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Why are double network hydrogels so tough?

Jian Ping Gong*
Received 18th November 2009, Accepted 9th February 2010
First published as an Advance Article on the web 9th March 2010
DOI: 10.1039/b924290b

Double-network (DN) gels have drawn much attention as an innovative material having both high
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water content (ca. 90 wt%) and high mechanical strength and toughness. DN gels are characterized by
a special network structure consisting of two types of polymer components with opposite physical
natures: the minor component is abundantly cross-linked polyelectrolytes (rigid skeleton) and the
major component comprises of poorly cross-linked neutral polymers (ductile substance). The former
and the latter components are referred to as the first network and the second network, respectively, since
the synthesis should be done in this order to realize high mechanical strength. For DN gels synthesized
under suitable conditions (choice of polymers, feed compositions, atmosphere for reaction, etc.), they
possess hardness (elastic modulus of 0.1–1.0 MPa), strength (failure tensile nominal stress 1–10 MPa,
strain 1000–2000%; failure compressive nominal stress 20–60 MPa, strain 90–95%), and toughness
(tearing fracture energy of 1001000 J m2). These excellent mechanical performances are comparable
to that of rubbers and soft load-bearing bio-tissues. The mechanical behaviors of DN gels are
inconsistent with general mechanisms that enhance the toughness of soft polymeric materials. Thus,
DN gels present an interesting and challenging problem in polymer mechanics. Extensive experimental
and theoretical studies have shown that the toughening of DN gel is based on a local yielding
mechanism, which has some common features with other brittle and ductile nano-composite materials,
such as bones and dentins.

I. Introduction friction (cartilage), and robust contraction (muscle).1 These soft

tissues, containing 30–80% water, are excellent soft & wet
Besides bones, tooth, and nails, human body consists of soft materials. Seeking artificial soft tissues to substitute damaged
tissues, such as tendons and ligaments (fixing the bone skeleton), real ones has been a challenging task for material scientists.
cartilage (adsorbing the shock and reducing the friction of bone There is only one candidate: that is the hydrogel.
motion), and muscle (generating force to move the bone). These A hydrogel, consisting of cross-linked macromolecules and
load-bearing soft tissues present excellent mechanical perfor- water, is also a soft & wet material. As a combination of solid and
mances, such as high toughness, shock absorbing, low sliding liquid components, hydrogels have a high permeability to small
molecules and undergo reversible volume change by exuding or
absorbing water in response to a wide range of stimuli, such as
Graduate School of Science, Hokkaido University, Sapporo 060-0810,
Japan. E-mail: [email protected]
light, temperature, pH, ionic strength, chemical reactions.2–8 In
the past two decades, sensing and actuating properties of
hydrogels have been extensively studied based on the volume
Jian Ping Gong received her changes.3–11 Owing to the similarity between hydrogels and soft
Bachelor’s degree in electronic tissues, recently, bulk hydrogels have drawn great attention as
physics from Zhejiang Univer- biomaterials,12 such as extra-cellular matrix,13–15 artificial bio-
sity, China. She received her organs,16–18 and phantom tissues in medical device
PhD for research on high Tc development.19
superconductors in 1993 from However, conventional hydrogels, which are usually
Tokyo Institute of Technology. composed of single network (SN) of hydrophilic polymer, are
She joined the faculty of science, soft, weak, and brittle. They usually fail at a tensile stress less
Hokkaido University in 1993. than sub-MPa and strain less than 100%. On the other hand,
She has been focused on the load-bearing biological soft tissues are much stronger. For
fundamentals and functions of example, cartilage, containing 75 wt% of water, exhibits an
soft and wet materials, such as compressive fracture stress of 36 MPa,20,21 which allows the
surface friction, toughening and cartilage to sustain a daily compression of several MPa.22
Jian Ping Gong fracture of gels. She received Hydrogels also show very low resistance against crack propa-
Wiley Polymer Science Award gation. Reported values to the fracture energy of the conven-
in 2001 for the study on surface friction of polymer gels, and the tional hydrogels fall within a range of 101–100 J m2,23–26 which
Award of the Society of Polymer Science, Japan for developing the are much smaller than those of cartilages (102–103 J m2)27 and
double network gels. the usual rubbers (103 J m2).26 The weak, brittle mechanical

