperature.1,9
V(l) which would permit yielding at a critical strain ec ¼ lc1. We subsequently discovered that crack healing was fairly
What was most interesting about this model was that at high ubiquitous in polymer materials and systematically studied
strain, e.g. l ¼ 10, during stress relaxation, the applied mechan- microvoid healing, craze healing and crack healing in a variety of
ical work was stored reversibly in the new surfaces created, and materials, such as crazes in polystyrene,10,11 microvoids in SBS
would cause the stress to eventually increase before relaxing block copolymer elastomers12 and others which are reviewed in
completely. This could result in materials with most peculiar ref. 1. In a seminal study, Kausch and co-workers13–15 showed
mechanical properties, such as negative creep compliances J(t) that single cracks that were formed at room temperature in frac-
and reactive stress relaxation moduli G(t) where the stress would ture mechanics specimens of PMMA could be completely
first decrease with time and then suddenly increase at constant rehealed when the surfaces were rejoined and welded above the
strain,4 which bemused unsuspecting visitors to our lab. Such glass transition temperature Tg. Much work has been done by
self-healing material elements can now be made with intercalated our group16–25 and others26–68 to understand the concept of
nanoclays and carbon nanotube bundles.5–7 Elastomers based on strength development at polymer–polymer interfaces and poly-
functionalized fatty acids were found to critically intercalate and mer–solid interfaces69–75 in terms of the fundamental dynamics
partially exfoliate nanoclay galleries. The nanoclay galleries were of entangled polymers. Using DeGennes’ reptation dynamics

Fig. 1 (a) The stress–strain response of a healing element is shown where the two parallel surfaces interact by an anharmonic non-bonded potential
function. (b) Viscoelastic elements made with the healing element in series and parallel with a viscous dashpot [Wool 1978].

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 400–418 | 401
Fig. 4 Schematic drawing of hollow fiber fluid-release design to repair
cracks in fiber-filled composites (courtesy of C. Dry, University of
Fig. 2 SEM micrographs showing the surfaces of a 2.78 tex (25 denier, Illinois).
hard elastic polypropylene after extensions of: (a) up to 50%; (b) up to
100% (note the appearance of the surface cracks; (c) up to 200% (note
the widening of the cracks); (d) the surface of (c) at higher magnification. This is very important for thermosetting composite matrices,
Final magnifications are (a–c) 1500x, (d) 3900x. (courtesy of Ludmila which are typically highly cross-linked, and for glassy amor-
Konapasek). phous polymers and semicrystalline materials. Carolyn Dry, an
architect at the University of Illinois, presented an interesting
solution to self-healing materials to me. She was interested in
self-healing of fiber filled composites,77–79 for both polymer and
concrete matrices, and had developed several patents based on
these novel materials. In collaboration with N. Sottos, she devel-
oped a system of hollow fibers filled with a reactive fluid, which
was released by mechanical trauma and subsequently reacted to
heal the local cracks, as shown in Fig. 4.79
C. Dry had analyzed passive self-healing materials in the
following 5 steps, as described in ref. 1 (chapter 12): (1) the mate-
rial must be subjected to gradual deterioration, for example by
dynamic loading that induces microcracks; (2) the fiber must
contain self-repair fluid; (3) the fibers require a stimulus to
release the repairing chemical; (4) a coating or fiber wall must
be removed in response to the stimulus; and (5) the fluid must
promote healing of the composite damage.
Fig. 3 Cyclic stress–strain curves of a HPP fiber with intervening
Several interesting self-repair tests were conducted by Dry and
healing times from 10 to 1000 min at room temperature.1,9 co-workers on polymer matrices with different fibers. Experi-
ments were performed on polymer samples containing an
and the entanglement percolation model,17,76 we derived a unified embedded continuous metal fiber with two self-repair fibers in
theory for the strength development of polymer–polymer inter- its vicinity, one containing a (epoxy) monomer and the other
faces.17 While these relations are useful for welding above Tg containing the diamine cross-linking agent. They first mechani-
using molecular mobility and interdiffusion processes, they cally debonded the metal fiber in a fiber-pullout test without
also provide the keys to the important molecular and micro- disturbing the self-repair fibers. At this point, the metal fiber
scopic connectivity relations necessary to promote self-healing had very little adhesion with the matrix and could be readily
in materials below their Tg values where molecular mobility is removed with little stress. They then subjected the composite
more restricted, typically. to sub-critical loads, which released the fluids from the self-repair
fibers. The fluids mixed and diffused to the polymer–metal inter-
face and acted to repair the interface damage, which resulted in
1.2 Design of self-repair materials
a considerable gain of the fiber pullout stress.
A major issue for rigid materials below their Tg value, e.g., This approach to self-repair is very flexible with regard to the
composite matrices, is how to induce or design for self-healing. design of fiber, number of fibers, healing fluid, fiber construction,

402 | Soft Matter, 2008, 4, 400–418 This journal is ª The Royal Society of Chemistry 2008
fiber coating and so forth. The healing fluid could be a cross-
linking epoxy or polyester, a chemical agent that reacts with
the matrix, or one that reacts selectively with the damaged
surface. For example, one could use vinyl monomers in places
where microcracks in the matrix generate free radicals. The
free radicals would then polymerize the fluid and help promote
strength. Matrix solvents could also be used to promote solvent
bonding in microvoids. Thermally induced healing can also be
induced by exothermic reactions of the self-repair fluid, either
with itself or with components of the composite. We will return
to this passive self-healing mechanism later.

1.3 Autonomic self-repair design


An interesting variant of the passive self-healing method was
developed by White and Sottos in 2001,80–83 where instead of
using hollow fibers, they used spheres of healing fluid as shown
in Fig. 5. They describe the autonomic healing concept as
follows: a microencapsulated healing agent is embedded in
a structural epoxy matrix containing a catalyst (Grubb’s)
capable of polymerizing the healing fluid. (a) Cracks form in
the matrix wherever damage occurs. (b) The crack ruptures the
microcapsules releasing the healing agent into the crack plane
through capillary action. (c) The healing fluid contacts the
catalyst, which is randomly distributed in the matrix and triggers Fig. 6 (a) Healed fracture toughness KIC as a function of microcapsule
the polymerization reaction that helps to heal the damage by concentration. (b) Healing efficiency KIC(healed)/KIC(virgin) vs. concen-
bonding the crack surfaces closed. tration for microcapsule diameters 180 mm and 50 mm. The healing time
This approach was successfully demonstrated for both frac- was 24 h (courtesy of S. White et al.).
ture and fatigue healing in composite matrices80–84 and was
discussed by this author in a companion paper.85 Using a tapered (Brown et al., 2003). It is clear with these experiments that they
double cantilever beam (TDCB), which permits stable crack are capable of recovering about 80% of the virgin KIC values of
propagation, they first propagated a crack with known length. their material through this unique self-healing mechanism. In
The propagating crack ruptured the urea formaldehyde spheres, terms of fracture energy GIC, since GIC  KIC2 in the linear elastic
which released the dicyclopentadiene fluid. In the rest state, the fracture mechanics approximation, this corresponds to about
released fluid contacted the ruthenium (Grubb’s) catalyst 64% energy recovery.
embedded at random in the epoxy matrix, which initiated the Similar experiments in fatigue (sub-critical crack growth with
polymerization of the fluid and repaired the crack. A second cyclic stress) showed that the initial fatigue crack propagation
loading of the TDCB gave a measure of the fracture energy of rate (da/dN) could be recovered due to this healing process.82
the repaired original crack length. They report about 75% Fig. 7 shows related work of Brown et al. (2005) on fatigue
recovery of the fracture toughness, or maximum load ratio at the healing.
same crack length. Fig. 6 shows the fracture toughness healing The slowly propagating crack is attempting to heal due to
experiments as a function of microcapsule size and concentration release of the healing fluid from the ruptured microcapsules.

Fig. 7 Crack extension in fatigue (5 Hz) shows that the precrack had
healed and required  3000 cycles to reopen. Subsequently, the crack
Fig. 5 The autonomic self-healing system developed at the University of extension per cycle shows regions of constant slope and retardation
Illinois [Courtesy of S. White and N. Sottos]. due to healing during propagation (courtesy of S. White et al.).

