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PUBLISHED ONLINE: 11 NOVEMBER 2012 | DOI: 10.1038/NNANO.2012.192

An electrically and mechanically self-healing

composite with pressure- and flexion-sensitive
properties for electronic skin applications
Benjamin C-K. Tee1†, Chao Wang2†, Ranulfo Allen2 and Zhenan Bao2 *

Pressure sensitivity and mechanical self-healing are two vital functions of the human skin. A flexible and electrically
conducting material that can sense mechanical forces and yet be able to self-heal repeatably can be of use in emerging
fields such as soft robotics and biomimetic prostheses, but combining all these properties together remains a challenging
task. Here, we describe a composite material composed of a supramolecular organic polymer with embedded nickel
nanostructured microparticles, which shows mechanical and electrical self-healing properties at ambient conditions. We
also show that our material is pressure- and flexion-sensitive, and therefore suitable for electronic skin applications. The
electrical conductivity can be tuned by varying the amount of nickel particles and can reach values as high as 40 S cm21.
On rupture, the initial conductivity is repeatably restored with ∼90% efficiency after 15 s healing time, and the mechanical
properties are completely restored after ∼10 min. The composite resistance varies inversely with applied flexion and tactile
forces. These results demonstrate that natural skin’s repeatable self-healing capability can be mimicked in conductive and
piezoresistive materials, thus potentially expanding the scope of applications of current electronic skin systems.

structural safety12, enabling new biological applications18,19, creating

he remarkable ability of human skin to self-repair allows it
to function as a protective barrier, despite being subjected to long-lived super-hydrophobic coatings20,21, increasing the lifespan
constant damage, while continuously sensing the external of materials and improving environmental sustainability12,16,22.
environment. An ideal biomimetic electronic sensor skin should In spite of the great promise these systems provide, there is one
demonstrate similar mechanical sensing and repeatable self- striking omission in their properties—a lack of high bulk electrical
healing capabilities, the fulfillment of which will simultaneously conductivity in the self-healing materials. This shortcoming limits
require self-healing electrodes (conductivity .1 S cm21) and their potential use in electronic applications. Bielawski and col-
tactile sensors. For practical use, both electrodes and sensors must leagues proposed the use of organometallic polymer thin films
further demonstrate repeatable electrical and mechanical healing as self-healing conductors, but these demonstrated very low conduc-
at room temperature, even at the same damage location, much tivities (1023 S cm21) and required high temperatures and organic
like human skin. Electronic skins are approaching human skin- solvents for cracks to be healed23. White, Moore and co-workers pio-
like properties and performance in terms of mechanical sensing neered the use of microcapsules containing various types of liquid-
and form factor1–9, but the ability to repeatably self-heal has not precursor healing agents for structural healing24,25, and have recently
been demonstrated in electronic skins so far. Such ambient repeata- used capsules filled with various conductive agents or solvents for
ble self-healing and mechanical-sensing capability will be useful in autonomous electrical healing of thin metal films26,27. In these
bioprosthetics and the emerging field of soft robotics10,11, where systems, the local healing agent is depleted after capsule rupture,
robots are made entirely of soft, flexible and conformable materials. having actioned just a single local healing event28. In addition,
In recent years there has been intense research into self-healing these conductive healing agents do not allow simultaneous struc-
materials, but this has largely focused on designing unique stimu- tural healing. To impart conductive healing to thin films, Li and col-
lus-responsive polymer systems for the restoration of mechanical leagues recently used water as the self-healing agent29. However, the
properties. Chen and colleagues used thermally reversible Diels– use of potentially volatile plasticizers as additives or healing agents is
Alder reactions with dynamic covalent bonds to create a tough undesirable in electronic systems because of the risk of contami-
epoxy-like polymer that can structurally heal when heat-treated nation or electronic short circuits arising from escaped additives.
above 120 8C (ref. 12), whereas Burnworth and colleagues showed Furthermore, no self-healing tactile sensors have been reported30,31.
that a metallo-supramolecular polymer can be selectively healed Clearly, combining repeatable self-healing, force sensitivity and high
by converting an optical stimulus to localized heat13. Recently, bulk electrical conductivity remains a challenge.
Leibler and co-workers pioneered a repeatably healable thermo- Here, we show the first repeatable, room-temperature self-
plastic elastomer material based on the use of supramolecular inter- healing electronic sensor skin, using a supramolecular organic–
actions for spontaneous healing14,15. In the area of fault-tolerant soft inorganic composite. A conductivity as high as 40 S cm21 was
electronics, Yuan and colleagues first demonstrated the use of measured for our composite, which is four orders of magnitude
high-strain-capable carbon-nanotube electrodes that can selectively higher than previously reported self-healing conductive organome-
combust or ‘self-clear’ in localized short circuits to maintain con- tallic polymer films23. The composite material is mechanically flex-
stant operation of the dielectric elastomer actuators16,17. These ible, and is capable of sensing tactile and flexion forces. Although
smart material systems are tremendously useful for enhancing there has been substantial research into conductive polymer

