Article

Cite This: Chem. Mater. 2019, 31, 2347−2357 pubs.acs.org/cm

Tailoring the Hard−Soft Interface with Dynamic Diels−Alder

Linkages in Polyurethanes: Toward Superior Mechanical Properties
and Healability at Mild Temperature
Thuy Thu Truong, Son Hong Thai, Ha Tran Nguyen, Dung Thuy Thi Phung, Loc Tan Nguyen,
Hung Quang Pham, and Le-Thu T. Nguyen*
National Key Laboratory of Polymer and Composite Materials & Faculty of Materials Technology, Ho Chi Minh City University of
Technology (HCMUT), Vietnam National University−Ho Chi Minh City (VNU−HCM), 268 Ly Thuong Kiet, District 10, Ho
Chi Minh City 700000, Vietnam
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*
S Supporting Information
Downloaded via CHUNG YUAN CHRISTIAN UNIV on August 21, 2022 at 23:34:08 (UTC).

ABSTRACT: The current thermoremendable polyurethanes

(PUs) based on reversible Diels−Alder (DA) chemistry
featuring both good mechanical properties and efficient
macrodamage healability are up to now built with the DA
bonds located in the hard domains with restricted mobility,
which hinders the DA reversibility. Thus, the healing process
in these materials requires predissociation of DA bonds via the
retro reaction at high temperatures (110−180 °C) followed by
DA re-formation, which may compromise the material
performance integrity. Here, we show a design of thermoset
PUs containing dynamic DA entities engineered at the
interface between the hard and soft domains that combine
high modulus and toughness with mild-temperature-triggered
molecular mobility, which is a prerequisite for efficient healing capability. This concept of molecular design enables PUs to have
great mechanical properties (Young’s modulus ∼80−225 MPa, ultimate tensile strength ∼16−30 MPa, and toughness ∼26−96
MJ m−3) and simultaneously remarkable healing ability at mild temperatures (60−70 °C) of macroscratches, punctures, and
complete cuts. The mechanical and healing properties can be tuned by varying the DA bond content. These materials are the
first reported DA-based PU materials showing excellent healing efficiency at mild temperatures without compensation of their
great mechanical properties.

1. INTRODUCTION thermoreversible covalent bonds such as furan−maleimide

Polyurethanes (PUs) stand out as one of the most well-known
high-quality plastic materials with excellent performance and
versatile properties for numerous applications such as
automotive industry, civil engineering, electronics, and
medicine.1 The superior properties of PUs are defined by
their molecular architectures built from microphase-separated
“soft” and “hard” domains, mimetic to the multiblock
supramolecular structures of strong and extremely tough
natural spider silk and nacre.2 Hard domains are made of H-
bonding assembled urethane bonds derived from isocyanates
and low-molecular-weight diol chain extenders, whereas soft
domains comprise of flexible polyol segments. Nature is also a
great source of conceptual inspiration for designing synthetic
self-healing materials.3,4 With the advances in developing self-
healing polymers, huge attention has been on PUs integrated
with scratch and cut healability. The developed approaches to
designing self-healing PUs have shifted from extrinsic healing
operating by a pre-embedded healing agent5−9 to intrinsic
healing via dynamic interactions, including noncovalent π−π
stacking and hydrogen bonding,10−12 ionic interactions,13
Diels−Alder (DA) adduct,14−30 triazolinedione−indole DA
adduct,31 (aromatic) disulfide,32−39 thiuram disulfide,40
(aromatic) diselenide,41,42 aromatic pinacol,43 and alkoxy-
amines44 as well as photoresponsive linkages such as
dihydroxyl coumarin,45 oxetane,46,47 oxolane,48 and disele-
nide.49 Among these, the furan−maleimide DA adduct is the
most prominently studied dynamic covalent bond for PUs.
The DA reaction between furan and maleimide exhibits “click”
and thermally reversible characteristics, occurring at low
temperatures (below 90 °C) and reverting at ∼110−130
°C.50 Moreover, the shape-memory effect triggered by polymer
thermal phase transitions has been effectively employed in PU
materials, alone51−53 or in combination with a reversible
chemistry14−16,22,23 to satisfy the need for crack closure
without external forces, assisting the recovery of broken
bonds located in the crack surfaces.
Received: November 4, 2018
Revised: March 8, 2019
Published: March 10, 2019

© 2019 American Chemical Society 2347 DOI: 10.1021/acs.chemmater.8b04624

Chem. Mater. 2019, 31, 2347−2357
Chemistry of Materials Article

Figure 1. (a) Design concept for the healable PU materials with reversible DA cross-links at the hard−soft interface. (b) Healing efficiencies
(tensile strength recoveries) after 24 h at 65 °C of the cut-in-half and respliced DA-PU samples versus tensile toughness. (c) Synthetic scheme of
functionalized PCL polyols, PUs containing DA bonds at the hard−soft interface 6a, and reference material 6b.

