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Biobased, self-healable, high strength rubber with

Cite this: DOI: 10.1039/c7nr05011a
tunicate cellulose nanocrystals
Liming Cao,a Daosheng Yuan,a Chuanhui Xu*a,b and Yukun Chen *a

Received 11th July 2017,
Accepted 13th September 2017
DOI: 10.1039/c7nr05011a
rsc.li/nanoscale
Cellulose nanocrystals represent a promising and environmentally friendly reinforcing nanoller for poly-
mers, especially for rubbers and elastomers. Here, a simple approach via latex mixing is used to fabricate
biobased, healable rubber with high strength based on epoxidized natural rubber (ENR). Tunicate cellulose
nanocrystals (t-CNs) isolated from marine biomass with a high aspect ratio are used to improve both
mechanical properties and self-healing behavior of the material. By introducing dynamic hydrogen bond
supramolecular networks between oxygenous groups of ENR and hydroxyl groups on the t-CN surface,
together with chain interdiusion in permanently but slightly cross-linked rubber, self-healing and
mechanical properties are facilitated signicantly in the resulting materials. Macroscopic tensile healing
behavior and microscopic morphology analyses are carried out to evaluate the performance of the
materials. Both t-CN content and healing time have signicant inuence on healing behavior. The results
indicate that a synergistic eect between molecular interdiusion and dynamic hydrogen bond supramo-
lecular networks leads to the improved self-healing behavior.

1. Introduction products during service often lead to mechanical malfunctions

Cellulose nanocrystals (CNs) are a class of highly crystalline
and rod-like nanofillers. Due to their excellent mechanical pro-
perties, biocompatibility, low cost and rich surface chemistry,
CNs represent a promising and environmentally friendly
alternative to conventional reinforcement nanofillers, such
as carbon black, silica, glass fibres, etc., used in polymer
nanocomposites.16 Since the first publication related to the
use of CNs as the reinforcing filler in polymer-based nano-
composites by Favier et al.,7 there has been growing interest in
the field of nanocomposites due to their appealing intrinsic
properties such as nanoscale dimensions, unique morphology,
high surface area, etc.811
Rubbers are a technologically critical class of materials which
could recover from enormous extensibility to their original
shape and dimensions on release of stress.1214 Various studies
have been carried out on using CNs to reinforce rubbers. The
results showed that low modulus rubbers could be eciently
reinforced with introduction of CNs isolated from a variety of
biosources (e.g., cotton, wheat straw, sisal, or tunicates).1518
However, the formation and propagation of crack of rubber
a
Lab of Advanced Elastomer, South China University of Technology,
Guangzhou 510640, China. E-mail: cyk@scut.edu.cn
b
School of Chemistry and Chemical Engineering, Guangxi University,
Nanning 530004, China. E-mail: xuhuiyee@gxu.edu.cn
Electronic supplementary information (ESI) available. See DOI: 10.1039/
c7nr05011a
until the material eventually fails. To address this problem and
greatly extend lifetime and functionality of rubber based
products, self-healing rubbers have been developed and have
attracted significant attention in recent years.12,19,20 Various
approaches including reversible covalent bonding, H-bonding,
supramolecular chemistry, stacking, ionic interactions, etc.
have been explored to access such capacity.2124
In 2008, Leibler et al. described a supramolecular rubber
with multiple hydrogen bonds based on small molecules,
which can be simply repaired at room temperature and can be
repeated many times.12 This pioneering work provided decisive
motivation for developing new self-healing rubbers. Recently,
Das et al.25 converted bromobutyl rubber (BIIR) to a healable
rubber by introducing ionic interaction via imidazolium modi-
fication. Hernandez et al.26,27 turned cured natural rubber
(NR) into a self-healing material based on the dynamic charac-
ter of di- and polysulfide bonds in covalently cross-linked
rubbers. We also fabricated a natural rubber based self-
healing material via a reversible ionic supramolecular
network,28,29 which showed high healing eciency with a
short healing time. Other researchers also studied healing be-
havior of rubbers.3033 However, the research mentioned above
focused on either biobased rubbers with limited strength and
external stimuli are required for healing, or the materials used
are non-biobased. From this point of view, focusing our eorts
on the development of biobased rubber with excellent strength
and high healing eciency without external stimuli seems to
be a beneficial choice.