Department of Electrical Engineering, Stanford University, David Packard Building, Stanford, California 94305, USA, 2 Department of Chemical Engineering,
Stanford University, 381 North–South Mall, Stanford, California 94305, USA. † These authors contributed equally to this work. *e-mail:


© 2012 Macmillan Publishers Limited. All rights reserved.


a b

C6H13 H H
7 N
C8H15 H H




H15C8 Nanostructured
O µNi particle

H13C6 N N




Figure 1 | Preparation of the self-healing composite. a, Proposed interaction of oligomer chains with mNi particles. Pink lines, linear and branched polymers
form the randomly branched network; blue and purple shapes, urea groups at the ends of the branched polymers form the primary hydrogen bonds between
the polymer chains. b, SEM of the wetting of the oligomer on the preserved nano-corrugated surface of the mNi particles. Scale bar, 1 mm. c, Manufacturing
process flow. Left: an initial randomly branched oligomer network in chloroform is synthesized from Empol 1016 and diethylenetriamine (DETA). Middle: mNi
particles are mixed in to form a homogeneous suspension of the oligomer network. Right: optical image of the compression-moulded self-healing electronic
composite material, demonstrating the flexibility of the material. Scale bar, 1 mm.

composites, this is the first demonstration of a self-healing conduc- (mNi) particles with nanoscale surface features (Fig. 1a). The supra-
tive composite made using a supramolecular polymer host. molecular polymeric hydrogen-bonding network provides the self-
healing function via the large number of weak hydrogen bonds,
Materials fabrication which break preferentially (instead of the stronger covalent bonds)
Figure 1 presents a schematic of material preparation. Our material during a mechanical damage event. These ‘broken’ hydrogen
consists of two components: (i) a supramolecular polymeric hydro- bonds have been shown to dynamically associate and dissociate at
gen-bonding network with a glass transition temperature Tg below room temperature to provide a passive healing mechanism at
room temperature and (ii) chemically compatible micro-nickel the fracture surface14,15,32–35. Additionally, a low Tg enables the


© 2012 Macmillan Publishers Limited. All rights reserved.