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characteristic of hydrogels hinders the extensive use of this Then the first gel is immersed in an aqueous solution of a second
material. Thus far, hydrogels have been limited to the usage monomer with a low ratio of cross-linking agent and carrying out
where the mechanical properties are not highly concerned, such a second polymerization in the first network.37 Owing to the
as drug delivery devices,28 water-absorber.29 polyelectrolyte nature, the first polyelectrolyte gel highly swells in
One reason for the lack in mechanical strength of a hydrogel is the second monomer solution. As a result, the first gel network is
its solution-like nature, i.e., low density of polymer chains and highly extended in the final product and the amount of the
small friction between the polymer chains. Another reason is the second network in the final gel is in large excess to that of the first
heterogeneity of the network structure of the hydrogel formed network.
during the gelation.30,31 When a force is applied to a gel with Although this double network structure has been found
heterogeneous structure, stress is concentrated around the effective to many kinds of combination, among all the polymer
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shortest chain, and this leads to a failure of the sample at a very pairs studied so far, the one made of poly (2-acrylamido,
low force. Accordingly, many efforts have been made to 2-methyl, 1-propanesulfonic acid) (PAMPS) polyelectrolyte and
synthesize hydrogels with a homogeneous network structure, polyacrylamide (PAAm) neutral polymer stands out with
such as the slide-ring (SR) gels (a hydrogel with sliding cross- unusually properties.
linking points),32,33 and the tetra-PEG gels (a hydrogel from Hereafter, the DN gels are referred to as P1-x1-y1/P2-x2-y2,
tetrahedron-like macromonomers).34 These gels exhibit high where Pi, xi and yi (i ¼ 1,2 for the first and second network,
stretching ratio without fracture owing to the homogeneous respectively) are the abbreviated polymer name, in feed molar
structure. Nanocomposite (NC) hydrogels (a hydrogel from the concentration of monomer, and the cross-linker concentration
mixture of polymer and clay) have also been shown to effectively (in mol% with respect to the monomer for the i-th network),
improve the mechanical strength.35,36 respectively. Fig. 1 shows a photo of tough PAMPS-1-4/PAAm-
Different from the above approaches that concentrates on 2-0.1 DN gel against deformation. Fig. 2 shows compressive
developing a gel with a homogeneous structure, an alternate nominal stress-strain curves for the PAMPS-1-4/PAAm-2-0.1
approach, whereupon the heterogeneity of the hydrogel was DN gel, the PAMPS-1-4 and the PAAm-2-0.1 SN gels. The DN
incorporated preferentially, was discovered and has been devel- gel holds up to a nominal stress of 17.2 MPa, where the vertical
oped by the author’s group. This new class of hydrogel is known compressive strain 3 is about 92%. On the other hand, the
as double-network hydrogels (DN gels), in which a high relative PAMPS gel and PAA gel break at stresses of 0.4 MPa (3 ¼ 41%)
molecular mass neutral polymer network is incorporated within and 0.8 MPa (3 ¼ 84%), respectively.
a swollen heterogeneous polyelectrolyte network.37 The The strength of DN gel increases when the molar ratio of the
mechanical properties of DN gels prepared from many different second network to the first one increases (Fig. 3a). The
polymer pairs were shown to be much better than that of the mechanical behavior of the DN gel sensitively changes with
individual components. Under an optimized structure, the DN the cross-linker density of the second network, even if all the
gels, containing about 90 wt% water, possess hardness PAMPS/PAAm DN gels show almost the same elastic modulus,
(elastic modulus of 0.1–1.0 MPa), strength (failure tensile stress water content, and molar ratio of the second network to the first
110 MPa, strain 1000–2000%; failure compressive stress 20– network (Fig. 3b).36 For a long time, it had been a puzzle why the
60 MPa, strain 90–95%), and toughness (tearing fracture energy DN gel became the toughest when the 2nd polymer was
of 100–1000 J m2).38–43 These excellent mechanical performances synthesized without the cross-linker.37,39,41 A recent study42 has
had never been realized before in synthetic hydrogels, and are elucidated that when the first PAMPS gel was synthesized, some
comparable to and even exceed some soft load-bearing tissues.1 divinyl-crosslinker N,N0 -methylenebis(acrylamide) (MBAA) was
Similar enhancement in strengths by the double network concept reacted only on one side and un-reacted double bonds were still
have been observed in some other works, such as polyethylene- remained in the first PAMPS gel; when the second PAAm was
oxide/polyacrylic acid double network gels,44,45 and the modified- synthesized in the first PAMPS gel, AAm and the remained
hyaluronan/poly(N,N0 -dimethylacrylamide) DN hydrogels.46 double bonds were co-polymerized and then the second PAAm
Combination of bacterial cellulose (BC) with neutral polymers, was chemically cross-linked with the first PAMPS gel. Accord-
such as gelatin, or synthetic polymers as PAAm also exhibits an ingly, usual DN gels have inter-cross-linked (connected) double
enhanced mechanical performance.47
The DN gel shows that microstructure control can lead to
greatly enhanced strength and toughness in gels. The super
strength and toughness of the DN gels cannot be described by the
classic Lake–Thomas theory,26 and it is based on a local yielding
mechanism that has common features with other tough mate-
rials, such as metals, glassy polymers, rubbers, and even bone.
This paper reviews the optimized structure, mechanical behavior,
and toughening mechanism of DN gels.