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Epoxidized natural rubber (ENR) is a derivative derived
from NR and retains most of the properties of NR. Norvez
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et al.34 have recently reported that the chain relaxation process
plays an important role in the adhesion or healing properties
in slightly cross-linked ENR, due to the molecular mobility of
the free chain ends which allows interpenetration. In addition,
hydroxyl groups and carboxyl groups could be formed via
some epoxide ring-opening during the synthesis of ENR.35,36
As a consequence, more intermolecular hydrogen bonds
formed at the interface of rubber joints, which gives ENR auto-
nomous self-healing capacity. Rahman et al.21,37 explored self-
healing behavior based on ENR via T-peel and ballistic tests,
and found that both molecular interdiusion and hydrogen
bonds contributed to the self-healing of ENR. However, the
slight cross-linking density leads to poor mechanical pro-
perties, which are of limited practical application.
Therefore, in this study, we detail the method of using tuni-
cate cellulose nanocrystals (t-CNs) as an eective way to
improve mechanical properties of self-healable ENR based
elastomers. In our previous study, we have demonstrated that
hydrogen bonds formed between oxygenous groups of ENR
and hydroxyl groups of t-CNs, which play an important role in
reinforcing ENR.38 In addition, the hydrogen bond supramole-
cular networks have been recognized as an eective way to
build self-healing materials. Therefore, the incorporation of
t-CNs into the ENR matrix may be beneficial for the self-
healing behavior of the resulting materials. It is expected that
the hydrogen bond supramolecular network between the
rubber and filler will bring an excellent self-healing behavior
and outstanding mechanical properties to ENR based
elastomers.
2. Experimental section
2.1. Materials
ENR latex with an epoxidation degree of 40% and a solid
content of 25% was kindly supplied by the Agricultural
Products Processing Research Institute, Chinese Academy of
Tropical Agricultural Science, Zhanjiang, China. Tunicate,
which was used for isolating CNs, was obtained from Weihai,
China. Dicumyl peroxide (DCP) was purchased from
Sinopharm Chemical Reagent CO. Ltd (China), and was
recrystallized from alcohol before use.
2.2. Preparation of ENR/t-CN nanocomposites
Cellulose nanocrystals were isolated from mantles of sea tuni-
cates after hydrolysis with sulfuric acid, and abbreviated as
t-CNs. The detailed procedure for extracting t-CNs was carried
out according to previous publication.38 For fabricating nano-
composites, a desired amount of t-CN suspension was added
into the ENR latex and stirred for 30 min. Then the mixture
was co-coagulated by adding alcohol as the flocculating agent.
The co-coagulated compounds were washed with de-ionized
water several times until neutral. After that, the compounds
were dried at 50 C overnight until they acquired constant
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weight. Then the dried compounds were compounded with
DCP (0.5 phr according to 100 phr ENR matrix to obtain
slightly cross-linked rubbers21) through a two-roll mill and
subjected to compression molded at 140 C for 1 h. A series of
nanocomposite films with a thickness of around 0.5 mm were
prepared and abbreviated as ENR/t-CNs-x, where x is phr of
t-CNs in the nanocomposites ( per hundred of rubber).
2.3 Characterization methods
Fourier transform infrared (FT-IR) spectra was recorded on a
Tensor 27 FT-IR spectrometer (Bruker, Germany) for neat ENR
and nanocomposites. The specimens were placed flat on the
crystal surface. Each of the spectra was collected over 32 scans
with a resolution of 4 cm1 in the range of 6004000 cm1.
The background spectra were recorded with Ge crystals in
contact with air in the absence of the specimen.
Transmission electron microscopy (TEM) was used to
observe the dispersion state of t-CNs in the ENR matrix.
Specimens were cryo-microtomed at 80 C using a Leica EM
UC6 equipment. Images were recorded without any prior stain-
ing using a JEM-2100F operating at 200 kV.
The morphology and dimensions of the t-CNs were charac-
terized via Atomic Force Microscopy (AFM) and Scanning
Electron Microscopy (SEM). AFM was carried out by using a
Multimode 8 (Bruker, Germany) in a tapping mode. A drop of
the t-CNC suspension was deposited on the freshly cleaved
mica substrates and dried overnight under room temperature.