A high healing efficiency as a result of considerable cross-link
recovery usually requires high molecular mobility of dynamic
units, although highly flexible polymer chains are tailored for
materials with low mechanical performance.54,55 Despite
numerous advances in dynamic covalent PU materials, so far,
only soft rubbery PUs effectively self-repaired damages at mild
temperatures (from room temperatures to 60
°C).33−35,38,40,42,44,45 These mild-temperature healable PU
thermosets exhibited undesirable ultimate tensile strengths of
∼0.5−7 MPa and Young’s moduli of ∼0.5−3 MPa. On the
other hand, recovery of fairly high mechanical strength by mild
heating has been realized by only a few materials other than
PUs, such as a poly(ethylene adipate) cross-linked with DA
adducts56 and polyisoprene dually cross-linked with hydrogen
bonds and Zn−triazole coordination bonds.12
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Up to now, PUs exhibiting thermoremendability and
simultaneous high elastic moduli (>50 MPa) and tensile
strengths (>15 MPa) have been fabricated with the DA bonds
located in the hard domains comprising isocyanates and low-
molecular-weight diol bearing either a furan, maleimide, or DA
moiety.16−28 Consequently, the molecular motion of the DA
bonds was restrained, and the dissociation of these bonds via
the retro reaction occurring at ∼110−180 °C or under focused
ultrasound prior to DA reformation reactions was a
prerequisite for repairing macroscopic fractures.16−19,21−26,30
Generally, prolonged exposure to temperatures above 100 °C
could cause partial undesirable homopolymerization of
maleimide groups and oxidation of furan moieties, and hence
loss of dynamic property.57,58 High mending temperatures may
also result in decrease in material integrity and restrict the
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Figure 2. Comparison of the 1H NMR spectra of DA-PCL polyol, which was synthesized by the DA reaction between furan-PCL diol and 3-
maleimido-1-propanol, with those of furan-PCL diol and 3-maleimido-1-propanol. The signal denoted as a′ corresponds to the protons of HO−
CH(R)− groups of terminal glycidyl ether units. The signal denoted as i′ corresponds to the methylene protons of the caprolactone units next to
glycidyl ether units.

application area. Therefore, in previous reports, the shape-
memory-assisted repair of scratches at 50−60 °C in thermoset
PUs combining a semicrystalline polycaprolactone (PCL) soft
phase and DA bonds in the hard phase has been
investigated.14,15 In these materials, although crack closure
was enabled by the shape-memory effect induced by the
melting transition of PCL switching segments, such mild
heating programs failed to heal more severe damages like
complete cuts and punctures.14,15 Another possibility for
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enhancing the flexibility of reversible units is to synthesize
polyurethanes with pendant functional groups attached along
the soft segment polyols. However, covalent cross-linking
across soft segments may interrupt their crystallization, giving
rise to poor shape-memory-effect-assisted crack closure and
usually causes the loss of material toughness and extensibility.
Herein, our key idea is to integrate in the PU structure
reversible furan−maleimide DA entities strategically residing at
the interface between the hard domains and the soft domains
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Chemistry of Materials
Figure 3. (a) DSC thermograms (endo up) of the prepared PU materials. (b) ATR FT-IR spectra of DA-PU-100 in three thermal cycles (120 °C
(rDA) for 1 h and subsequently 65 °C (DA) for 24 h in each cycle).
composed of semicrystalline PCL segments (Figure 1a). Two
sets of dynamic bonds (H-bonding urethane assemblies in the
hard phase and reversible DA bonds at the hard−soft
interface) are combined for achieving high stiffness and
toughness and mendability. The healing process can be
initiated by melting of the soft phase at mild temperatures
(∼50−70 °C) to activate simultaneously many effects: the
shape-recovery effect to close the crack, strenuous polymer
chain motion required for the bound dissociated furan groups
to readily associate with neighboring maleimide moieties, and
the occurrence of DA reaction favorable at this temperature
range. This concept of molecular design makes the PUs
possess parallely high mechanical properties and efficient
macroscopic healability under a moderate temperature
condition (≤70 °C) without the need for a prestep of rDA
de-cross-linking reaction. Reference experiments were per-
formed to prove that the observed healing is requisitely
enabled by the action of reversible DA upon activating the soft
phase mobility at 60−70 °C. By fine tuning the content of DA
netpoints, a good balance of stiffness, toughness, and
healability can be accomplished (Figure 1b). For instance,
DA-PU-70 with the best healing behavior has a tensile
toughness of 65 MPa J−1. After being cut in half, respliced, and
heated at 65 °C, this material exhibited tensile strength
recoveries of 70% after 0.5 h and 88% after 24 h. On the other
hand, DA-PU-50 with the highest toughness of 96 MPa J−1
showed healing efficiencies of 58% after 0.5 h and 71% after 24
h at 65 °C.