II. Synthesis and optimized structure

The DN gel is synthesized from monomers in the presence of
a cross-linker via a two-step network formation: the first step is Fig. 1 Images of a tough PAMPS/PAAm DN gel. A movie is available
forming a tightly cross-linked network gel of polyelectrolyte. at http://altair.sci.hokudai.ac.jp/g2/index_e.html.

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Fig. 2 Compressive nominal stress–strain curves for the PAMPS/PAAm

DN gel (:), PAMPS gel (B) and PAAm gel (,). Cross-linking density:
4 mol% for PAMPS, 0.1 mol% for PAAm. (Revised with permission from
the literature.37)

network structure (so named ‘c-DN’ gels in Fig. 4a), and usual
DN gels reached a high strength even without adding any cross-
linker of the second network by the inter-connection between the
two networks through covalent bonds. It was further clarified
that truly independent-DN gels (named ‘t-DN’ gels), which do not
have any covalent bonds between the first and the second
networks, cannot be toughened by the un-crosslinked second
network. Furthermore, it was found that the t-DN gels become
stronger than the c-DN gels when the second network is loosely
cross-linked at an optimal cross-linker density of 0.01 mol%, as
shown in Fig. 4b. This optimal cross-linker density indicates
that the PAAm partial chains between neighboring cross-
Fig. 3 Relationship between the mechanical strength of PAMPS/PAAm
linking points have a very high molecular weight (higher than DN gels and their structure parameters. (a) Relationship between the
106 g mol1). molar ratio of the 2nd network to the 1st network and the compressive
Therefore, the essential feature of DN gels is that it consists of nominal stress at fracture for the PAMPS-1-4/PAAm-x2-0.1 DN gels.
two kinds of polymers with strong asymmetric structure, as The different composition ratios of the 2nd to the 1st network were
summarized below, which is different from conventional inter- obtained by immersing the 1st network gel in monomer solutions
penetrated networks (IPN). constituting the 2nd network with various concentrations. Numbers in
(1) Rigid and brittle polymer, such as polyelectrolyte, as the the figures denote the value of the monomer concentration x2 for poly-
first network; soft and ductile polymer, such as neutral polymer, merizing the 2nd network. Data at zero molar ratios denote the values of
as the second network. single network gels. (Reproduced with permission from the literature37)
(b) Dependence of the fracture energy G at v ¼ 0.5  102 m s1 (B) and
(2) The molar concentration of the second network is 20–30
the compressive nominal fracture stress sm (,) of PAMPS-1-4/PAAm-2-
times the first network.
y2 on the cross-linking density y2 of the second component, PAAm.
(3) The first network is tightly while the second network is (Revised with permission from the literature.41 For the correct values of
loosely cross-linked, which requires a very high molecular weight the fracture energy G, the data in the original figure were multiplied by
of the second polymer. a factor of 2 in this figure.)
By adjusting the structure parameters of the two networks, one
can reach a wide range of the mechanical performance of the DN fracture surfaces, U is a bond dissociation energy, and n is the
gels (Fig. 5).48 This makes it possible to tailor the modulus, average number of monomer units between cross-linkers.26 This
strength, and toughness of hydrogels in order to fit mechanical equation means that when a general cross-linked polymer is
performance into any functional matrix. broken, only the polymer chains located at a crack tip are cut off.
Recently, it has been further found that ultrathin double- The energy is dissipated to break the chemical bond, and before
network (UTDN) hydrogels, of ca. 100 mm thickness, show the chemical bond failures, the energy is stored elastically and
a high strength and toughness comparable to that of the bulk DN there is no hysteresis in the stress–strain curve. This well explains
hydrogels, indicating that the double network concept is appli- the fracture of various single network hydrogels at a moderate
cable even at a hundred micrometre dimension.49 fracture velocity.24,33,34
On the contrary, the fracture behavior of the DN gels is
distinctly unusual. Systematic loading and unloading experi-
III. Mechanical behavior—necking and hysteresis
ments in uniaxial tension and compression show a significant
The classical Lake–Thomas theory predicts that the ideal frac- hysteresis during the first loading cycle, increasing very strongly
ture energy Gc of cross-linked polymer systems can be calculated with the applied maximum deformation (Fig. 6).50 Such a large
by Gc ¼ rnU, where r is the area density of polymer chains on hysteresis was velocity-independent and never observed during