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 400–418 | 403
They observe that if the fatigue is halted and the sample rested,
the cracks will heal up. These results are particularly impressive
since fatigue is quite insidious in that cracks which appear to
have healed in terms of strength can remain quite weak in
fatigue: for example, we have observed that for welding of poly-
mer–polymer interfaces that full strength could be obtained in
terms of KIC measurements after a certain weld time but the
weld remained very weak in terms of fatigue crack propagation
rates.21 Thus in Fig. 6 where they show 80% healing of KIC,
one might suspect that fatigue healing would be substantially
impaired but this is not the case, as shown in Fig. 7 and related
experiments of Brown et al. Several significant advances have Fig. 8 Healed EMMA film following puncture (courtesy of S. Kalista).
been made in both the chemistry and self-repair methodology
of this unique system81–85 and are discussed in Section 5.
The work by White and Sottos et al. is considered by many to content of the polymer was not important for healing and that
represent the current leading edge of the field of self-healing self-repair occurred by a two-stage process: Stage 1 involved
materials. However the field has become very active and several melt elastic recovery followed by Stage 2 with sealing and poly-
papers have been presented by various groups where other chem- mer-chain interdiffusion. Kalista et al. conclude that the impact
ical means were used to initiate healing of the fluid or matrix.86–90 energy of the projectile was sufficient to melt the polymer in the
Balazs et al.91 explored the use of nanoparticle migration to crack damage zone and melt recoil followed by interdiffusion
tips in thin films by computer simulation and found that this promoted self-repair.
migration could lead to substantial healing processes. The nano- A minimal energy balance analysis of this process would give
particles become localized in nanoscale cracks, the precursors to the temperature rise, DT ¼ T (impact)  T (sample), in the
microcracks, and effectively form patches to repair the damaged damage zone of radius R and mass m as:
region. This approach assumes that the nanoparticles have suffi- DU  m DHf
cient mobility in the polymer matrix where the test temperature DT ¼ (1)
m Cp
was assumed to be greater than Tg. The repaired composites were
expected to recover 75–100% of their mechanical strength. Yu where DU ¼ 1⁄2 m(V12  V22) is the energy dissipated with impact
et al.92 (1995) examined the rate of crack closure during healing velocity V1 and exit velocity V2, DHf is the heat of fusion to melt
of several materials. They found that the rate of crack closure the polymer and the Cp is the heat capacity. The mass of the
during the wetting stage was relatively constant in solvent treated damage zone is m ¼ rpR2h. The impact velocity in Fig. 8 gives
(CCl4) polycarbonate, ethanol treated PMMA, cracks in single an energy of U1 ¼ 9.9 J (we do not know the exit velocity and
crystals of KCl under pressure and single crystals of LiF at DU should be smaller), R ¼ 2 mm, h ¼ 1 mm, Cp z 2.7 J K1
elevated temperatures. We note that crack surface wetting is g1, DHf ¼ 429 J g1 (PE value) and r z 1 g cc1. These values
a necessary but not a sufficient condition for mechanical recovery. give DT z 100  C in the damage zone, which is sufficient for
For example, in both crack and craze healing, the cracks can melting and rehealing with Tm ¼ 92  C and T (sample) ¼ 22  C.
disappear at the nanoscale during the wetting stage but the inter- However, at 30  C, this is not sufficient energy for melting. Also,
face remains weak until considerable interdiffusion has occurred.1 if the mass of the damage zone increases with increasing temper-
ature, the numerator in the above relation goes rapidly to zero
and healing will not occur, as observed by Kalista et al. In related
1.4 Ballistic impact self-repair
experiments, Kalista et al. demonstrated that the same polymer
Perhaps the most provocative self-repair experiment was the plates also self-repair when cut with a saw since the friction gener-
observation by R. Fall et al.93 and Kalista et al.94,95 that bullet ated by the saw is sufficient to thermally weld the surfaces
holes in a plastic plate would heal up instantly. The high velocity together. However, the polymer plate when cut with a very sharp
projectile could penetrate the polymer plate and the holes would razor blade did not self-heal due to insufficient mechanical energy
reseal faster than the eye could see. This phenomenon was dissipation at the crack interface. Room temperature projectile
explored in some detail by Kalista et al.95 They examined self- testing with LDPE films showed no tendency for self-repair.95
healing in several poly(ethylene-co-methacrylic acid) copolymers In general, one should be able to design most thermoplastics for
(EMMA) following projectile puncture. Fig. 8 shows a typical ballistic self-healing. These could find unique applications in
result where a 4.5 mm projectile of mass 0.51 g and velocity space-capsule protection against micro meteorites.
196.6 m s1 has penetrated an EMMA film of thickness 1 mm. In the Kalista ballistic-healing experiments, self-healing is
The polymer contained about 5.4 mol% methacrylic acid groups, obtained by transforming ‘‘hard matter’’ to ‘‘soft matter’’ due
which had been partially (60%) neutralized by sodium and had to mechanical action. Decker et al.96 have shown that ballistic
a melting point Tm ¼ 93  C. One sees in Fig. 8 that the central impact resistance can be obtained by transforming a liquid to
damage zone is about the size of the bullet cross-section but a solid, through the use of shear-thickening fluids (STF). The
has been healed. The healing was determined by a pressure burst STF consists of a colloidal particle suspension that percolates
test. Interestingly, when the samples were tested at elevated rigidity under high deformation rates and has become the basis
temperatures (60  C), and some, but not all at low temperature for the invention of ‘‘liquid armor’’ at the University of
(30  C), no healing occurred. They concluded that the ionic Delaware. The advantage of this system is that after impact, the

404 | Soft Matter, 2008, 4, 400–418 This journal is ª The Royal Society of Chemistry 2008
instantly rigidized matter returns to the liquid state and rapidly The use of solvent systems that promote surface segregation of
heals itself by restoring the local concentration of particles. chain ends for example, would be highly conducive to rapid
The STF suspensions when mixed with Kevlar fibers have shown healing of damage. The relation between solvent concentration
remarkable stab resistance when subjected to repeated high and surface-rearrangement dynamics needs to be quantified,
velocity trauma from sharp objects such as knives and ice picks.96 primarily through the effect of solvent on both the glass transi-
We further explore this mechanism in Section 4. tion temperature Tg and the relaxation times of the surface mole-
In this review, we examine several relevant theories for self- cules, as discussed in ref. 1 (chapter 7). The critical entanglement
healing and compare with experimental results. It is intended molecular weight Mc will also be changed with surface polymer
that this paper serve both as a review of work done in the field concentration 4 in the good solvent as,76
of self-healing materials and act as a design tool for future gener-
ations of these interesting materials which proffer the unusual Mc(4) ¼ Mc(1)45/4 (2)
promise of everlasting material life.
Where Mc(1) is the unperturbed Mc value with 4 ¼ 1. This means
2.0 Self-healing mechanisms that when a compatible healing fluid interacts with the polymer
surfaces, the entanglement molecular weight increases. Conse-
2.1 Stages of passive self-healing quently, the entanglement density n(4) decreases via:
Discussions with C. Dry (1993) resulted in the following anal-
n(4) ¼ n(1)49/4 (3)
ysis of self-healing systems using passive fluids, solvents, reacting
catalysts, etc. The results are applicable to both the passive heal-
Consequently, the plateau elastic modulus GN0 behaves as76
ing models of Dry77–79 and White and Sottos,80–85 models using
nanoscale healing elements,4 other general models using chemi- GN0 ¼ GN0(1)49/4 (4)
cal reactions,86–90 nanoscale segregation91 and ballistic impact
self-repair.95 Thus, the surfaces are expected to become quite soft in the
Five stages of crack healing were developed by Wool and O’ presence of a healing fluid and this could be quite beneficial
Connor19 in an effort to unscramble the complexity of strength to promote interdiffusion if necessary for healing. The local
development at polymer interfaces. That approach proved to reptation times t will be affected by solvents as,76
be successful in separating the multi-convoluted time dependen-
cies of the different mechanisms controlling crack healing and t ¼ t(1)45/4 (5)
their underlying molecular processes. Repair of cracks and
microscopic damage has been described in terms of the following in which t(1)  M3. The viscosity h of the surface layer will be
stages: (a) surface rearrangement; (b) surface approach; (c) changed accordingly as
wetting; (d) diffusion; and (e) randomization. These are discussed
with respect to self-healing materials in the following sections. h ¼ h(1)43.5 (6)