It should be emphasized that although previously reported
PUs combining a semicrystalline PCL soft phase and DA
bonds in the hard phase showed efficient closure of
macroscratches made on film surfaces by a razor blade, they
did not heal upon being cut in half (the cut and respliced
surfaces did not adhere) even at temperatures ranging from 60
to 120 °C.14,15,29 This clearly shows that the DA-PUs in this
study exhibited superior healing characteristics.
As a proof of concept, the healing functionality of the
coatings of these PUs was further demonstrated to be
applicable for protection of steel substrates against corrosion.
2. RESULTS AND DISCUSSION
The synthetic pathway is shown in Figure 1c. Following our
previous synthetic design of furan end-block-functionalized
PCLs (Scheme S1 and Figures S1 and S2, Supporting
Information),59 we synthesized a PCL polyol with the chain
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termini attached to the hydroxyl-bearing DA groups (DA-PCL
polyol 2, Figure 1c) using the DA reaction between a furan
end-functionalized PCL diol (furan-PCL diol 1, Figure 1c) and
3-maleimido-1-propanol with furan-to-maleimide equimolar
ratio. The successful occurrence of the DA reaction was
evidenced by 1H NMR (Figure 2) and Fourier transform
infrared (FT-IR) (Figure S4, Supporting Information) spec-
troscopy. As shown in the spectrum of DA-PCL polyol (Figure
2), the maleimide peak at 6.73 ppm and the furan peaks at
7.35, 6.30, and 6.18 ppm almost disappeared, whereas the
peaks attributed to the DA adduct bond signals appeared at
6.59−6.33, 5.23, and 3.27−2.87 ppm. By comparing the
integral ratio between the signal g1 (DA double-bond group, at
6.59−6.33 ppm) and the signal g (maleimide group, at 6.73
ppm) or the signal t (furan group, at 6.18 ppm), the DA
reaction conversion was determined to be around 97%. The
result revealed that in average, each DA-PCL chain contains
three pendant DA moieties and hence five hydroxyl groups.
More details about the synthesis procedures, results, and
spectroscopy data are provided in the Supporting Information.
The DA-PCL polyol was subsequently combined with a
nonfunctionalized PCL diol (5, Figure 1c) as the soft segment
to react with hexamethylene diisocyanate (HDI) isocyanurate
trimer (4, Figure 1c) in dry toluene with zirconium
acetylacetonate as the catalyst. The reaction solution was
casted on a teflon-coated plate and heated at 60 °C for 24 h,
followed by vacuum annealing at 70 °C for 24 h to produce
hard and tough solid DA-PU materials 6a. The density of DA
cross-links at the hard−soft interface and the crystallinity of the
soft domains, tunable by changing the weight ratio between the
DA-PCL polyol and PCL diol, could in principle influence the
PU mechanical properties and the ability to reversibly
exchange chemical bonds. Thus, a set of networks DA-PU-n
with variation in the weight fraction (n) of DA-PCL in the soft
phase was prepared (n = 100−85−70−50). Additionally, the
sample ref-PU, with the DA bond replaced by an alkylene
group, was prepared as a reference material using an analogous
hydroxyl end-functionalized PCL (ref-PCL polyol 3, Figures 1c
and S3) following an identical synthetic protocol.
Attenuated total reflection (ATR) FT-IR spectra of all PUs
featured no absorption bands at 2270 cm−1, corresponding to
the NCO stretching band and the appearance of urethane
vibrational bands at 3340 cm−1 (amide A), 1619 cm−1 (amide
I), and 1560 cm−1 (amide II) (Figure S5a). A comparison of
the ATR FT-IR spectra of DA-PU-100 and DA-PCL polyol
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Figure 4. (a, b) Optical microscopy (OM) images of a scratch and a puncture by a paper pin on DA-PU-70 films before (a1, b1) and after (a2, b2)
healing at 65 °C for 24 h. (c, d) SEM images of scratches on DA-PU-85 (c) and ref-PU (d) films before (c1, d1) and after (c2, d2) healing at 65
°C for 24 h. (e) DA-PU-70 film (28 × 8 × 0.46 mm 3) being cut in half, rejoined, and healed for 24 h at 65 °C, followed by a 1 kg lifting test
(Movie S1, Supporting Information), and OM images of both sides of the rejoined area after healing (e4, e5). (f) DA-PU-50 cylinder (28 × 5
mm2) cut through 75% of the cylinder width, shape-recovered, and healed at 65 °C for 24 h, followed by 10 kg at 30 °C and 2.5 kg at 70 °C lifting
tests (Movie S2a,b Supporting Information). The logo of HCMUT, VNU-HCM, also named as Bach Khoa University, is used with permission
from the HCMUT, VNU-HCM.