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Fig. 6 Successive loading cycles in compression of a PAMPS/PAAm

DN gel sample. (Reproduced with permission from the literature.50)

fairly soft, showing an elastic modulus ca. 1/10 of the virgin

sample, and sustains large elongation, up to an elongation strain
of around 20. The observations on the softened gels after the
tensile test demonstrate that irreversible structural change takes
place inside the gels, although their appearance is almost
unchanged.
Fig. 4 (a) Illustration of chemical structures of connected-DN (c-DN) From the above experimental findings and the fact that the
gels and truly independent-DN (t-DN) gels. (b) The fracture energy G of PAMPS SN gels are quite brittle and break into small pieces at
connected-DN gels and truly independent-DN gels, as a function of the small extensions (several percent of strain), it shows that in the
effective cross-linking density of the second network. The upper hori-
course of necking deformation, the 1st PAMPS network frag-
zontal axis indicates the subchain molecular weight of PAAm network.
ments into small clusters; and the clusters play a role of cross-
Open symbols indicate too weak samples to be measured by tearing test.
Solid straight lines are the fitted curve to the experimental equation linker of long PAAm chains (Fig. 8), because the 2nd network is
as described in literature. (Reproduced with permission from the loosely cross-linked. The fragmentation should involve dissipa-
literature.42) tion, which is reflected in the hysteresis of the loading curves in
Fig. 7. Assuming that the concept of fracture energy applies to
the microscopic fragmentation of the 1st PAMPS network in the
DN gel, and that the fracture energy for the fragmentation can be
substituted by the fracture energy G for the bare PAMPS SN gel

Fig. 5 Comparison of the mechanical strength of various polymer

materials. Accessible tensile nominal fracture stress and fracture strain
range for PAMPS/PAAm DN gels prepared by change the structure
parameters is shown.

a second loading cycle. Accordingly, it was attributed to the

fracture of covalent bonds in the first network.
Furthermore, yielding phenomenon was observed in some
tough DN gels.39,51,52 For example, on tensile tests of DN gels
that made from relatively sparse (fragile) first networks, nar-
rowing zones (‘‘necks’’) appear in the sample and grow up with
further stretching, as shown in Fig. 7.39,51 During the neck Fig. 7 Loading curve of PAMPS/PAAm DN gel under uniaxial elon-
propagation, a plateau region appears in the loading curve. The gation at an elongation strain rate of 0.13 s1, and pictures demonstrating
plateau value of the tensile stress hardly depends on the the necking process. The insert alphabets represent the correspondence
stretching rate. After the neck propagation, the gel becomes between the pictures and the arrowed data points.