polymer chains on fractured interfaces to rearrange, wet and together. Figure 2d describes the time evolution of a typical electrical
diffuse36, thereby allowing healing under ambient temperatures. A healing process. An open circuit was formed following complete
low Tg alone, without hydrogen-bonding sites, does not allow self- severance of the self-healing conductor. As the edges of the compo-
healing. For example, polydimethoxysilane (PDMS) has a Tg of site were brought into contact, the conductivity increased and the
,2100 8C, but due to the lack of reversible polymer bonding, resistance dropped to several kilo-ohms. At this stage, the opposite
PDMS composite systems cannot self-heal. halves of the bifurcated samples were not self-supporting. However,
A mixing process that preserves the nanofeatures of the mNi par- when a gentle pressure was applied for a duration of 15 s, the con-
ticles (Fig. 1b) was used (see Methods) to disperse the mNi particles ductivity returned to close to its initial value, and the composite
into the polymer network, followed by thermal crosslinking with became self-supporting. At release, a very slight increase in resist-
urea (Fig. 1c). mNi particles disperse well in the supramolecular ance was observed initially. This increase can be explained by the
hydrogen-bonding network for two reasons. First, the relatively slight viscoelastic nature of the composite, which slightly increased
large size of the spherical particles leads to a reduction in phase the conduction path distance. However, as the healing progressed,
aggregation, while the nanometre-scale corrugated surface provides the resistance gradually decreased. As electrical conductivity is
an adequate surface area for wetting. Second, the well-known pres- determined by the proximity of the filler particle, the re-association
ence of a thin native oxide layer on the particles37 provides an affi- of the hydrogen bonds within the polymer at room temperature
nity for hydrogen bonds in our synthesized supramolecular enables high electrical healing efficiencies by allowing the particles
oligomers. The presence of reversible hydrogen bonding allows to be closely packed at the healing interface under gentle contact
the composite material to self-adhere (without the use of adhesives) pressures (50 kPa, similar to the pressure applied to a minor cut
to flexible substrates such as oxygen plasma-activated polyethylene wound on skin; Supplementary Fig. S6).
terephthalate (PET) sheets. The laminated composite can withstand We can define the conductive healing efficiency term, helec , as
flexing into various conformations (Supplementary Fig. S1). The the proportion of conductivity restored relative to the original
composite material can be as thin as 600 mm, a limit currently set conductivity. Figure 2e shows that successive cuts at the same
by the compression moulding set-up. location were also healed with high helec , demonstrating excellent
repeatable restoration of electrical performance in our self-healing
Electrical characterization of self-healing composite electronic composite. The duration of contact is an important
Figure 2a shows the composite cross-section morphology with factor in determining helec , indicating that mechanical healing is
increasing nickel volume fraction, obtained using scanning electron essential for conductive healing. A 15 s contact resulted in a
microscopy (SEM) analysis. No phase aggregation of nickel particles nearly full restoration of the electrical properties, with helec reaching
was observed up to 31% volume fraction (75 wt%) of mNi particles. as high as 98% (Supplementary Fig. S7). A battery-powered
To further assess the dispersion of the nickel particles, the variation circuit was constructed to demonstrate further the potential of
of resistance within each sample was measured. The resistance was electromechanical self-healing for electronic circuits (Fig. 2f,
found to be linearly proportional to the distance between the probes Supplementary Movie S1).
(Supplementary Fig. S2), implying good dispersion and a lack of
phase aggregation of nickel particles in the supramolecular host. Mechanical characterization of self-healing composite
The conductivities of each composite were measured using a four- Figure 3a shows that increasing the mNi particle concentration ben-
point probe technique. Six samples for each volume fraction (total eficially strengthens the polymer network and increases the Young’s
54 samples) were measured, and the average volume conductivities modulus and maximum tensile stress that the composite can
are plotted with error bars (standard deviation) in Fig. 2b. At 31% withstand. Mechanical healing efficiencies can be quantified using
volume fraction, the conductivity reached 40 S cm21 (average toughness, because this takes into account the restoration of both
18 S cm21), making this composite suitable for use in electrodes stress and strain (area under the stress–strain curve). We define
in electronic devices38. The nanostructures on the surface of the the mechanical healing efficiency hmech as the proportion of tough-
nickel microparticles are essential for imparting high conductivity, ness restored relative to the original toughness. Figure 3b shows a
because they facilitate interparticle quantum tunnelling by enhan- representative stress–strain curves for a 31% nickel volume fraction
cing the local electric field at the asperities of the surface41. As composite under different healing conditions. From these curves,
shown in Fig. 2b, the conductivity of the composite with smooth hmech was found to be a function of healing time. The longer the
nickel microparticles remained below 1 × 1026 S cm21, even at healing time, the higher the value of hmech , as hydrogen bonds con-
high loading (Supplementary Fig. S3). tinue to re-associate with one another between the interfaces
The trend of an increase in volume conductivity as a function of (Fig. 3b). Even at the highest nickel volume fraction of 31%, the
nickel volume ratio agrees well with percolation theory39, which toughness recovery of the composite increased by a factor of three
describes an exponential increase above the percolation threshold to 41% after a healing time of 10 min, compared to 13% for
(solid red line in Fig. 2b; for derivation see Supplementary 5 min, at room temperature. The partially healed composite broke
Fig. S4). The percolation threshold was found to be 0.15 volume at the site of initial fracture, possibly due to remnant defects.
fraction of the mNi particles, which is close to the ideal percolation However, full restoration of the toughness was achieved at a gentle
threshold value of 0.16 for spherical particles. Below the percola- heating temperature of 50 8C for 10 min and the fully healed
tion threshold, the conductivities were considerably lower and rela- sample fractured at a different site upon tensile testing. The tough-
tively constant, which also agrees with percolation theory40. ness recovery was higher than that of the original composite, which
The composite material displayed the typical linear, non-hysteretic is a phenomenon that has been observed in other supramolecular
current–voltage characteristics expected of a good electrical conductor self-healing polymer systems13. For superficial damage, such as a
(Supplementary Fig. S5). Figure 2c shows that the conductive compo- scratch, the scar at the damaged interface could be fully healed
site can be used in conducting wires in an electronic circuit for devices (Fig. 3c) after 5 min at 50 8C.
such as light-emitting diodes (LEDs). A turn-on resistance of 200 V Supplementary Fig. S8 presents a comparison of the mechanical
was observed, as indicated by the linear region of the current–voltage healing efficiencies of a different nickel volume fraction using three
curve (due to parasitic resistance from two thin 50-mm-diameter stain- samples at each composition. As the nickel particle concentration
less steel wires used as the flexible leads to the voltage source meter). increased, hmech decreased, because part of the surface area of the
To investigate electrical healing, the conductor was completely fractured interface was now occupied by nickel particles. Both
bifurcated using a scalpel and the two fractured surfaces brought mechanical and electrical healing were also negatively affected if