showed the preservation of the band at 862 cm−1 ascribed to
the DA bond and negligible typical maleimide absorption
bands at 829 and 696 cm−1 and furan “ring breathing” signal at
1010 cm−1, indicating that all the DA bonds were intact
(Figure S5b). The differential scanning calorimetry (DSC)
thermograms of all PUs displayed an endothermic transition of
the crystallized PCL soft phase in the range of 34−64 °C, with
maxima at 47−56 °C, corresponding to the transition
temperature (Ttrans) to trigger the shape-recovery effect (Figure
3a). The melting maximum and melting endotherm of PCL
segments in DA-PUs slightly decreased with the increasing
weight fraction of DA-PCL polyol, which declined the
crystallinity of the soft phase due to hindered polymer chain
alignment. The relatively lower Ttrans of DA-PUs with higher
DA moiety contents can be beneficial to enable partial shape
recovery at room temperature. Additionally, the DSC thermo-
grams of DA-PUs showed an endothermic peak starting at 100
°C and ending at 170 °C, attributed to the rDA reaction and
indicating the cleavage of reversibly cross-linked bonds,
whereas it was not observed for ref-PU. Based on the thermal
analysis, 65 °C was chosen as the healing temperature to
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trigger both shape recovery and the DA reaction, allowing for a
mild, single-temperature healing process.
The DA reversible cross-linking in the solid DA-PUs was
monitored using ATR FT-IR spectroscopy, and the repre-
sentative results are shown for DA-PU-100 in Figure 3b. The
spectrum of the sample after heating to 120 °C for 1 h, without
subsequent quenching, clearly shows the appearance of
maleimide bands at 696 and 829 cm−1 and simultaneously a
decrease in intensity of the DA band at 862 cm−1. This clearly
suggests the partial cleavage of the DA linkages, although some
re-cross-linking could occur during sample handling and
measurement at room temperature. Subsequently, mild heating
at 65 °C reconstructed the disconnected linkages through DA
reaction, as evidenced by the decrease in the maleimide band
intensity and the regaining of DA band intensity. The
repeatability of the DA and rDA reactions was demonstrated
for three cycles.
Wide-angle powder X-ray diffraction (XRD) measurements
were conducted for a further morphological investigation of
the DA-PUs. For a comparison purpose, a PU (named as PU1)
consisting of a semicrystalline PCL soft phase and DA bonds in
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Figure 5. (a) Stress−strain curves of PU materials. (b) Stress−strain measurements of the original and healed DA-PU-70 samples acquired in the
cut-in-half and large deformation experiments. (c) Recoveries of tensile properties for DA-PUs in the cut-in-half healing experiments after healing at
65 °C for 30 min (open symbols) and 24 h (filled symbols). (d) Recoveries of tensile properties for DA-PUs in the large tensile deformation (to a
strain of 75% of the strain of break) experiments.
the hard phase was prepared by repeating the previously
reported structural design and synthetic procedure (Scheme
S2).14 PU1 was composed of PCL diol (5, Figure 1c), HDI
isocyanurate trimer (4, Figure 1c), and a DA adduct tetra-ol
(formed by reacting 2,5-bis(hydroxymethyl)furan with bisma-
leimide), and had a hard segment content of 22 wt %
analogous to that of DA-PU-70. Figure S6 compares the XRD
spectra of PU1, DA-PU-70, and DA-PU-100. The XRD
patterns of both PU1 and DA-PU-70 revealed strong and
sharp peaks at 2θ = 21.5, 22.1, and 23.8° and weak reflections
at 15.7 and 29.9° attributed to the crystalline PCL soft
domains. For DA-PU-100, these peaks were significantly
weakened, suggesting a low degree of crystallinity in the soft
phase due to high cross-link content. Two relatively diffused
reflections at around 13 and 20° (beneath the diffraction peaks
of PCL crystals) were observed for PU1 and DA-PU-70.