Thus, a 50% decrease in polymer concentration on the surface as


2.2 Surface rearrangement
it mixes with the healing fluid would reduce its local viscosity by
When the freshly damaged surfaces or microvoids are created in 0.09 times its original value. Solvation to 10% causes a decrease
fracture or fatigue, one should consider the roughness or topog- of the viscosity to 3  104 times h(1). Since these effects basically
raphy of the surface and how it changes with time, temperature occur at room temperature, an important role of the healing
and pressure following contact with the healing fluid. In frac- fluid could be to enhance molecular mobility of the surfaces
tured polymers, rearrangement of fibrillar morphology and other and facilitate the other stages of healing. The dynamics of the
factors affect the rate of crack healing. Chain-end distributions surface-layer rearrangement is similar to that in some bulk
near the surface can change as molecules diffuse back in to the processes, but in general, the surface molecules should have
bulk.20 If the chain ends are needed for reaction with the fluid, enhanced mobility due to higher degree of freedom and an
they could be designed to preferentially migrate to the surface altered photon density of states reducing both the Tg and heat
using lower surface tension moieties on the chain ends. Spatial capacity of the surface layers. Because surfaces have a lower
changes of the molecular weight distribution can also occur, heat capacity, less energy is required to raise their temperature.
for example, where the low molecular weight species preferen- For polymer–solid interfaces as commonly encountered in
tially migrate to the surface. Nanoparticles in the bulk could composites, surface restructuring dominates the mechanism of
preferentially migrate into nano voids.91 In time-release solvents adhesion between the polymer and the solid. When a mole
or adhesives, surface rearrangement is affected by the polymer– fraction of sticker groups f(X) is used to bond the polymer to
solvent interaction. Chemical reactions, for example oxidation the surface, an optimal sticker group concentration f*(X) is
and cross-linking can occur on the surface and complicate the needed to maximize adhesion while minimizing cohesive failure
dynamics of diffusion. Solvents used in the passive healing exper- in the boundary layer adjacent to the solid.69–75 When f < f*,
iments could also cause additional damage for example, by adhesive failure dominates, the fracture energy G1c  f and the
causing crazes and microvoids to swell and allow them to prop- solid separates cleanly from the polymer. When f > f*, cohesive
agate further. failure occurs in a polymer layer adjacent to the surface and G1c
Each material and self-repair release technique posses unique  1/f. What happens to this balance in the presence of a healing
surface-rearrangement processes that may need to be quantified. fluid? This restructuring is quite delicate and important to soft

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 400–418 | 405
materials. The f* value is determined from the entanglement
percolation theory to be75

f* ¼ 4j(Mj/Mc) (7)

where Mj is the molecular weight per bond of a random walk


chain (e.g., Mj ¼ 14 g mol1 for PE). The critical entanglement
molecular weight Mc is determined by the random walk charac-
teristic ratio CN and Mj as76

Mc ¼ 62CNMj45/4 (8)

Combining the latter two relations, we obtain the f* value in the


presence of the solvent as

f* ¼ (0.0745/4)/Cf (9)

Since Cf is of order 7–20 for many polymers, then f*  1%, as


observed.69–75 Thus, in the presence of a healing fluid, surface
restructuring would produce a new value of f* which is consider-
Fig. 9 Schematic of a time-dependent wetting process W(t) in a portion
ably less than the original. The resulting restructuring could
of a polymer–polymer interface. The wetted shaded pools of radius r are
result in a very weak polymer–solid interface since the weak cohe-
nucleated at different times and propagate until coalescence is achieved,
sive failure mode would be favored. The surface-restructuring and the fractional wetted area W ¼ 1.
kinetics of polymer–solid interfaces are complex and have been
examined by Gong and co-workers and Lee and co-workers.69–75 Wetting can occur in a time-dependent fashion at the inter-
face. For our purposes we provide a brief phenomenological
2.3 Surface approach description of wetting to illustrate potential problems in evalu-
ating the time-dependence of healing. Fig. 9 shows a schematic
In controlled laboratory healing experiments, this stage is
region of the plane of contact of a polymer interface.19 Due to
considered fairly trivial since surface preparation and suitably
surface roughness, etc., good contact and wetting are not
applied pressure usually ensures that the surfaces are brought
achieved instantaneously at all locations. Typically, wetted
together. However, this stage could be the most critical for
‘‘pools’’ are nucleated at random locations at the interface and
self-healing materials. Simply, no healing occurs if the surfaces
propagate radially until coalescence and complete wetting are
are not brought together or the gap is not filled with the healing
obtained. This problem has been treated as a two-dimensional
fluid. Thus, any debris left over from the damage process could
nucleation and growth process such that the fractional wetted
pry the surface apart to prevent surface approach and terminate
area, W(t), is given empirically as:19
the self-healing process. Surface approach applies to crack
surfaces that are brought together to heal alone or in the pres- W(t) ¼ 1  exp(ktm) (10)
ence of the healing fluid. This stage of healing considers the
time-dependent contact of the different parts of the surfaces to where k and m are constants depending on the nucleation func-
create the interface. Surface approach may be especially impor- tion and radial-spreading rates. This function predicts that 100%
tant in composites where the nature of the damage can involve wetting will occur eventually, but this may not be the case
the polymer matrix, fibers and the matrix–fiber interface. If the depending on how the surfaces are permitted to approach or
healing fluid only bonds to one surface, then little or no healing be filled in with the healing fluidFor crack healing, we have
will occur. The healing solvent may also force the surfaces observed that the wetting function W(t) convolutes with the
together by the pressure of swelling. interdiffusion function H(t) and affects the fracture energy of
the interface via:
2.4 Wetting ðt
G1c ¼ Hðt  tÞdW =dt dt (11)
When the damaged surfaces approach, they need to wet each
O
other and form an interface before the healing process can
continue. With self-repair fluids, the wetting and compatibility in which t is the dummy variable of the convolution integral.
of the damaged surface by the fluid must also be considered. For polymer welding, H(t) is controlled by the average interpen-
The topic of wetting and spreading of a fluid on a surface has etration contour length L, which behaves as,22
been treated by Brochard.97 In the capillary action required by
the Sottos and White model to fill the voids, the wettability of L(t)  (t/M)1/2 (12)
the surfaces by the fluid can be determined as part of the self-
healing design; some fluids may be better than others. One could Under high pressure surface contact, if the wetting rate is
also inquire if the fracture surfaces have been altered by oxida- constant dW(t)/dt  W0, then the convolution process predicts
tion due to chain fracture and are no longer wettable by the fluid. that the fracture energy should increase as

406 | Soft Matter, 2008, 4, 400–418 This journal is ª The Royal Society of Chemistry 2008
ðt
G1c  W0 LðtÞdt  t3=2 (13)
0

For self-healing reacting materials, the wetting function will


convolute with the reaction kinetics relation for strength devel-
opment. In the absence of diffusion at polymer–polymer inter-
faces, the wetting process delivers very little strength. However,
for rebonding the polymer matrix to a solid substrate such as
a composite fiber, the wetting stage should be rate determining,
coupled with surface rearrangement of sticker groups.