© 2012 Macmillan Publishers Limited. All rights reserved.


a 75% μNi b 102

Nanostructured μNi
101 Smooth spherical Ni particles
Percolation theory fit


Conductivity (S cm−1)

Increasing conductivity
50% μNi 1 μm



10−6 1 μm

30% μNi 10−7


0.05 0.10 0.15 0.20 0.25 0.30
Ni volume fraction

c d
3.0 109

Resistance (Ω)
Current (mA)

1.0 103
Pressed Released

−0.5 10−1
−1 0 1 2 3 0 20 40 60 80 100
Voltage (V) Time (s)

e 109 f
1st cut 2nd cut 3rd cut
Resistance (Ω)

1 2



10−1 3 4
0 200 400 600 800 1,000 1,200 1,400 1,600
Time (s)

Figure 2 | Electrical and conductive healing efficiency characterization of self-healing composite. a, Cross-sectional SEM images of composite materials
showing decreasing particle separation distance as mNi concentration increases. No aggregation was observed even at a high mNi loading of 31 vol% (75 wt%).
Scale bar, 20 mm for all images. b, Volume electrical conductivity as a function of mNi particle concentration from four-point probe measurements. Error bars
represent standard deviation from six samples per volume fraction (Supplementary Table S2). Inset: SEM images of the nanoflower-like surface of the mNi
(top) and the comparatively smooth surface of comparison spherical nickel particles (bottom). The microparticles (as from the manufacturer) have a small
size distribution around a diameter of 2–5 mm. Red line represents the best-fit line for conductivity above percolation threshold using percolation theory
(Supplementary Fig. S4). c, Current–voltage curve of a commercial LED using self-healing electrically conductive composite wire moulded into an ‘S’ shape.
Inset: image of circuit taken at 2.5 V (scale bar, 10 mm). d, Time evolution of the electrical healing process using resistance measurements for 15 s healing
time at room temperature. e, Repeated electrical healing for three cuts at the same severed location. f, Demonstration of the healing process for a conductive
composite with an LED in series with a self-healing electrical conductor. 1, undamaged conductor; 2, completely severed conductor (open circuit); 3, electrical
healing (inset shows conductor being self-supporting); 4, healed film being flexed to show its mechanical strength and flexibility after only 5 min at room
temperature (Supplementary Movie S1).