The dimensions of t-CNs were estimated from 50 measure-
ments using the associated software. SEM was conducted on a
Merlin (Zeiss, Germany) apparatus, and a drop of the t-CN sus-
pension was deposited on a microslide and dried overnight,
and then coated with a thin gold layer before observation. In
addition, SEM was also conducted to observe the cut line of
the healed sample, and the healed sample was stretched
slightly and then coated with a thin gold layer for observation.
An optical Microscope (DM2500 P, Leica, Germany) was
used to observe the healing behavior of the cut line. Two
dierent surfaces were observed, one is the surface of the
contact area, and the other is the cross section of the contact
area.
Dynamic mechanical analysis (DMA) was conducted on a
DMA 242 C (NETZSCH, Germany) with a film in tension mode
fixture. Rectangular samples of 4 mm 0.5 mm cross section
and about 8 mm in length were used for tests. Heating ramps
were applied at 3 C min1 in the temperature range from
60 C to +30 C at a frequency of 1 Hz.
Dierential scanning calorimetry (DSC) measurements were
carried out on a NETZSCH DSC 204 F1 (Germany) under a
nitrogen atmosphere. Two heating ramps were performed in
temperature range of 50 to 20 C at a scanning rate of
10 K min1, and the glass transition temperature (Tg) was
determined from the second heating cycle.
Equilibrium swelling experiments were employed to deter-
mine the cross-link density of the resultant materials. Three
weighed test pieces of the specimen (m0) were immersed in
toluene at ambient temperature in sealed dark vials. Then, the
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swollen samples were periodically taken out of toluene and
wiped with tissue paper to remove the excess solvent and
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immediately weighed (w1) on an analytical balance. The weight
measurements were continued until the samples achieved
constant weight (about 3 days). The cross-link density () was
calculated from the FloryRehner equation,38,39
ln1  Vr Vr xVr 2
ve   
Vr
V1 Vr 
1=3
2 Eoriginal
where
mr
r
Vr m mr
s
s r
V1 and x are the molar volume and interaction parameter of the
solvent (V1 = 106.2 cm3 mol1, x = 0.39, for toluene), respect-
ively. mr and r are the weight and density of rubber (for ENR,
d = 0.96 g cm3), and ms and s are the weight and density of
the solvent (for toluene, s = 0.865 g cm3), respectively.
Tensile tests were performed at ambient temperature from
dumbbell-shaped specimens of 4 mm width, 20 mm gauge
length, and about 0.5 mm thickness, based on ASTM D638-10.
A tensile testing machine UCAN Series UT-2080 (Taiwan)
was used at a constant crosshead displacement rate of
500 mm min1, and at least three samples were tested per
sample. Tensile tests were used both to characterize the mech-
anical properties and to evaluate their self-healing behavior.
For self-healing tests, dumbbell-shaped samples were cut in
the middle of the gauge length with a clean razor blade, and
the two cut surfaces were brought back in contact by hand
Fig. 1 (a) Schematic illustration of the method of isolating t-CNs; (b) AFM image; and (c) SEM image of the obtained t-CNs.
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after waiting for a certain time. Once the two cut surfaces were
brought together, the samples were allowed to autonomous
heal at ambient temperature without any external stimulus.
After autonomous healing for a certain time, the healed
samples were subsequently tested on the test machine with
the same crosshead rate. The healing eciency was calcu-
lated from the formula
1
Ehealed
%  100 3
where Eoriginal and Ehealed correspond to the tensile energy (E)
for the original and healed samples, respectively. And they
were measured as the area below the stressstrain curves.
2
3. Results and discussion
3.1. Characterization of ENR based nanocomposites
For this study, we chose to use CNs isolated from a sea animal
known as tunicates (styela clava) to reinforce ENR and facilitate
self-healing behavior. CNs from tunicates (t-CNs) show a high
aspect ratio (length (l)/diameter (d )) of about 80 and high
tensile modulus up to 140 GPa.40,41 The t-CNs were obtained
via sulfuric acid hydrolysis of the tunicate mantles (Fig. 1a),
and as a consequence the t-CN surface is decorated with nega-
tively charged sulfate groups, which makes the t-CNs form an
aqueous suspension with high stability (Fig. S1). Atomic
Force Microscopy (AFM) and Scanning Electron Microscopy
(SEM) (Fig. 1b and c) show that these isolated t-CNs have