These peaks could be assigned to irregular packing of the hard
segments, which is overshadowed by the presence of the
crystallized PCL phase. Such typical reflections ascribed to
low-order arrangement of hard segments have been previously
reported for some HDI isocyanurate trimer-based and other
PUs.60−62 The difference of the XRD pattern of DA-PU-100
indicates that increasing the number of chemical cross-links
suppressed both crystallization of soft segments and
segregation of hard segments. Moreover, only PU1 displayed
a small diffraction peak at 4.57 Å (19.4°), suggesting that it
could be a result of a small fraction of hard segment stacking.62
Despite the modest microphase separation of the hydrogen
bonding, hard domains from the soft PCL domains in DA-PUs,
as the DA bonds are attached to both soft chains and urethane
moieties, must be located in the vicinity of both domains. Such
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a chemical structure would increase the “solubilization” of hard
segments in the soft segment phase, which, to some extent,
could be advantageous for the molecular motion of DA bonds.
Both ref-PU and DA-PU samples showed good shape
recovery ability at above 60 °C (an illustration of the shape-
memory effect is shown in Figure S7). However, only DA-PUs
possessed efficient healability. The healing properties were first
evaluated by a surface cut recovery test using optical
microscopy (OM) and scanning electron microscopy (SEM).
Scratches were applied to the materials using a scalpel blade to
generate macroscratches. The microscopic images of the
scratches before and after healing at 65 °C for 24 h are
shown in Figures 4a−c, S8, and S9 (Supporting Information).
All DA-PUs achieved full scratch recovery, whereas ref-PU
showed incomplete scratch healing despite considerable
reduction in the scratch width as a result of the shape-memory
effect (Figure 4d). When applying the same surface cutting
protocol, the scratch width (before healing) was smaller for
DA-PUs with higher DA-PCL polyol content (Table S1). This
is attributed to lower shape-memory Ttrans values of DA-PU-
100 and DA-PU-85 (with DSC melting peaks starting at ∼35
°C and ending at ∼55 °C) resulting in partial shape-recovery
effect at room temperature. Nevertheless, DA-PU-70 and DA-
PU-50 exhibited a slightly better scratch-healing performance.
After healing, the scratches on the surface of these samples
almost disappeared, whereas slight incision scars were observed
on the surfaces of DA-PU-100 and DA-PU-85. In another
qualitative assessment test, a puncture by a paper pin of around
1 mm diameter was applied to the materials (Figures 4b and
S10−S13, Supporting Information), followed by heating at 65
°C for 24 h. Although all DA-PUs were able to close the
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Table 1. Summary of the Mechanical Properties of PU Materials
sample Young’s modulus (MPa) yield stress (MPa)
DA-PU-100 81.2 ± 11.5 13.3 ± 1.7
DA-PU-85 95.8 ± 12.0 15.9 ± 2.3
DA-PU-70 215.9 ± 19.1 17.1 ± 2.0
DA-PU-50 226.8 ± 21.3 18.9 ± 1.9
ref-PU 97.2 ± 12.3 16.3 ± 2.4
puncture damages, only DA-PU-70 and DA-PU-50 showed
complete healing with the damage sites remaining sealed when
stretching the healed samples. A comparative puncture test was
also performed on a cured natural rubber material as a
reference sample, showing that the puncture was closed upon
removal of the pin due to rubber elasticity but not healed
(Figure S14).
To demonstrate the superior healing properties of DA-PUs,
a DA-PU-70 film (28 × 8 × 0.46 mm3) was cut in half and
respliced under heating by a hair dryer to manually attach the
cut surfaces, followed by keeping at 65 °C for 24 h. The healed
sample was able to lift a weight of 1 kg without tearing (Figure
4e and Movie S1, Supporting Information). The OM images of
both sides of the rejoined film after healing revealed complete
connection of the cut halves, with only a slight interface
mismatch (Figure 4e4,e5). To confirm that the cut halves were
chemically recombined, the healed film was immersed and
remained intact in chloroform (Figure S15, Supporting
Information). For a cut and respliced film of ref-PU after
heating at 65 °C for 24 h, the rejoined halves were detached
due to swelling (Figure S16, Supporting Information). Using
the same test, similar results showing good healing of complete
cuts were also observed for the other DA-PUs (Figures S17−
S19, Supporting Information).
To further show the cut healability with the assistance of the
shape-memory effect, a DA-PU-50 cylinder (28 × 5 mm2) was
cut in a direction perpendicular to the axial length and with a
cut depth of about 75% of the cylinder width, resulting in two
almost separate halves attached together at one edge. Heating
the cut cylinder by a hair dryer within one min quickly closed
the cut gap due to the shape-memory effect without the need
for any manual pressing. Subsequent heating at 65 °C for 24 h
to enable full recovery of the broken DA bonds gave
completely healed sample, which sustained a hanging weight
of 10 kg (Figure 4f and Movie S2a, Supporting Information).