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a b c
15 vol% µNi
100 23 vol% µNi 100
31 vol% µNi
Tensile stress (MPa)

Tensile stress (MPa)

x xx

10−1 10−1
2 min RT
5 min RT
10 min RT
5 min 50 °C
10−2 10−2
0 20 40 60 80 100 0 10 20 30 40 Damaged Healed
Strain (%) Strain (%)

Figure 3 | Mechanical and healing efficiency characterization of the self-healing composite. a, Tensile measurements of composites with different nickel
volume ratios. b, Typical stress–strain curves of original and healed samples for different healing times and temperature for 31 vol% mNi composite. RT, room
temperature. c, Optical microscope image of damaged sample and complete scar healing for 31 vol% mNi composite. Scale bar, 1 mm.

the interfaces were left in ambient air for over 2 min free-standing film, one side is compressed but the other side
(Supplementary Fig. S9). This can be attributed to a loss of hydro- is stretched.
gen-bonding ability due to absorption of moisture from the ambient Similarly, a tactile sensor could be completely constructed from
air14. This suggests that hydrogen bonding is essential for the self- our self-healing materials by using a parallel-plate structure with
healing mechanism. the piezoresistive composite sandwiched between layers of the con-
To further study the effect of hydrogen-bonding density on ductive composite. The piezoresistive response of this arrangement
electrical and mechanical healing, a control polymer, composite A, is shown in Fig. 4b. The increase in conductivity is exponentially
was synthesized to have similar mechanical properties and Tg , but dependent on stress, similar to other piezoresistive sensors based
significantly fewer hydrogen-bonding sites (Supplementary on carbon black42. Although such dynamically healing polymer
Fig. S10). This was achieved by using oxalyl chloride instead of systems typically suffer from a viscoelastic effect (creep), which
urea, followed by loading the polymer with nanostructured mNi affects the time response to mechanical forces, the addition of
particles to obtain similar electrical conductivities. Composite A elec- nickel particles significantly reduces the viscous modulus, and the
trically healed to only 7% of its original value, whereas the original piezoresistive sensors can track mechanical loads without showing
polymer composite healed to 90%, indicating the importance of significant relaxation times, as shown by the tracking of various
proper tuning of the number of hydrogen-bonding sites and strength. ramped loads in Supplementary Fig. S13. The flexion and tactile
We also synthesized another control polymer, composite B, in which sensors were then characterized at temperatures up to 40 8C
the hydrogen-bonding density was lowered by decreasing the (Supplementary Fig. S14). The sensitivities increased as a result of
amount of urea (Supplementary Fig. S11). Composite B demon- thermal expansion and slight decrease in modulus at elevated
strated reduced mechanical and electrical healing efficiencies, temperatures.
further indicating that hydrogen bonding was driving the healing. As a step towards achieving the goal of using our self-healing
If there is no mechanical healing at the interface, the conductivity composite as electronic skin, we integrated the tactile and flexion
between the fractured pieces will not be effectively restored once sensors into a humanoid mannequin (Fig. 4c). The sensors were
the pressure is released. For example, when a polymer such as located on the palm and elbow joint in the path of electric circuits,
PDMS without hydrogen bonding was used, electrical and mechan- using LEDs as indicators of mechanical forces. We demonstrated the
ical self-healing were not observed (Supplementary Fig. S12). ability to detect varying pressures and changes in the positions of
the limbs (proprioception; Fig. 4d,e, Supplementary Movie S2).
Self-healing composite as electronic skin The sensors modulated current flow through the sensor circuit by
Using lower mNi concentrations, with the particles spaced further means of changes in their resistance depending on pressure and
apart, we realized self-healing piezoresistive sensors. The larger flexion angle of the limb. This in turn changed the intensity of
particle spacing allows a more significant change in resistance as the respective LEDs depending on the pressure and flexion angle.
the compressive forces bring the mNi particles closer within the The flexibility of the material is clearly advantageous for detecting
polymer matrix. Such behaviour has been observed with other the position of movable joints.
non-self-healing composite systems, but here we apply it to a supra-
molecular composite with dynamic healing. At mNi concentrations Conclusions
near the percolation threshold (15 vol%), the composite material In summary, we have demonstrated the first ambient repeatable
can be used to sense mechanical forces such as a flexion (Fig. 4a) self-healing electronic composite material that can be used to
and a tactile pressure (Fig. 4b). When the composite material was sense mechanical forces. Although the Tg of the polymer is
flexed, compressive stresses built up at the inner curvature. The –20 8C, the addition of nanostructured mNi particles with nano-
mNi particles therefore approached closer to one another and structured surfaces significantly enhances the mechanical properties
thereby reduced the composite’s resistance. The greater the flexion and raises the Tg to 10 8C (Supplementary Fig. S15). Furthermore,
angle u (defined in Fig. 4a), the lower the resistance. The change mNi-composite samples have healing efficiencies that decrease
in resistance was repeatable both in forward (increasing u) and with surface exposure time, indicative that healing is driven by
reverse (decreasing u) directions. Electronic skins are often fabri- hydrogen bonding re-association between the cut surfaces.
cated by mounting sensors or circuitry on flexible substrates such Although the Tg of the composite sets the lower bound of the oper-
as PET sheets. Our sensor was mounted on 50-mm-thick PET ating temperature range for efficient healing, as the polymer chains
and a similar trend in response was found. The slight differences are less mobile at or below Tg , this potential limitation can be
can be attributed to the different deformation modes taking place overcome by tuning the mechanical properties of the supramole-
on a free-standing film versus a mounted film—in the case of a cular binder by controlling its crosslinking density and/or using