dimensions of 1020 nm in diameter and 500 nm to 2 m in
length, and with an aspect ratio of about 75. These dimensions
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are similar to those isolated from tunicate mantles previously
reported.41,42
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To maximize the reinforcing eciency, homogeneous dis-
persion of fillers within the matrix is desirable. The most
eective way to achieve this would be to use a common solvent
for both the matrix and filler that is subsequently removed to
produce a homogeneous blend. Fig. 2 shows the schematic
fabrication process of ENR nanocomposites with a supramole-
cular network via a facile aqueous mixing method. The abun-
dant hydroxyl groups are expected to establish hydrogen bonds
with oxygenous groups (e.g., epoxides, carboxyls and hydroxyl)
of ENR to form a supramolecular network in the biobased
rubber nanocomposites (Fig. 2c).
The dispersion of t-CNs in the ENR matrix is evaluated by
TEM. Fig. 3 illustrates TEM images of nanocomposites with 10
phr and 20 phr t-CNs, respectively. It can be seen that homo-
geneous dispersion of t-CNs without any obvious aggregates is
Fig. 2 (a) Molecular structure of the used materials; (b) processing method of the nanocomposites; (c) schematic illustration of the nanocomposite
structure containing both hydrogen bonds and covalent cross-links.
Fig. 3 TEM images of (a) ENR/t-CNs-10; (b) ENR/t-CNs-20 nanocomposites.
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observed in the ENR/t-CNs-10 nanocomposite. However,
several large aggregates are observed with 20 phr t-CN incorpo-
ration; this inevitable aggregation is mainly ascribed to the
massive hydroxyl groups on the t-CN surface.
3.2 Characterization of supramolecular interaction
To confirm the hydrogen bond interaction and the formation of
a supramolecular structure in the nanocomposites, FTIR ana-
lyses of neat ENR and the nanocomposites were conducted. As
shown in Fig. 4a, obvious vibrational modes of ENR are
observed in the spectrum of neat ENR, such as absorption
bands at 1257 and 870 cm1 corresponding to the stretching
vibrations of COC. The broad peak in the range of
32003500 cm1 is associated with the presence of hydroxyl
groups. In addition, the small peak around 1725 cm1 indicates
the presence of the CvO group. Several articles have reported
that epoxide ring-opened products (i.e., CvO, OH, etc.) could
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Fig. 4 (a) FTIR spectra of neat ENR and nanocomposites; (b) FTIR spectra of neat ENR and nanocomposites in the carbonyl (left) and epoxy (right)
regions; (c) the hydrogen bond fraction of the nanocomposites; and (d) the hysteresis loops of neat ENR and nanocomposites with 10 phr and 20
phr t-CNs during loading-unloading cycles.
form during the synthesis of ENR due to the high temperature,
low pH, or longer synthesis time.35,36 The ring-opened products,
which may enhance the intermolecular hydrogen bonds, are
beneficial for the self-healing behavior of ENR.21
It is worth noting that with the incorporation of t-CNs, the
peak around 3450 cm1 corresponding to hydroxyl groups in
ENR is consistently decreased with increasing t-CN content.
Moreover, the bands around 1725 and 1257 cm1 corres-
ponding to the stretching vibration of CvO and COC on
ENR chains shift to a lower wavenumber with increasing t-CN
content (Fig. 4b), indicating the formation of dynamic hydro-
gen bonds between the surface hydroxyl groups of t-CNs and
oxygenous groups of ENR (i.e., epoxides, hydroxyls, and carbo-
nyls), as depicted in Fig. 2c.38
The quantity of the hydrogen bond interactions could be
represented by the hydrogen bond fraction (FH-bond) and
calculated from the following equation:43,44
AH =rH=f
FHbond
AH =rH=f Af
where AH and Af are the peak areas of H-bonded and free com-
ponents of oxygenous groups, respectively, and rH/f is the
specific absorption ratio of the above two bands.
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Considering that the epoxy groups dominate the oxygenous
groups on ENR chains, we intend to use the position change
of epoxy groups to calculate the hydrogen bond interactions.
However, as shown in Fig. 4b, the position change between the
free and H-bonded epoxy groups is not significant, which
makes it dicult for multi-peak Gauss fitting. Therefore, in
this work, we intend to take the position at 1248 and
1257 cm1 as the H-bonded and free epoxy groups, respect-