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Fig. 9 Comparison of the loading curves for PAMPS-1-2/PAAm-2-0.02

DN gel after necking (open circles) and a PAAm single network gel with
the same acrylamide concentration and initial Young’s modulus (filled
circles). (Reproduced with permission from the literature.39)

the tearing test revealed that the fracture energy G ranges from
Fig. 8 Illustration of the network structure of the DN gel before (a) and
after (b) necking. Above a critical stress, PAMPS fractured to clusters
102–103 J m2, which is 100–1000 times larger than that of normal
and the PAMPS clusters behave as a sliding cross-linker of PAAm. The PAAm gels (100 J m2) or PAMPS gels (101 J m2) with similar
DN gel becomes soft after the necking. polymer concentrations to the DN gels.38–42 Furthermore, G
shows weak dependence on the crack velocity V.41,52
in water, the typical size x of the PAMPS clusters in terms of These behaviors of DN gels are inconsistent with general
macroscopic observables, i.e., the critical stress sc (¼0.7 MPa), mechanisms that enhance the fracture strength of soft polymeric
the strain at the point where the necking finishes 3c (¼11), and the materials, i.e., viscous dissipation for chain-pulling processes
fracture energy of PAMPS in water, GPAMPS(z1 J m2), can be around crack tips,56,57 and bulk viscoelastic losses accompanying
estimated, xzGPAMPS/sc3c ¼ 0.1 mm. The value of x may reflect crack propagations.58 Several theories for the origin of the high
quenched inhomogeneity of the 1st network of DN gels found in fracture energies have been developed.59–63 Among them, the
neutral scattering study.53 The SANS measurements further local yielding and hardening model at the crack tip is considered
indicate that deformation of DN-gels results in a periodic and as the most promising.60,61
mesoscale (1.7 mm under a uniaxial stretching strain of 50%) Based on the necking phenomena39 and the large hysteresis of
compositional fluctuations in both PAMPS and PAAm.54 Recent DN gels,50 Brown60 and Tanaka61 have independently proposed
studies on the surface of ultra thin DN gels films (ca. 100 mm) at a similar phenomenal model for explaining the extra-ordinary
the necking region reveals a network-like morphology that might high fracture energy of DN gel: the model assumes that on the
be related to this fracture structure.55 strongly stretched region in front of the crack tip, necking similar
The softened gel after necking is a fascinating system. First, the to the tensile test occurs, and the gel transform into a very soft
PAMPS clusters, playing a role of cross-linker, are not chemi- one with an intrinsic fracture energy G0, and then the crack tip
cally bonded (except for a few inter-cross-linked points for passes through the softened (damaged) zone by further stretching
‘c-DN’ gels) to the PAAm chains; thus, the ‘‘molecular weight (Fig. 10). Using the energy balance concept of fracture
between cross-linking’’ can be adjusted by chain sliding in mechanics, a scaling level expressions has been proposed, in
response to deformation. The capability of chain sliding is in which the effective fracture energy of DN gel, G, is expressed in
common with the slide-ring gels that are ductile.32,33 Further- terms of the yielding stress sc, the size of the softened zone h, the
more, the PAMPS cluster can be re-divided; when a cluster in intrinsic fracture energy G0, and the strain where the necking
a deformed sample suffers a larger stress than other ones, the finishes 3c.61
inequality of stress can be corrected by the re-division. Owing to
these effects, the resultant network structure has less mechanical G ¼ G0 + sc 3c h
defects. Due to the above structural features, the softened DN gel
showed an excellent extensibility (fracture strain 3f ¼ 19), which
is much larger than that of a usual single network PAAm gel The critical width h above which the crack can propagate at
(fracture strain 3f ¼ 8) of the same PAAm concentration and given G0 and sc is determined by balancing the surface energy
elastic modulus, as shown by Fig. 9.39 cost and the elastic energy release U(sc) for a crack propagation
at a unit length.61
G0 Est
h ¼ G0 =Uðsc Þz 2
IV. Toughening mechanism—formation of local sc
damage zone
Here, Est is the modulus at 3c where the necking finishes.61 An
The fundamental toughening mechanism of DN gels is of great order estimation of G using the numerical data from the necking
interest to researchers. Measurement of the fracture energy G by gel predicts that the necking zone is in an order of 100 mm.61

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Fig. 10 Illustration of local damage zone at the crack front of DN gels.