To exclude the possibility that the connection of the cut
surfaces was only caused by intermolecular attractive forces
originating from PCL crystallization at the cut interface, the
healed sample was heat-softened at 70 °C due to melting of the
PCL soft phase and was then shown to sustain a 2.5 kg hanging
weight. The same cutting−healing−weight-lifting test was
repeated at the same site, demonstrating repeatable healability
(Movie S2b, Supporting Information). On the contrary,
applying a similar test on ref-PU revealed hardly any chemical
healing, since the heat-softened sample was immediately
fractured completely at the cut site when subjected to a
weight load (Movie S2c, Supporting Information). This
reference experiment strongly proved that the healing was
enabled by the action of reversible DA chemistry.
The mechanical properties of the PUs were evaluated by
tensile tests. Figure 5a shows the tensile stress versus strain
curves at 30 °C and the derived mechanical parameters are
summarized in Table 1. All PU samples exhibited high
mechanical properties, with Young’s moduli of 81.2−226.8
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yield strain (%) stress of break (MPa) strain of break (%)
31 ± 5 16.2 ± 5.1 193 ± 45
30 ± 6 18.6 ± 4.7 245 ± 56
28 ± 5 25.4 ± 7.6 344 ± 70
22 ± 7 30.5 ± 9.0 445 ± 78
23 ± 9 15.8 ± 5.3 360 ± 55
MPa, yield stresses of 13.3−18.9 MPa, maximum stresses of
16.2−30.5 MPa, and ultimate strains of 193−445%. Both
cross-linking density and PCL crystallinity play key roles in the
mechanical performance. A clear trend of increasing Young’s
modulus, stress, and strain of break values upon decreasing
DA-PCL polyol/PCL diol content ratio was observed,
attributed to the increased crystallinity of the PCL soft
phase. DA-PU-70 and DA-PU-50 achieved superior Young’s
modulus and tensile strength values of above 200 and 25 MPa,
respectively. However, DA-PU-70 exhibited the best healing
properties (vide supra), suggesting the crucial requirement of
both high DA group density and PCL crystallinity. Endowed
by the rigid DA groups, DA-PU-70 also showed a better tensile
performance than ref-PU with an analogous composition.
To evaluate the healing efficiencies of the DA-PUs, tensile
tests were conducted on damaged and subsequently healed
samples. Two kinds of damages, cutting and large tensile
deformation, were investigated. A comparison of the stress−
strain curves of the healed and original DA-PU-70 samples is
shown in Figure 5b. In the cutting recovery test, DA-PU
dumbbell-shaped specimens were cut in half in the middle
along the width and perpendicular to the stretching direction.
The specimen halves were then heated at 65 °C for less than 1
min and the cut surfaces were manually rejoined, followed by
heating at 65 °C for 30 min or 24 h. The healing efficiency was
determined as the ratio of the healed to the initial values of
maximum stress, Young’s modulus, and ultimate strain. The
results are summarized in Figure 5c. The recovery of
mechanical properties varied significantly for different
compositions. The healing efficiencies of the DA-PUs
increased in the following order: DA-PU-100 < DA-PU-50
< DA-PU-85 < DA-PU-70. After only 30 min at 65 °C, all DA-
PUs showed recoveries of Young’s modulus of 42−87% and
maximum stress of 39−70%, whereas maximum healing
efficiencies (51−89% for Young’s modulus and 45−91% for
strength) were obtained for samples healed for 24 h. This is
generally in line with the kinetics of the DA reaction that
mainly takes place during the first hour but requires a long
afterward reaction time of up to 24 h to reach the maximum
conversion.15,24 In accordance with the increased recoveries of
tensile strength and modulus, a longer heat treatment for 24 h
also considerably enhanced the ultimate strain by 2−3 times.
Except for DA-PU-100, the rest materials are of great interest
for the recovery of modulus and strength to more than 88 and
70%, respectively. It is suggested that two factors are required
for efficient healing of cuts: (i) a sufficiently high extent of
PCL crystallinity, which is beneficial to good shape-memory
properties and thus is crucial for the damaged edges to close
effectively, and (ii) the maintenance of a certain high level of
dynamic DA bonds, which is a prerequisite for chemical
ligation of the cut surfaces.