ively, and the semi-quantitative calculation of the FH-bond
could be obtained through the simplified form of eqn (4):
IH
FHbond 5
IH If
where IH and If are the intensities of H-bonded and free com-
ponents of epoxy groups, respectively. As shown in Fig. 4c,
with increasing t-CN concentration, the FH-bond value gradually
increased from 0.33 for ENR/t-CNs-5 to 0.63 for ENR/t-CNs-20.
This indicates the stronger hydrogen bonds with more t-CN
4
concentration in the nanocomposites. It should be noted that
the increase from 15 to 20 phr t-CNs slowed down compared
with lower t-CN concentrations, which might be due to the
slight agglomeration of t-CNs within the matrix, as shown in
Fig. 3.
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To further characterize the reversibility and recovery of the
dynamic hydrogen bonds in the nanocomposites, cyclic tensile
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tests of neat ENR and nanocomposites with 10 phr and 20 phr
t-CNs were performed. As shown in Fig. 4d, all the samples
exhibit typical hysteresis and permanent residual strain
behavior.25 It is worthwhile to mention that neat ENR shows a
considerable residual strain of 21% due to the physical
entanglements of ENR chains, which is higher than fully
cross-linked rubbers.45,46 Physical entanglements ascribed to
the slight cross-linking are beneficial for the chain interdiu-
sion process, which is important for the self-healing of the
materials.21,34 In addition, both residual strain and hysteresis
increased significantly with the incorporation of t-CNs, which
indicates that more energy is dissipated during the loading-
unloading cycle as a result of the rapture-reformation of the
dynamic hydrogen bond network. This demonstrates that the
stronger supramolecular network was constructed by dierent
types of hydrogen bonds with the incorporation of t-CNs.
Fig. 5 shows the calculated cross-link density based on
swelling experiments for neat ENR and nanocomposites.
Fig. 5 Cross-link density of neat ENR and the nanocomposites with
various t-CN contents.
Fig. 6 (a) Heat enthalpy curves of the nanocomposites as recorded by DSC and (b) tan
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Strong hydrogen bonds formed between ENR chains and t-CNs
as discussed above, which kept the filler-filler and filler-rubber
chains bound together strongly and made it dicult for the
solvent to permeate into the matrix. A higher t-CN content in
the nanocomposites increased the quantity of hydrogen
bonds. Therefore, increased crosslink density was observed
with higher t-CN content.
The increased cross-link density that resulted from the
massive hydrogen bonding network between the filler and
rubber may lead to an increase in glass transition temperature
(Tg). Therefore, DSC and DMA measurements were conducted,
and the results are shown in Fig. 6. It should be noted that the
cross-linking agents used in neat ENR and the nano-
composites were kept at 0.5 phr (according to per hundred of
rubber matrix), which means that the covalent cross-linking
density is almost the same in all the samples. The glass tran-
sition temperature (Tg) of the nanocomposites increased with
the incorporation of t-CNs. As there is not much change in the
covalent cross-linking density, the increase in total cross-
linking density mainly comes from the physical cross-linking
density (mainly attributed to hydrogen bonds between the
rubber and filler), which indicates the improved hydrogen
bonds between the rubber and filler. In addition, the tan
peak intensity consistently decreased with higher t-CN
content, which suggested a continuous decrease in chain
mobility ascribed to the supramolecular interaction between
the rubber and filler.
All the above mentioned results indicate the successful con-
struction of hydrogen bond supramolecular networks within
the nanocomposites, due to the strong interactions between
the hydroxyl groups on the t-CN surface and oxygenous groups
on ENR molecular chains. The supramolecular structure will
play an important role in improving the mechanical properties
and self-healing behavior of ENR based nanocomposites.
3.3. Tensile testing analysis
A series of stressstrain tests were carried out to examine the
reinforcement of the t-CNs in the ENR matrix. Fig. 7 and
Table 1 show the typical stressstrain curves and mechanical
temperature dependence of selected nanocomposites.
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Fig. 8 Digital images of the twisting, bending and stretching shapes of