2.5 Diffusion stage


Fig. 10 Fractal interface formed by interdiffusing polymer chains. Only
The diffusion stage is the most critical stage of strength develop- one side is shown. (Green region) Chains connected with other side at
ment for both crack healing and self-healing systems at polymer– bottom. (Yellow chains) Those chains which have reached their equilib-
rium-diffused distance and continue to diffuse away but are no longer
polymer interfaces. It is a dominant stage in the ballistic
connected top the other side. (Red region) The fractal diffusion line sepa-
self-healing experiments when the elastically recoiling melt from
rating the non-connected from the connected chains which provide
the penetration hole rapidly wets and interdiffuses to make strength at the interface. [Wool and Long]
a good seal across the bullet hole.
The molecular aspects of interdiffusion of linear entangled
polymers (M > Mc) during welding of polymer interfaces are gradient of interdiffused chains, as shown by Wool and Long.51
summarized in Table 1.1 Gradient percolation theory104 requires that chains, which
The reptation dynamics and the interface structure relations in contribute to the interface strength (green), straddle the interface
Table 1 have been demonstrated experimentally by a series of plane during welding, such that chains in the concentration
interdiffusion experiments with selectively deuterated polymers gradient that have diffused further than their radius of gyration
using dynamic secondary ion mass spectroscopy (DSIMS) and (yellow) cease to be involved in the load-bearing process at the
neutron reflectivity.98–103 The scaling laws and the complete interface. We have shown that this amounts to a very small
concentration profiles have been calculated by Kim and Wool22 number and for narrow molecular weight distributions, can be
and Zhang and Wool23 The important result for the contour ignored.1,51 However, for broad molecular weight distributions,
length L  (t/M)1/2, was also supported by welding computer the fraction of non-connected chains expressed through gradient
simulations of Windle et al.49 Initially, as the symmetric (A ¼ B) percolation, can be significant.105 When the local stress exceeds
interface wets by local rouse segmental dynamics, we find that the yield stress, the deformation zone forms and the oriented craze
rapid interdiffusion occurs to distances of the order of the radius fibrils consist of mixtures of fully entangled matrix chains and
of gyration of the entanglement molecular weight, ca. 30 A. This partially interpenetrated minor chains. Fracture of the weld
can also occur below Tg when the top surface layer becomes more occurs by disentanglement of the minor chains, or by bond
mobile than the bulk and can be explained by finite size rigidity rupture. It is interesting to note that if the stress rises to the point
percolation theory17 (Section 4). However, at this point, the where random bond rupture in the network begins to dominate
interface is very weak and fracture can be described by the nail the deformation mechanism, instead of disentanglement, then the
solution.57 At the wetting stage, the frictional pullout of weld will appear to be fully healed, regardless of the extent of inter-
intermeshed chain segments, which have ‘‘elbowed’’ their way diffusion. This can occur at high rates of testing when the minor
across the interface, determines the fracture energy. As welding chains cannot disentangle and bond rupture pervades the inter-
proceeds, S minor chains of length L diffuse into an interface face, breaking both the minor chains and the matrix chains.
of width X and considerable strength develops. The diffusing
chains are fractal random walks and interpenetrate with the 3. Damage and healing theories
matrix chains, which are fully entangled (ignoring surface
3.1 Percolation theory of damage and healing
reflection configuration effects on entanglement density).
The structure of the diffuse weld interface in Fig. 10 resembles We can learn about healing processes in materials by studying
a green box of average width X, with fractal edges containing a their damage mechanisms. A useful approach to evaluating the

Table 1 Molecular aspects of interdiffusion at a polymer–polymer interface

Molecular aspect Symbol Dynamic relation, t < Tr Static relation, Ht ¼ Tr r, s

General property H(t) tr/4Ms/4 M(3rs)/4 r, s


Average contour length l(t) t1/2M1/2 M 2, 2
Number of chains S(t) t1/4M5/4 M1/2 1, 5
Number of bridges P(t) t1/2M3/2 M0 2, 6
Average monomer diffusion depth X(t) t1/4M1/4 M1/2 1, 1
Total number of monomers diffused N(t) t3/4M7/4 M1/2 3, 7
Center of mass diffusion Xcm t1/2M1 M1/2 2, 4

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 400–418 | 407
Fig. 11 The microscopic entanglement structure, e.g. at an interface or
in the bulk, is related to the measured macroscopic fracture energy G1c
via the RP theory of breaking connectivity in the embedded plastic
zone (EPZ) at the crack tip. The RP theory determines smax in the
EPZ, which is related to G1c via Hutchinson’s J-integral theory. The
percolation parameter p, which is a measure of damage and healing, is
related to the interface molecular structure via p SL/X, where S is
the number of chains of length L in an interface of width X.1
Fig. 12 The role of percolation in the random fracture of bonds in
a model net at constant strain is shown. (a) The net of initial modulus
fracture energy G1c, of a healing interface of A–B polymers, is
E, is stressed in uniaxial tension to a stress s. (b) Release of stored strain
represented in Fig. 11.1 In this double cantilever beam (DCB) energy by random bond fracture in the net results in a percolating system
system, a crack propagates through the interface region preceded near the fracture threshold and a very broad distribution of stress on the
by a deformation zone at the crack tip. For cohesive failure, the bonds.1
fracture energy can be determined by the J-integral method, as
described by Hutchinson and Tvergaard,106–108 where G1c is the
The stored strain energy dissipation per unit volume Uf, to
integral of the traction stresses with crack opening displacements
fracture a network consisting of n bonds per unit volume is,
d, in the cohesive zone, following yielding at a local yield or craze
stress sY. The cohesive zone at the crack tip breaks down by Uf ¼ nD0[p  pc] (16)
a percolation process,17,18 as described herein, at a maximum
stress value, sm > sY. where Do is the bond fracture energy, and [p  pc] is the percola-
Typical ratios of sm/sY are about 4–5.106 The yield stress domi- tion fraction of bonds which must be broken to cause fracture in
nates the fracture process for non-crazing matrices such as ther- the network. In this approach, the strain energy U, is first stored
mosets and this is determined by the twinkling fractal theory in the net and we inquire if this energy is sufficient to break
(TFT)109 described in Section 4. Both sm and d are rate dependent n[ppc] bonds per unit volume when it releases at a critical strain
and in the simplest case, the fracture energy is determined by: energy density U*¼ s*2/2E, such that at the critical condition,

G1c ¼ smdm (14) U* $ Uf (17)

where dm is the critical crack opening displacement. Both smand Substituting for U* and Uf in eqn (17) and solving for the critical
dm depend on the damage-zone structure and the microscopic stress s*, we obtain the ‘‘net solution’’ for the critical fracture
deformation mechanisms controlling the percolation fracture stress as
process via disentanglement and bond rupture. To convert these
percolation concepts into quantitative fracture terms for healing s* ¼ {2EnD0[ppc]}1/2 (18)
processes, consider the experiment shown in Fig. 12.1
This experiment can be used to interpret fracture and healing This relation was found to be applicable to damage and heal-
on any 2d or 3d lattice with initial tensile modulus E and subject ing events in carbon nanotubes.18 Applications of eqn (18) to
to random bond fracture. Random bond scission causes the a range of polymer materials are shown in Table 2 where the
formation of microvoids, which coalesce into larger voids and entanglement density is v ¼ r/Mc.
facilitate a macroscopic crack propagating through the net at Eqn (18) predicts that the fracture stress increases with the
the percolation threshold. The Hamiltonian for the stored elastic square root of the bond density n  1/Mc. The percolation
energy can be formulated using the Kantor and Webman110 parameter p, is in effect, the normalized bond density such that
approach for specific lattices,111–115 the Born and Huang for a perfect net without defects, p ¼ 1, and for a net that is
method,116 or using the simple engineering strain energy density damaged or contains missing bonds, then p < 1. Obviously, as
approach as follows. The stored elastic strain energy density U, p approaches pc, the fracture stress decreases towards zero and
(energy per unit volume), in the lattice due to an applied uniaxial we have a very fragile material. The fatigue lifetime is also calcu-
stress s is determined by, lated using this concept and is presented in a later section. This
fracture relation could therefore be used to evaluate durability,
U ¼ s2/2E (15) fatigue damage accumulation, healing processes, or retention