In addition, the same cutting test protocol was carried out
for DA-PU-70 but with varying mild healing temperatures. A
comparison of the strength recoveries after healing at
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Figure 6. (a) Bode plots of DA-PU-70 coated on stainless steel before and after scratching and the scratched coating after healing at 65 °C for 30
min and 24 h. (b) Impedance (at 0.1 Hz) comparison of coated DA-PU films in the healing experiments. (c) Bode plots of a free-standing DA-PU-
70 film before and after scratching and the scratched coating after healing at 65 °C for 30 min and 24 h. (d) Impedance (at 0.1 Hz) comparison of
free-standing DA-PU films in the healing experiments.
temperatures in the range of 50−75 °C is presented in Figure
S20. Insignificant difference in healing efficiency (∼87−88%)
was observed at 65−75 °C, whereas it dropped down to 45 and
8% at 60 and 50 °C, respectively. This indicates that
temperatures of at least 10 °C above Ttrans was neccessary
for the shape memory to be effective for gap closure between
the cut surfaces.
The role of the shape-memory effect in assisting the healing
process was further elucidated in elongation-recovery experi-
ment. The samples were subjected to large tensile
deformations at strains of 75% of the corresponding strains
of break. After an instantaneous elastic recovery when releasing
the load, the elongated sample was heated to 65 °C for 24 h to
enable full shape recovery and reformation of the broken DA
bonds (Figure 5b). All DA-PUs showed excellent shape
memory recoveries but different mechanical healing efficiencies
(Figure 5d). The healing efficiencies increased in the order:
DA-PU-50 < DA-PU-100 < DA-PU-85 < DA-PU-70. Strain
recoveries over 100% were observed in some cases at the
expense of reductions in Young’s modulus and maximum
stress. The best result was obtained for DA-PU-70 with
recoveries of strength over 95% and Young’s modulus of 100%.
The effects of several healing cycles on the materials were
further investigated using DA-PU-70 (Figure S21). In the
cutting test, tensile strength recoveries were 88.3, 72.5, 51.9,
and 38.7% for the first, second, third, and fourth healing cycle
at 65 °C for 24 h, respectively. Such relatively large decreases
in the mechanical properties over multiple cycles could arise
from two factors: the breaking of permanent bonds that were
not able to recover and the mismatch of the cut surfaces after
multiple cuttings at the same position. Nevertheless, in tensile
deformation test where the healing process did not encounter
the challenge to ensure good contact between cut surfaces,
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DA-PU-70 only showed a slight drop of total ∼10% in strength
recovery after 4 cycles of stretch to a strain of 75% of the
strain-of-break and subsequent heating at 65 °C for 24 h (with
healing efficiencies of 95.4, 94.0, 89.9, and 85.1% for cycles 1−
4, respectively). The network deformation in this strain regime
was likely mainly the result of the dissociation of hydrogen and
DA bonds, which are weaker than other covalent bonds,63
along with the crystal slip in the semicrystalline PCL domains.
Thus, the recovery process was enabled via recombination of
broken reversible bonds in combination with the interdiffusion
and entanglement of PCL segments in a high entropy elasticity
state. An analogous cyclic stretching test was further
performed, but with the samples subjected to a very large
stretch with a strain of 95% of the strain-of-break of the
previous cycle. Healing efficiencies of 88, 79.6, 60.6, and 44.1%
for cycles 1−4, respectively, were obtained. This indicates that
under very extensive deformation, other irreversible covalent
bonds could also be broken but could not reform, therefore
decreasing the material properties over multiple cycles.
In addition, to assess the effect of high healing temperature
in comparison with the mild conditions studied, an analogous
tensile deformation to a strain of 75% of strain-of-break test
was applied to DA-PU-70, using a high healing temperature
program. In every cycle, after releasing the load, the elongated
sample was first heated to 130 °C for 2 h and subsequently at
65 °C for 24 h. The strength recovery considerably decreased
after each cycle, showing efficiencies of 95, 87, 68, and 50% for
cycles 1−4, respectively. This suggests that although the
preheating at a high temperature of 130 °C might promote
cleavage of bonds, giving rise to enhanced mobility of dynamic
groups, it decreases the ability of the material to repeatedly
heal damages due to loss of maleimide and furan moieties via
DOI: 10.1021/acs.chemmater.8b04624
Chem. Mater. 2019, 31, 2347−2357
Chemistry of Materials
side reactions, therefore showing the advantage of mild healing
temperatures.