the healed sample with 20 phr t-CNs. The cut surfaces were brought
Fig. 7 Stressstrain curves of ENR nanocomposites with dierent t-CN together by hand without waiting after damage, and then autonomous
loadings. healing at ambient temperature for 1 h without any external stimulus.

Table 1 Summary of mechanical properties of neat ENR and the

nanocomposites

Tensile Stress at Tensile

strength Strain at 100% strain modulus
Sample (MPa) break (%) (MPa) (E, MPa)

ENR 1.15 0.08 306 15 0.59 0.04 2.40 0.12

ENR/t-CNs-5 2.03 0.11 253 13 0.88 0.06 4.62 0.10
ENR/t-CNs-10 2.87 0.13 216 11 1.28 0.06 8.54 0.18
ENR/t-CNs-15 3.78 0.15 206 10 1.73 0.05 12.71 0.21
ENR/t-CNs-20 4.04 0.18 198 12 2.21 0.09 16.30 0.25

properties, respectively. Increasing t-CN content resulted in a

dramatic increase in tensile strength and tensile modulus
(E, 5% strain) (from 1.15 and 2.40 MPa of neat matrix to 4.04
and 16.30 MPa for ENR/t-CNs-20, respectively), along with a
Fig. 9 Optical microscopy images of self-healing behavior: (a) the top
slight decrease in elongation at break, which are consistent surface and (b) the cross-section of neat ENR; (c) the top surface and (d)
with the mechanical reinforcement of CNs in the polymer the cross-section of nanocomposites with 20 phr t-CNs. All samples
matrix.9,47 The high reinforcement of t-CNs is mainly ascribed were healed under ambient conditions for 24 h. Scale bars: 40 m.
to the formation of a sti, percolating network of t-CNs and
strong hydrogen bonds between the rubber and filler.9,38

nanocomposite ascribed to the hydrogen bonds between the

3.4. Tensile self-healing study
The self-healing behavior of nanocomposites with dierent
shapes after healing is demonstrated in Fig. 8. As can be seen,
the healed sample did not fracture at the joint position even
under strong twisting, bending, or stretching. As for neat ENR
without t-CNs, it stretched to fracture at a lower extension with
the same healing conditions (ESI Video).
The self-healing behavior of the junction position was eval-
uated via optical microscope analysis, as shown in Fig. 9. From
the top surface observation, more visible crack between cut
pieces of neat ENR (Fig. 9a) as compared with the nano-
composite (Fig. 9c) can be observed. And only partial self-
healing was achieved in neat ENR as shown in the cross-
section image in Fig. 9b, however, the crack of the nano-
composite from the cross-section was almost indiscernible in
Fig. 9d, confirming the improved self-healing behavior of the
rubber and filler.
SEM images of the cut line after healing for 24 h under stretch-
ing of ENR/t-CNs-20 are shown in Fig. 10. A well-fused weld line
with some wrinkle marks is visible between the two joint sections
of the cut sample. Notably, no macrocracks are observed around
the cut line even under stretching, indicating the excellent self-
healing behavior of the obtained nanocomposites.
In this system, we envisioned that slight cross-linking and
reversible hydrogen bond supramolecular networks in the
nanocomposites should aord self-healing behavior. Indeed,
all the samples exhibit spontaneous self-healing behavior at
room temperature without external stimuli such as heat,
pressure, irradiation, etc. For healed materials with various
healing times, stressstrain curves follow closely the shapes of
the original uncut sample, and longer healing time leads to
better healing eciency, as shown in Fig. 11a and b. With

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Fig. 10 SEM images showing the cut line under stretching after self-healing for 24 h at room temperature of ENR/t-CNs-20.