408 | Soft Matter, 2008, 4, 400–418 This journal is ª The Royal Society of Chemistry 2008
Table 2 Comparison of RP theory and experimental fracture stress18 G/GN ¼ [1  Mc/M(t)]/[1  Mc/Mf]. (21)

s (theory)/ s (expt)/ Thus healing in this system involves repairing the molecular
Polymer Mc/g mol1 104MPa Mc1/2 MPa T/ C Ref.
weight from Mc back to its original value Mf. This could be
PE 4000 158 160 196 118 done using a liquid monomer, which reacts with catalyst to
PP 7000 119 98 120 118 make new chains in a crack zone, as suggested by White
PVC 11 000 95 142 180 118 et al.80 and Wudl et al.88
PMMA 18 400 74 68 60 118
145 140 118
PC 4800 144 3.3 Fracture and healing of an ideal rubber
120 20 117
PS 31 000 57 56 20 118
PTFE 13 200 87 117 196 118 For an ideal rubber, p ¼ 1, the modulus E ¼ vkT where v is the
PLA 12 000 65 (E ¼ 1 GPa) 64 20 5 cross-link density. Thus, eqn (18) predicts:
Starch 200 000 22 — 20 5
s(t)/sN ¼ E(t)/EN (22)

strength of a material by tracking damage through a single G(t)/GN ¼ v(t)/vN (23)


parameter p. For thermosets, p is related to the extent of reaction
of the cross-link groups and this could be critical in the fiber– An ideal rubber with a perfect lattice was essentially unbreakable
matrix interface of composites.120 at low strains (l < 4) since insufficient strain energy could be
The time dependence of healing R(t) can be described from stored to break the requisite percolation number of bonds, but
eqn (18) as: fracture could occur by strain hardening to produce a ten-fold
increase in modulus E, by introducing defects (p z pc) via fatigue
R(t) ¼ s(t)/sN ¼ [(p(t)  pc)/(1  pc)]1/2 (19) or radiation, by decreasing the bond energy D0 an order of
magnitude, or by raising the temperature to 3000 K. Alterna-
in which sN is the virgin strength with p ¼ 1 and p(t) is the time- tively, by making the cross-links through the use of partially
dependent bond fraction recovery. For example, if a diffusion intercalated nanoclays, damage occurs by opening the
process controls p  t1/2, then R  t1/4, as observed for crack heal- nanobeams of the clay (similar to Fig. 1) and reducing the
ing.13–15,119 The latter equation is similar in some respects to the cross-link density. However, this system can self-repair through
generic kinetic healing rate equation we proposed for mechanical diffusion and intercalation to restore the original cross-link
recovery in solid rocket propellants, filled elastomers, block density, as noted by Zhu and Wool7.
copolymers and hard elastic polypropylene:1
3.4 Fracture and healing of thermosets
R(t) ¼ 1  [1  R0]/[1 + Kt]a (20)
With highly cross-linked materials such as typical unsaturated
Here R0 is an instantaneous recovery fraction, which is depen- polyesters and epoxies used in composite materials, the percola-
dent on the initial extent of the damage, K is a temperature- tion theory predicts:
dependent parameter and a is a rate constant. This empirical
relation gives R ¼ R0 at t ¼ 0 and R ¼ 1 as t goes to infinity s(t)/sN  [v(t)/vN]1/2 (24)
and was found to adequately describe many healing processes.1
The repair of the cross-link density v(t) can be done by chemical
means, as suggested by White et al.,80 Dry and Sottos79 and Chen
3.2 Fracture and healing by bond rupture and repair
et al.88 for thermally re-mendable cross-linked materials.
The percolation theory predicts that fracture by bond rupture of Raghavan and Wool90 examined a matrix of possibilities for
linear polymers is in accord with Flory’s suggestion of the chain- healing and repair in thermoset polymers as shown in Table 3.
end effect, via p ¼ 1  Mc/M and pc ¼ 1  Me/Mc, such that:18 The results are summarized in Fig. 13.

Table 3 Table of interfaces encountered during repair, recycling, joining and manufacturing of polymer composites

Solid with As-cast Solid with fractured Solid with fractured


Liquid B (L) curface (SV) surface (SF) and treated surface (SFC)

L–SV repair and


Liquid A (L) L–L virgin (control) L–SF repair and recycling L–SFC repair and recycling
recycling
Solid with as-cast surface (SV) SV–SV wielding SV–SF welding and repair SV–SFC welding and repair
Solid with fractured surface (SF) SF–SF crack healing SF–SFC wear and repair
Solid with fractured and treated
SFC–SFC wear and repair
surface (SFC)

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 400–418 | 409
Again, it should be possible to improve on this healing mecha-
nism with free-radical transfer agents.
7. Liquid–solid fracture, chemically treated interface (L–SFC).
This interface involves first treating the fracture surface with
a chemical treatment, such as styrene monomer which would
polymerize along with the liquid. This is important in repair
and recycling. The in situ polymerization of styrene gave the
best results with G1c ¼ 320 J m2, which is still considerably
less than the virgin state (500 J m2). As shown in Fig. 13, with
increasing molecular weight of the PS samples, the repair
strength decreased.
8. Solid virgin with solid fractured chemically treated interface
(Sv–SFC). This interface is relevant to welding and repair. Super-
glue gave a repair strength of 107 J m2, which is 22% of the
Fig. 13 Results of fracturing the A–B thermoset interfaces listed in virgin state.
Table 3.90 9. Solid fracture–solid fracture chemically treated interface
(SF–SFC). This interface is important in wear and repair. Typical
Here we examined a compact tension (CT) fracture mechanics values with adhesives (Superglue) gave strengths z 100 J m2.
specimen made with bottom part A and top part B (see inset in This interface resembles that used in the autonomic healing
Table 3) with the A–B interface along the crack plane. The 10 experiments of White and Sottos where the healing fluids are
A–B interfaces considered were as follows: contained in the UF spheres and released to the interface when
1. Liquid–liquid thermoset (L–L). This is the virgin state for damage occurs.
reference after curing the vinyl ester (Dow Derakane 411-C50) 10. Solid fracture chemically treated–solid fracture chemically
by free-radical polymerization using an organic peroxide initi- treated interface (SFC–SFC). The results were similar with the
ator (USP 245). For reference, the virgin L–L thermoset had chemical treatments giving some of the best results with fracture
a fracture energy G1c z 500 J M2. energies near 300 J m2. One of the chemical treatments consisted
2. Liquid–solid virgin interface (L–Sv). The liquid was cured of using 2 wt% solutions of polystyrene in toluene. The PS
on a virgin solid made from the same liquid. This is important molecular weights were 220, 596 and 4340 kDa. The idea was
in composite repair and recycling processes. This interface that connectivity between the solid interfaces could be achieved
surprisingly only achieved values of G1c z 15–200 J M2, which by diffusion of the PS chains into the cross-linked network,
is substantially less than the virgin state. Many different forms of which would have been swollen by the toluene solvent. This
cure were attempted but the result was always the same, a pre- result is encouraging for the design of solvent-healing systems.
cured solid sample does not bond with 100% strength to its The results of this work are summarized in Fig. 13.
own liquid, which could be a major problem in the design of
autonomic self-healing materials. Perhaps a chain-transfer agent 3.5 Healing of polymer–polymer interfaces
would have helped to promote additional connectivity between
the polymerizing liquid and the solid cross-linked material. Self-healing of thermoplastic polymer–polymer interfaces occurs
3. Solid virgin–solid virgin interface (Sv–Sv). This was a welding during ballistic impact, solvent bonding and sub-Tg surface
experiment with the two solid virgin surfaces. This interface welding. For healing of symmetric A–A interfaces, the gradient
showed some strength development when welded above Tg and percolation width X is the average monomer interdiffusion
G1c ¼ 66–107 J m2, The best results were obtained with the distance (see Fig. 10), the percolation parameter p ¼ SL/X,
lowest cross-link density. This interface clearly can benefit where S is the areal density of minor chains of interdiffused
from the release of self-healing fluids. contour length L, and the percolation threshold pc z Lc/M z 0.
4. Solid virgin–solid fracture interface (Sv–SF). The fractured In the general healing case where the chain ends are randomly
surface was welded with a virgin surface. No strength was devel- distributed in space near the interface, then S/X 1/M (see Table
oped after welding above Tg, as might be expected from the very 1) L  (t/M)1/2, then the fracture energy increases as G z L,
difficult wetting stage involving the rough fracture surface and
G(t)/GN ¼ [t/t*]1/2 (25)
the smooth virgin cured surface.
5. Solid fracture–solid fracture interface (SF–SF). This is where the weld time t*  M, when M > M*, and t  M3, when
a crack healing experiment and little strength was developed at M < M*. Typically, M* z 8Mc.
healing temperatures above Tg with G1c ¼ 8 J m2. Below Tg, When the chain ends are segregated to the surface, which
healing fluids would have to be released into the interface. could occur due to fracture or the presence of low surface energy
6. Liquid–solid fracture interface (L–SF). The fractured solid is chain ends, S is constant with time since all the chains begin
cured in contact with its own liquid. This is important for auto- diffusing at the same time and we obtain:
nomic healing processes where the healing liquid in the hollow
fibers or UF spheres is similar to the matrix. This interface G(t)/GN ¼ [t/t*]1/4. (26)
behaved like the L–Sv interface and only a small fraction of
the strength was recovered, again raising a warning signal for where again, t*  M. This allows healing to occur faster
autonomic self-healing design in highly cross-linked thermosets. compared to eqn (25). In ballistic self-repair experiments, the