The existence of the damage region has been verified by

observation. Using AFM measurements, a softened region was
successfully detected just below the fracture surfaces, which
supports the assumption of localized damage accumulation.64
Furthermore, the localized damage zone around the crack tip of
the DN gel was directly observed by a 3-dimensional violet laser
scanning microscope, as shown in Fig. 11.52 A special zone that
looks different from the other regions can be observed around
the crack in the images, indicating the existence of a damage
zone. The thickness of this damage zone h is in the order of Fig. 11 Images of the crack tip observed after tearing. (a) Photographic
several 100 mm, which is consistent with the predictions of image captured using a conventional optical microscope; (b) high-low
Brown–Tanaka models. Further, a proportional relationship image captured using a color 3D violet laser scanning microscope;
between the thickness of the damage zone h and the fracture (c) illustration of the damage zone (grid) and the undamage zone (blank).
energy G was observed. The ratio of G/h, which is equal to sc 3c V is tear velocity, F the tear force, and h the thickness of damage zone.
(Reproduced with permission from the literature.52)
according to the model61 (an alternative interpretation of G/h is
the energy needed to fracture the PAMPS network into clusters
per unit volume), was found to be velocity-independent, and sc and the cluster size x of PAMPS, and how the stress is
showed a value about 6 times smaller than sc 3c estimated from transferred from the second network to the first network via
the tensile test. This is different with the model that predicts a distance as large as hundred of mm. The value of sc is much
G/h z sc 3c. Several possible reasons have been considered for larger than the fracture stress of a single network PAMPS,
this discrepancy.52 Recent observations on the surface of ultra indicating that in the presence of PAAm, the fracture of the
thin DN gels films (ca. 100 mm) at the crack region suggests that brittle PAMPS does not percolate to the whole sample until to
the discrepancy is mainly due to an over-estimation of h by the a much high stress, nevertheless the stress–strain curve follows
3-dimensional violet laser scanning microscope.55 Accordingly, the behave of the single network PAMPS (Fig. 2). Small-angle
the phenomenological models proposed by Brown and Tanaka neutron scattering (SANS) study has revealed a strong hetero-
catch the essential feature of DN gels. In terms of the fracture geneity in the first network density (Fig. 12),53 which explains the
mechanics, DN gels are quite similar to glassy polymers which hysteresis results even at a small deformation.54 However, it is
shows toughness by forming a crazing zone at the crack tip.65 not clear if the strong heterogeneity of the PAMPS first network
However, from the viewpoint of the molecular level, several plays an intrinsic role for the specific fracture behavior and if the
questions still remain, such as what determines the yielding stress value of x is related to this heterogeneity. Dynamic light

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scattering (DLS) study shows that fluctuation dynamics of both without strong physical association between molecules, the
PAMPS and PAAm components is tightly coupled,40 indicating fracture energy of the gel is consumed only by bond scission on
the strong entanglement between the two polymers, which may the fracture surface that is not higher than several 10 J m2, as
account for the force transmission from PAAm to PAMPS to described by the Lake–Thomas theory. Accordingly, once the
form the mesoscale softened zone. Furthermore, SANS size of a flaw is larger than the critical value determined by the
measurements on PAMPS/PAAm DNgels and their solution Griffith fracture criterion,66 the crack will grow catastrophically.
blend counterparts indicate that the two polymers interact Although there is no report on the study of fracture, such as
favorably with each other while in water.53 This favorable a tear test, for slide-ring gels and tetra-PEG gels, it is reasonable
PAMPS/PAAm interaction given by the condition, cPE-NP  to assume that these gels have a low resistance against the frac-
cPE-water < cNP-water, where c is the Flory-Huggins interaction ture propagation, and therefore, are easy to break once a crack is
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parameter. A molecular interaction mechanism is proposed for induced.