Fig. 11 (a) Typical stressstrain curves of ENR/t-CNs-20 nanocomposites before and after healing for various times at room temperature; (b) com-
parison of the self-healing eciencies of ENR/t-CNs-20 for dierent healing times; (c) initial tensile behavior of a cut sample healed for 30 min is
compared with the stressstrain curve of the pristine sample.

shorter healing times, fewer bridges across the interface are
formed and the sample fractured at low extension, showing a
lower healing eciency. Notably, the initial modulus and
stress at 20% strain recovered almost quantitatively after only
30 min of healing time (Fig. 11c).
To quantify the healing eciency, mechanical properties of
samples with various t-CN contents were explored by tensile
testing, as shown in Fig. S3 (ESI). The healing eciency was
calculated from the tensile energy before and after healing,
which is shown in Fig. 12. As can be seen, the healing
eciency improved with increasing t-CN content. A healing
eciency of up to 86% is obtained for ENR/t-CNs-20, as com-
pared with 48% for neat ENR, showing an improved healing
behavior ascribed to the newly formed hydrogen bond supra-
molecular network between the rubber and filler with the
incorporation of t-CNs.

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Fig. 12 (a) Tensile energy for original and healed samples and (b) healing eciency for ENR and nanocomposites. All the samples were autono-
mously healed at room temperature for 24 h without any external stimulus.

Scheme 1 Schematic illustration of self-healing by molecular chain interdiusion assisted reconstruction of the hydrogen bond network.

Based on the observed results, the self-healing mechanism

is illustrated in Scheme 1. Three reasons should be responsible
for the observed self-healing behavior. The first involves with
the slight cross-linking of rubber, as molecular mobility of the
free chain ends allows interpenetration at the interface, which
can serve as a driving force for the healing process.34,48,49 The
second deals with the eective polar interactions governed by
the polar groups in ENR.21,37 The third relates to the enhanced
intermolecular force between the rubber and filler. The intro-
duction of t-CNs facilitates the formation of a hydrogen bond
supramolecular network, and the reversible hydrogen bonds
easily dissociate and rearrange during the self-healing process,
which make great contribution to the improved self-healing
behavior.
In the end, we further investigated the eect of separation
Fig. 13 Time dependence of self-healing properties for ENR/t-CNs-20
time on self-healing performance of ENR based nano- with various waiting times before recombining the two cut faces. The
composites. As shown in Fig. 13, a longer waiting time before samples were autonomously healed for 24 h after bringing the two
the cut surfaces were re-contacted resulted in reduced mechan- halves together.

This journal is The Royal Society of Chemistry 2017 Nanoscale


Paper
ical property recovery. Similar results have been found in pre-
vious hydrogen bonds self-healing systems.49,50 This can be
Published on 14 September 2017. Downloaded by CTRO UNIV DE CIENCIA EXACTAS E IGN - (CUCEI) on 13/10/2017 10:33:29.
contributed to the dangling free groups near the fracture
surface which find partners within the broken part during the
waiting time, which reduced the number of non-associated
groups available for bridging when the surfaces were brought
back into contact. However, this time-dependent self-healing
performance may be irrelevant in applications, as the material
should autonomously start the healing process immediately
after the microcrack happened.51
4. Conclusions
By using biosourced, rigid, and high aspect ratio tunicate cell-
ulose nanocrystals (t-CNs) isolated form marine biomass, we
have developed high strength, self-healable ENR nano-
composites with improved mechanical properties and healing
behavior. The reversible hydrogen bond supramolecular
network between the rubber and filler facilitates the self-
healing process and improves mechanical properties of the
elastomers. Increasing t-CN content dramatically increased the
healing eciency, tensile strength and tensile modulus.
Healing eciency also increased with extended healing time,
while it decreased with increased waiting time before recom-
bining the two cut surfaces. With 20 phr t-CNs, tensile
strength and modulus increased to 4.04 and 16.3 MPa, which
are 350% and 7-fold over those of neat ENR, and nearly 86% of
tensile energy could be recovered compared with 48% of neat
ENR. The improved self-healing behavior of the nano-
composites is attributed to the synergistic eect between mole-
cular interdiusion via slightly cross-linked rubber and the
enhanced hydrogen bond supramolecular network between
the rubber and filler.
Conicts of interest
There are no conflicts to declare.
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