To explore whether the DA-PU materials could serve as
thermally remendable coatings for corrosion protection,
electrochemical impedance spectroscopy (EIS) was performed
on coated films using a standard three-electrode setup based
on the method previously reported.53,64,65 The Bode plots of
unscratched films of DA-PUs coated on stainless steel
substrates are shown in Figure S22. DA-PU coatings exhibited
film resistances higher than 108 Ω cm2 as determined from the
plateau observed in the low-frequency regions of the Bode
plots, showing the characteristic properties of effective
protection against corrosion. To assess the corrosion resistance
of coatings before and after healing, the coating resistance was
measured both immediately after scratching by a razor blade
and after healing at 65 °C for 30 min and 24 h. Figure 6a
depicts the typical impedance spectra of DA-PU-70 coating
before and after scratching and after healing, whereas the
spectra for the other DA-PUs are shown in Figure S23
(Supporting Information). Figure 6b compares the film
resistance (impedance values at 0.1 Hz) before and after
healing for all DA-PUs. The impedance amplitude in the low-
frequency region (∼4 × 109 Ω cm2 at 0.1 Hz) dropped by
about 3 orders of magnitude after scratching due a decrease of
corrosion resistance. For all DA-PUs, healing at 65 °C for 30
min was already sufficient to regain the barrier properties with
the impedance values at 0.1 Hz recovered to above 108 Ω cm2,
which were further enhanced after 24 h healing. The
impedance values in the low-frequency region of the healed
samples were somewhat lower compared with the unscratched
ones. This could be due to either the started corrosion attack
below the coating during immersion before healing or a healing
efficiency below 100%. DA-PU-70 showed the best healing
effect with the impedance returning to nearly the same value as
before scratching after 24 h at 65 °C.
Assessment of the scratch healability of free-standing DA-PU
films (of ∼200 μm thickness) was also conducted by EIS
characterization using a two-electrode setup. A DA-PU
specimen was prepared in a capacitor-like manner, with both
its surfaces spray-coated with a conductive silver paste as the
external electrodes. The diffusion of the silver paste through
the cut-through scratch caused a significant drop in the
resistance, and scratch healing was indicated by a recovery of
the resistance (Figures 6c and S24 (Supporting Information)).
Figure 6d compares the impedance values at 0.1 Hz before and
after healing for all the DA-PU free-standing films. The
impedance values of DA-PU-100 and DA-PU-85 were
recovered considerably but were still lower than the pristine
values before scratching. The pristine resistances of DA-PU-70
and DA-PU-50 could be fully recovered after healing for 24 h
and 30 min at 65 °C, respectively. This arises from more
efficient scratch closure induced by the shape-memory effect as
a result of higher PCL crystallinity. It is indicated that the
effect of the shape memory in assistance healing is more
prominent for free-standing films. The results are in good
accordance with the OM and SEM observations.
3. CONCLUSIONS
In summary, we developed PU materials with high stiffness,
strength, and toughness and highly efficient healability at mild
temperatures (∼60−70 °C). These materials feature reversible
furan−maleimide DA bonds at the interface between the hard
and soft domains, along with a crystalline PCL soft segment-
2355
Article
assisted toughness and shape-memory effect. The key is the
residence of the DA cross-links at the hard−soft interface that
do not interfere with the soft segment crystallinity and can also
provide sufficient mobility for the re-association of discon-
nected furan and maleimide entities at temperature above the
melting temperature of the crystalline PCL phase. Therefore,
effective reformation of DA groups could be enabled at mild
temperatures, without the need for prior DA adduct
decomposition at high temperatures to avoid potential
degradation (polymerization) of maleimide moieties. As the
materials showed good mechanical properties and were also
able to repair complete cuts and macrodamages by a one-step
heating at mild temperature, this is going beyond the current
state-of-the-art for intrinsic thermohealing materials based on
DA chemistry (Table S2).14−31
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.chemma-
ter.8b04624.
Experimental details, NMR, FT-IR, and XRD spectra,
EIS spectra, optical microscopic images, and photo-
graphs of healed PU samples (PDF)
Healing of cut PU samples (AVI) (AVI) (AVI) (AVI)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: nguyenthilethu@hcmut.edu.vn.
ORCID
Le-Thu T. Nguyen: 0000-0002-6452-2639
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research is funded by Vietnam National University
Hochiminh City (VNU-HCM) under grant number B2017-20-
06. We thank Hang Phung Tran from Bayer Vietnam Ltd. for
advice on isocyanate products. Coenraad Schaap (Perstorp
AB), Malin Falkman (Perstorp AB), and Alvin Kim (Perstorp
Chemicals Asia Pte Ltd) are acknowledged for advice and for
supplying polycaprolactone products.
■
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2357 DOI: 10.1021/acs.chemmater.8b04624

Chem. Mater. 2019, 31, 2347−2357