410 | Soft Matter, 2008, 4, 400–418 This journal is ª The Royal Society of Chemistry 2008
time t* is temperature dependent and the needed time for healing a rather subtle processing point, which is often not appreciated
competes with the cool-down process. by the manufacturing industry and is important for self-healing
When using healing fluids with monomers that are different design, namely that fatigue and strength are related but not
than the matrix monomers, one can encounter an asymmetric, similar in terms of healing parameters.
potentially incompatible interface. For asymmetric incompatible In fatigue of materials in general with applied stress sapp < sc,
A–B interfaces of width d  c1/2, where c is the Flory–Huggins the percolation theory suggests a new approach as follows: the
interaction parameter, we have again the percolation parameter lifetime t occurs when the initial fraction of bonds pi is reduced
for the diffuse interface as p ¼ SL/X. In this case, X  d, L  d2, to pf, such that fracture occurs at the applied stress in accord
and S is constant such that p  d. Since the fracture energy G  with eqn (18) as:
[d  dc], where dc is the tube diameter, then the fracture energy
depends on the normalized width w ¼ d/dc as,17 sapp ¼ {2ED0v[pf  pc]}1/2 (30)

G(t)/GN ¼ [w(t)  1]/[wN  1] (27) This gives the critical bond fraction pf for the applied stress as

The latter relation is supported by experimental data on a wide pf ¼ pc + sapp2/{2ED0v] (31)


range of A–B interfaces, which were analyzed by Benkoski
et al.39 and Cole et al.40 The time dependence of p can be deduced from a steady-state
Incompatible A–B interfaces are typically quite weak bond-fracture concept via
compared to welded homopolymers. To make such interfaces
stronger, they can be reinforced with A–B co-polymer compa- Pf ¼ pi  t(dp/dt) (32)
tiblizer chains, as demonstrated by Brown and co-workers41–48
such that the failure time t is the time required to reduce pi to pf
Thus, one could incorporate compatibilizers into the healing
at the prevailing breakage rate dp/dt. The rate of bond rupture
fluid, which when released would have sufficient mobility, e.g.
dp/dt can be given by a thermally activated state theory
in a solvent, to heal the interface. For incompatible A–B inter-
(reviewed in ref. 119) as:
faces reinforced by an areal density S of A–B compatibilizer
chains, an equilibrium diffuse interface is formed in which L dp/dt ¼ (1/t0)exp(Do[1  sapp/sc]/kT) (33)
and X are constant, such that the percolation parameter p  S
and pc  Sc. Thus, the fracture energy as a function of areal in which the energy for bond fracture D0 is linearly reduced by
chain density becomes:17 the applied stress. Substituting for dp/dt and pf and solving for
t, we obtain the lifetime of the material as:
G(t)/GN ¼ [S(t)  Sc]/[SN  Sc] (28)
t ¼ t0{[pi  pc]  sapp2/(2ED0v)}exp(D0[1  sapp/sc]/kT) (34)
The above connectivity relations for polymer interfaces are in
accord with much data obtained by several groups39–48 and are where D0/kT z 133 at room temperature and t0 z 1012 s is the
reviewed in ref. 1 and 17. They provide the keys to understanding vibrational period for the bonds being broken. For a material
damage evolution in fracture and its converse, healing. without defects, pi ¼ 1 and sc is determined from eqn (18) using
pf¼ 1. Note that the applied stress enters in both the front factor
3.6 Fatigue healing and exponential factor for t. When the applied stresses are small,
the exponential factors dominate and the ratio of two lifetimes at
For healing of thermoplastic interfaces the total interpenetration
applied stresses s1 and s2 would be:
of chains (X approaches Rg) is not necessary to achieve complete
strength when M > M* and t* < Tr. It is only necessary to diffuse t1/t2 ¼ exp[(s2  s1)/sc]D0/kT (35)
a distance equivalent to the radius of gyration of M*. However,
a word of caution: while complete strength may be obtained in When the damaged bond fraction is restored by self-repair
terms of critical fracture measures such as G1c and K1c , the dura- processes such that pi / 1 in eqn (34), the material is rejuvenated
bility, measured in sub-critical fracture terms, such as the fatigue and its lifetime is considerably extended. Thus, in Fig. 7, we see
crack propagation rate da/dN, may be very far from its fully that the healing fluids allowed the initial pre-crack to be
healed state at t*. We have shown that while the weld toughness completely healed (pi / 1) and that during fatigue, the self-
K1c increases linearly with interdiffusion depth X, as K1c  X, the healing fluids retarded the crack advance compared to the
fatigue crack propagation behavior of partially healed welds control as the rate of bond rupture dp/dt was reduced.
behaves as:21

da/dN  X5 (29) 4 The hard-to-soft matter transition


4.1 Twinkling fractal theory of Tg
which is a very strong function of interdiffusion and underscores
the penalty to pay for partial welding. Thus, the weld strength A topic that is most relevant to this discussion on self-healing is
may be near, or at the virgin strength, but the fatigue strength the fundamental understanding of the hard-to-soft and soft-to-
may be dramatically reduced below its maximum value. Thus, hard matter transition, typically called the glass transition. The
one should always design a healing time with respect to Tr to glass transition temperature Tg is arrived at by heating a hard
achieve maximum durability of welds and interfaces. This is cold glassy material to a suitable temperature Tg whereby it

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 400–418 | 411
becomes soft; or by providing sufficient mechanical energy to distance between the oscillators contracts, the volume V
make the material flow by yielding; or by making the sample decreases and the bond expansion factor x approaches its critical
dimensions sufficiently small, typically nanoscale where the Tg value xc, such that when x > xc, the molecules are in the ergodic
drops considerably; or by examining the top layer of a solid liquid state and when x < xc, the molecules on average exist
sample at T < Tg, where it appears to have a mobile layer; or in the non-ergodic solid state. The latter idea parallels the
by increasing the cross-link density; or by changing molecular Lindemann (1910) theory of melting, which states that when the
weight or by removing a solvent, etc. We could ask whether it vibrational amplitudes exceed a critical value of the bond length
is possible to get thermally induced self-healing below Tg, or (x z 0.11), melting occurs. In our case we have a Boltzmann
how does Tg affect the design of our chemically cross-linking distribution of oscillators at various quantized energy levels in
system? Can we change the nature of the material by the rate the anharmonic potential energy function of the atoms such
at which we explore it, such as in liquid armor114 where a very that at any temperature T, there exists a fraction Ps of solid
soft cloth-like material turns to apparent steel at high rates of atoms (x< xc) and a fraction PL of liquid atoms.
impact. Conversely, how do we utilize impact energy to change The solid fraction Ps at any temperature T is determined from
a hard material to a soft material, which can self-heal, as in the integral (0 to xc) of the Boltzmann energy populations 4(x):
the ballistic healing experiments? ð
xc
An understanding of the glass transition remains as one of the Ps ðTÞ ¼ fðxÞ dx (36)
unsolved problems in the physics community, as discussed by
0
Angell,121 and is essential for soft matter. The classical onset of
the glass transition temperature Tg is shown in Fig. 14 where in which 4(x)  exp[U(x)/kT]. As Tg is approached from
the slope of volume V vs. T changes at Tg. The slopes are the above, as shown for example in Fig. 16, the fraction of solid
thermal expansion coefficients ag and aL for the glass and liquid, atoms Ps grows with a cluster size distribution function deter-
respectively. We consider the anharmonic interaction potential mined by percolation theory and eventually percolates at the
U(x) of quasiharmonic diatomic oscillators (Fig 15) in the liquid critical percolation threshold Pc.
state as a function of temperature. The anharmonicity controls The rigid (black) percolation cluster has a fractal dimension Df
the vibrational frequencies u, with temperature T, pressure P and is not stationary but is quite dynamic since locally the solid
and stress s,122–124 and the extent of the anharmonicity controls and liquid atoms are in dynamic equilibrium. Thus at Tg, to the
the magnitude of the thermal expansion coefficient a (Fig 15). observer, there appears to exist a fractal structure which ‘‘twin-
The vibrational frequencies, degree of freedom (d ¼ 1, 2 or 3) kles’’ with a frequency spectrum F(u) as liquid and solid atoms
and their density of states G(u) determines the thermal proper- exchange. This ‘‘twinkling’’ fractal structure is invisible to the
ties such as the specific heat capacity Cp and thermal conduc- usual scattering experiments since the liquid and solid are essen-
tivity K. As Tg is approached from above, the average bond tially indistinguishable to such scattering experiments.
The existence of the twinkling fractal near Tg has a profound
effect on many properties, such as the mechanical loss peak. It
suggests that the onset of Tg is purely kinetic rather than thermo-
dynamic such that at very slow rates, the fractal appears liquid

Fig. 14 Volume–temperature curve for a glass former. Tg occurs at Ps ¼


Pc when the fractal structure form.