© 2012 Macmillan Publishers Limited. All rights reserved.


a b
1.0 Free-standing forward
Free-standing backward
Self-adhered PET forward
Self-adhered on PET backward
Relative resistance change


Resistance (Ω)

Force y = 104.7−6.6x
y = 1.0 − 0.01θ
102 Self-healing Self-healing
0.2 conductor tactile sensor

y = 1.0 − 0.03θ + 2 × 10−4θ2

0 10 20 30 40 50 60 70 80 0.0 0.1 0.2 0.3 0.4
Flexion angle θ (deg) Pressure (MPa)

c d


V 3V


Relaxed Flexed

No pressure ~50 kPa ~1 MPa ~2 MPa

Figure 4 | Characterization and application of the self-healing electronic sensor skin. a, Flexion sensor electrical response in both free-standing and
self-adhered modes on 50-mm-thick PET substrates. Inset: definition of flexion angle u. Equation represents least-squares fit (dotted line) relationship of
resistance and flexion angle. b, Tactile sensor response at increasing peak pressure values (inset: sensor schematic). Equation represents least-squares fit
relationship (dotted line) of resistance and applied pressure. c, Self-healing flexion and tactile sensor circuit schematic and mounting on a fully articulated
wooden mannequin. See Supplementary Movie S2 for a real-time demonstration. A flexion sensor was mounted on the inner elbow region. A tactile sensor
was mounted on the palm. LEDs (centre of body and eye region) are used to transduce the mechanical deformation into visible analogue light-intensity
outputs. d, Flexion sensor circuit demonstration: LED ‘eyes’ light up after the elbow is bent. The intensity increases with increasing elbow flexion. e, Tactile
sensor circuit demonstration. LED intensity responds as a function of increasing tactile pressure.

multiple composite materials tuned to a different temperature functional lifespan of the skin. Because they are electrically conduct-
operating range. ing, we can also effectively detect a severe damage event through a
Our self-healing composite is the first bulk conductive composite change in electrical resistance, and repair the skin by simply con-
that has an organic supramolecular polymer as host and inorganic tacting the fractured interfaces. The self-healing electronic skin
metal particles with nanostructured morphology as fillers. The demonstrated here represents just one possible sensing functionality
rate of electrical healing is rapid (within 15 s). These functional achievable with this supramolecular polymer system. We anticipate
self-healing electronic sensor skins potentially enhance the that other self-healing polymer systems might also benefit from such


© 2012 Macmillan Publishers Limited. All rights reserved.

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Acknowledgements and requests for materials should be addressed to Z.B.
The authors acknowledge funding support from the Air Force Office of Scientific Research
(grant no. FA9550-12-1-01906). B.C-K.T. acknowledges support from the National Science Competing financial interests
Scholarship (NSS) from the Agency for Science, Technology and Research (A*STAR). R.A. The authors declare no competing financial interests.


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