the force transmission from PAAm to PAMPS to form the On the other hand, the strategy of the DN gels is to increase
mesoscale softened zone.54 However, this seems in contradiction the resistance against the crack propagation by forming large
with the fact that tough DN gels need chemical cross-linking for damage zone at the crack tip, whereupon the heterogeneity of the
the second network PAAm (Fig. 4b).42 first, brittle network might be crucial. Further study on a DN gel
with a relatively homogeneous structure is necessary to clarify
the role of the heterogeneity of the brittle component. Yielding
V. A comparison to other hydrogels with excellent and hysteresis have also been observed in NC gels,67 indicating
mechanical performance a similar fracture mechanism as that of the DN gels for the NC
gels. In the case of the NC gels, the yielding is due to the
The failure of a material is via two processes: one is the initial detachment of the polymers from the adsorbing clay surfaces
crack formation (nucleation) and the other is the crack propa- which involves energy dissipation. Although there is no report on
gation (growth). The strategy to toughen the gel by forming the tear test, one expects a high resistance to crack propagation
a homogenous structure, as having been developed by slide-ring of this material.
gels and tetra-PEG gels,32–34 is to reduce the probability of initial
crack formation. This strategy is effective in increasing the
strength (the fracture stress or the fracture strain) of the gel, but VI. Conclusions and future directions
not the toughness (fracture energy). For a simple hydrogel As organic–inorganic hybrid composites, natural biological
materials, such as bones and dentins, exhibit superior mechanical
properties such as toughness and strength in comparison with
their constituent phases: the organic phase is usually very soft
and the inorganic phase very brittle.68–71 Although the concrete
molecular pictures are different, the toughening mechanism of
DN gel has some common features with that of natural organic–
inorganic hybrid composites. The rigid, brittle PAMPS first
network serves as a sacrificial bond that fractures at a relatively
low stress, while the soft, ductile PAAm serves as hidden length
that sustains stress by large extension afterwards, similar to
a picture proposed for the fracture of bones.69
It should be pointed out that this DN gel has a negligible
fatigue resistance, which will be a limitation in many practical
applications. This limitation arises from the fact that the
toughening is due to the irreversible failure of covalent bonds in
the first network. However, the same DN gel concepts can, in
principle, be applied to other self-healing types of materials,72,73 if
the covalent bonds are replaced by reversible bonds. The chal-
lenge is to obtain bonds that are both strong and reversible, but
this is presumably what is accomplished in a variety of tough,
biological materials, including the cartilage tissue that these
materials were designed to mimic. As Shull has emphasized, there
is a need to develop better understanding of fracture toughness in
these DN gels and in biological tissues.74

Fig. 12 SANS from (a) 2M PAAm linear chains in water and in DN Acknowledgements
gels; (b) PAMPS network in pure water and in DN gels. Data show that
the dense, inhomogeneous structure of PAAm and PAMPS (schematics c This research was financially supported by a Grant-in-Aid for the
& e respectively) polymerized in water gets homogenized when in the Specially Promoted Research (No. 18002002) from the Ministry
presence of each other (schematics d & f respectively). (Reproduced with of Education, Science, Sports and Culture of Japan. The author
permission from the literature.54) thanks T. Kurokawa, Y. Tanaka, H. Na, H. Furukawa,

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Y. Osada, and the graduate students in LSW for their contri- 38 H. Tsukeshiba, M. Huang, Y.-H. Na, T. Kurokawa, R. Kuwabara,
butions. The author also thanks C. Creton, W. L. Wu, H. Brown, Y. Tanaka, H. Furukawa, Y. Osada and J. P. Gong, J. Phys.
Chem. B, 2005, 109, 16304.
and M. Shibayama for useful discussions and contributions to 39 Y.-H. Na, Y. Tanaka, Y. Kawauchi, H. Furukawa, T. Sumiyoshi,
this work. J. P. Gong and Y. Osada, Macromolecules, 2006, 39, 4641.
40 M. Huang, H. Furukawa, Y. Tanaka, T. Nakajima, Y. Osada and
J. P. Gong, Macromolecules, 2007, 40, 6658.
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