Fig. 16 The twinkling fractal percolation cluster at Tg. The liquid


(white) regions are in dynamic equilibrium with the solid (black) clusters.
The twinkling fractal frequency spectrum mirrors the vibrational density
of states F(u)  uD exp([|U(T)  Uc|])/kT such that at temperatures
f1

ax 2
Fig. 15 Diatomic anharmonic Morse oscillator U(x) ¼ D0[1  e ] much greater or lower than Tg, the twinkling rate slows down in the
with Boltzmann energy levels and populations 4(x)  exp[U(x)/kT] pure liquid or very cold solid. Since the fractal is embedded in its liquid,
shows the liquid (X > Xc) and solid (X < Xc) phase diagram. it is invisible to the usual scattering experiments.

412 | Soft Matter, 2008, 4, 400–418 This journal is ª The Royal Society of Chemistry 2008
and at very high rates approaching u0, the fractal appears quite
rigid. This effect dominates the physics of the rate dependence of
yield in amorphous thermoplastic polymers and the physics of
liquid armor. The change in heat capacity DCp which appears
as a pseudo second order phase transition near Tg should be
determined predictably by the changes in the degree of freedom
of the oscillators from d ¼3 to d ¼ Df as well as the density of
states G(u)  ud , where df is the fracton dimension. The Tg value
f

of thin films will be affected by finite size percolation effects. The


Fig. 17 Finite size percolation effects are shown by the dark clusters for
existence of the twinkling fractal will also allow welding of glassy
one side of a thin film where p < pc. This also describes the surface of
polymers below their Tg via gradient percolation effects, where a thick film at T < Tg.126–129
the fractal danceswhile twinkling.
When the temperature drops below Tg, then the fractal has its
greatest manifestation on the evolution of the glassy structure. 4.2 Healing below the glass transition temperature
With decreasing temperature, the low frequency components of
the twinkling fractal spectrum slow down or become negligible Healing of polymer–polymer interfaces below Tg, as demon-
and the fractal becomes quite rigid such that the normal volu- strated by Boiko and co-workers67,68 can occur due to softening
metric contraction experienced in the liquid state deviates from of the surface layer as shown in Fig. 17. We have treated the
the extrapolated liquidus line VN and a non equilibrium surface layer softening as a gradient rigidity percolation issue.17
fractal-cavitation process commences resulting in the usual DV The surface rubbery layer concept in thick films is interesting
noted between Vg and VN(Fig. 14) Thus, the thermal expansion and this percolation theory suggests that for free surfaces there
coefficient in the glass ag is less than in the liquid state aL is a gradient of p(x) near the surface, where x < x (cluster size
approximately as ag z pcaL. For the Morse oscillator of equilib- correlation length) and hence a gradient in both Tg and modulus
rium interatomic distance R0, anharmonicity factor a, bond E. If the gradient of p is given by p(x) ¼ (1  x/x) then the value
energy D0, the critical distance xc z 1/3a and Tg is determined of xc for which the gradient percolation threshold pc occurs, and
from eqn (36), at pc ¼ ps, by: which defines the thickness of the surface mobile layer, is given
by the percolation theory as5,17
Tg z (1  pc)4D0/9k z 2D0/9k (37)
xc ¼ b(1  pc)/{pcv[1  T/Tg]v} (39)
The (linear) thermal expansion coefficient in the liquid is
obtained from the average position of the bond length using Here b is the bond length and n is the critical exponent for the
the integral of the Boltzmann populations (see Fig. 15) and is cluster correlation length x  [p  pc]n. For example with poly-
obtained in the quasi-anharmonic approximation as: styrene, when T ¼ Tg 10 K, Tg ¼ 373 K and using b ¼ 0.154
nm, pc ¼ 0.4, n ¼ 0.82, then the thickness of the surface mobile
aL ¼ 3k/[4D0R0a] (38) layer xc ¼ 3.8 nm. This could allow for healing to occur below
Tg assuming that the dynamics are fast enough.
which is related to Tg via eqn (37). For example, if D0 ¼ 3.5 kcal
If G1c  X2 for entangled polymers, then we could deduce that
mol1, eqn (37) gives Tg ¼ 391 K (118  C); using R0 ¼ 3A and a ¼
for sub Tg healing at DT ¼ Tg  T, as
2/A, then eqn (38) predicts that aL z 70 ppm K1 and ag z 35
ppm K1, which are typical values for engineering thermoplas- G1c  [1/DT]2n (40)
tics. It is interesting to note that the relation aLTg ¼ 1/(6aR0)
z 0.03, which was found to be true for many polymers and This appears to be in qualitative agreement with Boiko and
composite resins. Since the modulus E  D0, one also expects co-workers’ data68 who examined the fracture energy of polysty-
that E  1/aL. rene interfaces during welding at temperatures up to 40 K below
Physical aging occurs below Tg through the relaxation of DV Tg. The TFT also suggests the presence of some interesting
via the twinkling frequencies and is complex. Even well below dynamics in the mobile layer since the fractal clusters are essen-
Tg, there is a non-zero predictable fraction of liquid atoms tially ‘‘dancing’’ with a spectrum of frequencies related to the
remaining, which will cause the twinkling process to continue density of states G(u)  ud , where the Orbach fracton dimension
f

at an ever-slowing pace but allow the non-equilibrium structure df ¼ 1.33.


to eventually approach a new equilibrium value near VN. A
near-equilibrium glass can be made by removing the fractal
constraints in 3d at Tg by forming the material using 2d vapor
4.2 Twinkling fractal theory of yield stress
deposition, as recently observed by Ediger et al.125 They used The following analysis is important for the design of self-repair
vapor deposition of indometracin to make films, which were systems subject to ballistic impact and for the basic under-
reported to have maximum density and possess exceptional standing of rate effects on yield stress of solids and shear thick-
kinetic and thermodynamic stability, consistent with the liquid ening fluids. For an amorphous solid below Tg, subjected to
structure extrapolated into the glass. We have suggested that in triaxial stresses s1, s2, s3, the distortional strain energy function
this case with DV z 0, a critical observation would be that Ud is determined by (Von Mises) as:
ag ¼ aL. The latter experiment is currently being done (private
communication with Mark Ediger). Ud ¼ (1 + n)[(s1  s2)2 + (s2  s3)2 + (s2  s3)2]/6E (41)

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 400–418 | 413
in which n is the Poisson ratio and E is the isotropic elastic probability that the vibration will cause a ‘‘twinkle’’ or change
Young’s modulus. In the simple uniaxial case, we obtain the from solid to liquid or visa versa. Note that this energy difference
stored strain energy from eqn (41) with n ¼ 0.5 as U ¼ s2/2E. is always positive and is behaves as |U(T)  Uc|  [T2  Tc2]. In
This stored energy must be utilized to overcome a percolation a single mechanical cycle, the stored energy is released or dissi-
number of interatomic anharmonic oscillator bonds of energy pated by the twinkling process as liquid and solid clusters of
U(xc). For a Morse oscillator U(xc) ¼ 0.08 D0, which is the frequency u exchange at the fastest rates in accord with the
energy necessary to reach the Lindemann bond expansion at density of states G(u)  ud . As the temperature drops below
f

xc. The number of such oscillators per unit volume is 1/Vm, Tg, the percolating cluster increases in mass and the stored
where Vm is the molar volume. At the critical stored energy, energy increases. However, the twinkling frequencies decrease
we have yielding when the amorphous solid is raised to the twin- their rate due to the increased energy barrier DE ¼ |U(T)  Uc|
kling fractal state by the release of the mechanical energy and for the solid-to-liquid transition and the energy dissipation
flow begins in accord with: decreases. Near Tg, we can approximate the temperature depen-
dence of U(x) for a Morse oscillator as U(T) z a2D0a2T2, such
sy2/2E $ 0.08 D0 [ps  pc]/Vm (42) that the temperature dependence of F(u) is:

in which the solid fraction ps is given by eqn (36) and is both F(u,T) ¼ ud exp[b(T2  Tg2)/kT]
f
(47)
temperature and rate dependent. Thus, the yield stress is
obtained as:123,124 in which the constant b ¼ a2D0a2. Thus the activation energy DE
is temperature dependent approximately as DE  [(T/Tg)2  1]
sy ¼ {0.16E[ps  pc]D0/Vm}1/2 (43) and changes rapidly with T. When T > Tg, the rigid clusters
decrease, the stored energy decreases and the rate of liquid-to-
Note that the term D0/Vm corresponds to the traditional cohesive solid transitions decreases. Thus, tand will reach a maximum
energy density. For example, if E ¼ 1 GPa, p ¼ 1 (high rate of value near Tg typically. The twinkling fractal, though invisible
deformation), pc ¼ 1/2, D0 ¼ 3 kcal mol1, Vm ¼ 2M0/r, r ¼ 1 to scattering experiments could be the ‘‘dynamics engine’’ of
g cc1, the monomer molecular weight M0 ¼ 100 g mol1, then the amorphous state and plays an important role in complex
eqn (43) predicts that sY ¼ 71 MPa. This value is typical for processes such as physical aging and self-healing.
high performance amorphous polymers with Tg z 63  C.
The magnitude of ps is also rate and temperature dependent in
a manner determined by the twinkling fractal density of states. 5. Present and future advances in self-healing
As T approaches Tg from below, ps decreases towards pc and sy materials
decreases accordingly. At high rates of deformation, p increases
A new self-healing system that mimics a vascular healing system
and sy increases. At low rates of deformation, p decreases
in skin was developed by the Sottos–White group at the Univer-
towards pc and this is the basis for designing liquid armor with
sity of Illinois, using a micro-fluidics variant on their earlier
shear-thickening fluids, which are liquid layers with particles at
liquid sphere system as shown in Fig. 18.84 The advantage of
p > pc that turn into solids at high rates. Thus, ps(g)  [g/u0]df

this system over their earlier self-healing models, is that the


such that we can express eqn (43) as
embedded vascular system would allow multiple healing events
to occur. The encapsulated spheres were limited to one healing
sY/sN ¼ {[(g/u0)d  pc]/[1  pc]}1/2
f
(44)
event per crack. In the above case, cracks initiated in bending
in which sN is the yield stress at g ¼ u0. There exists a critical cause damage to the top coating (skin) which propagate and
deformation rate given by arrest at the coating–substrate interface (Fig 18c). The healing
fluid in the micro fluidic channels then wicks up the crack to
gc ¼ u0pc (45) the surface through capillary action. The fluid makes contact
with the epoxy skin, which contains the polymerizing agent
such that when g < gc, then the material is liquid-like and when g and the liquid-to-solid polymerization reaction is initiated.
> gc, then the yield stress increases from zero to its maximum They found that the healing fluid dicyclopentadiene (DCPD)
value at u0. Thus, the yield stress increases with rate of testing worked well with a Grubb’s catalyst, benzylidene bis(tricyclo-
and the higher the rate, the more stored energy is required, which hexylphosphine)dichloro ruthenium. This system has sufficiently
facilitates ballistic healing at high rates. low viscosity to allow facile flow to the skin surface and the cata-
The TFT concept of Tg suggests that twinkling fractal cluster lyst remains active both during and after the reaction. The
at Tg is quite soft, especially when sensed at low rates of authors successfully demonstrated that they could reheal the
deformation. One can immediately understand why the loss skin layer seven different times.
tangent tand ¼ E’’/E’(loss/storage modulus) reaches its In related experiments, White and Sottos et al. (private
maximum value near Tg. The twinkling fractal frequencies are communication) have found that in epoxy matrices, the DCPD
given by healing fluids along with the Grubb’s catalyst could be replaced
with a simple non-reactive solvent that was compatible with the
F(u)  ud exp[|U(T) Uc|]/kT
f
(46) epoxy. This is essentially a solvent healing system using the
autonomic or microfluidic delivery system. It is remarkable
Here the first term ud is the vibrational density of states for
f
that high levels of healing can be obtained in highly cross-linked
a cluster of frequency u and the second exponential term is the polymers using just solvents alone. The new solvent system will

414 | Soft Matter, 2008, 4, 400–418 This journal is ª The Royal Society of Chemistry 2008
Fig. 18 (a). Schematic diagram of a capillary network in the dermis layer of skin with a cut in the epidermis layer. (b) Schematic diagram of the
self-healing structure composed of a micro vascular substrate and a brittle epoxy coating containing an embedded catalyst. The sample is in a 4-point
bending fracture configuration monitored with an acoustic emission sensor. (c) High magnification cross-sectional image of the coating showing that
cracks which initiate at the surface propagate towards the micro channel opening at the interface (scale bar represents 0.5 mm). (d) Optical image of
self-healing structure after cracks are formed in the coating (with 2.5 wt% catalyst) revealing the presence of excess healing fluid on the coating surface
(scale bar represents 5 mm) (courtesy of S. White).

considerably lower the cost of autonomic self-healing systems original fracture toughness, and a composite with woven glass
that utilize both the urea formaldehyde spheres of healing fluid fibers achieved a healing efficiency of 68%.
and the biomimetic design discussed above. A thermally re-mendable cross-linked polymer was developed
Several other significant contributions to the design of self- by Chen et al.88 A highly cross-linked polymer was made using
healing materials have been made. Yamaguchi et al.86 utilized furan groups and maleimide, which would undergo a reversible
strong topological interactions of dangling chains in a polyure- Diels–Alder reaction. The tough material when damaged was
thane network polymer, which was obtained by eliminating the heated above 120  C and the molecular linkages would discon-
sol fraction of the weak gel just beyond the transition point. nect and then reconnect to reconstitute the network upon cool-
When cleaved with a razor blade at room temperature, complete ing. The process is completely reversible and was used to
healing was observed. This was attributed to the presence of the restore the strength of fracture samples several times. Perhaps
highly mobile long dangling chains near the gel threshold. this type of chemistry could also be used to develop recyclable
O’Conner20 had also observed healing of weakly cross-linked thermosets, in addition to re-mendable materials.
polyurethanes which were used as solid rocket propellant Zhu and Wool explored the role of nanoclay cross-linked elas-
binders. When cut with a razor, the cracks would slowly heal, tomers on their self-healing ability as shown schematically in
as measured by fracture mechanics. In Mazayuki’s material, Fig. 19.6,7 Linear polymer chains made from acrylated oleic fatty
the healing was very rapid by comparison, as if the weak gel acids methyl ester (AOME) were cross-linked through intercala-
behaves as a fluid. tion with nanoclay (Cloisite 30B). The mechanical properties
Yin et al.87 prepared a system similar to that of the Sottos– were shown to depend on the nanoclay concentration 4 as
White group. They used a two-component healing system follows: Modulus E  4, cross-link density v  4, fracture stress
whereby UF capsules (30–70 mm diameter) filled with an epoxy s  4. The mechanical properties are interrelated through rubber
were distributed in a matrix that contained a latent hardener. elasticity theory E  v and percolation theory for fracture stress
The latent hardener consisted of a complex of CuBr2 with as s  [Ev]1/2. When subjected to mechanical loading, the elasto-
2-methylimidazole, which was quite soluble and well dispersed meric network could absorb mechanical energy by opening the
in the epoxy composite matrix. When subjected to mechanical clay nanobeams, which would reduce the cross-link density.
stress, microcracks would form and break the UF spheres, Upon resting it was proposed that the nanoclay beams would
releasing the epoxy, which would then cure by contact with the reheal and reconstitute the original mechanical properties of
embedded hardener. They observed that the self-healing epoxy the elastomer. This elastomer, which is both biodegradable as
with 10 wt% spheres and 2 wt% hardener achieved 111% of its well as biocompatible with human tissue, can be optimized

This journal is ª The Royal Society of Chemistry 2008 Soft Matter, 2008, 4, 400–418 | 415
CREE-NRI, NSF, EPA, DOE and ARO, and his many
colleagues and fellow researchers who provided the grist for
expansion of his imagination.

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