polymers
Article
A Metal Coordination-Based Supramolecular Elastomer with
Shape Memory-Assisted Self-Healing Effect
Fang Xie 1,† , Zhongxin Ping 2,† , Wanting Xu 1 , Fenghua Zhang 2 , Yuzhen Dong 1 , Lianjie Li 1 , Chengsen Zhang 3
and Xiaobo Gong 3, *
Citation: Xie, F.; Ping, Z.; Xu, W.;
Zhang, F.; Dong, Y.; Li, L.; Zhang, C.;
Gong, X. A Metal Coordination-
Based Supramolecular Elastomer
with Shape Memory-Assisted
Self-Healing Effect. Polymers 2022, 14,
4879. https://doi.org/10.3390/
polym14224879
Academic Editor: Shazed Aziz
Received: 1 October 2022
Accepted: 11 November 2022
Published: 12 November 2022
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4.0/).
Polymers 2022, 14, 4879. https://doi.org/10.3390/polym14224879
1 School of Materials Science and Engineering, Harbin Institute of Technology at Weihai, Weihai 264209, China
2 National Key Laboratory of Science and Technology on Advanced Composites in Special Environments,
Harbin Institute of Technology, Harbin 150080, China
3 School of Naval Architecture and Ocean Engineering, Harbin Institute of Technology at Weihai,
Weihai 264209, China
* Correspondence: xiaobogong@hit.edu.cn
† These authors contributed equally to this work.
Abstract: Rubber materials are widely used in aerospace, automotive, smart devices and artificial skin.
It is significant to address the aging susceptibility of conventional vulcanized rubber and to impart it
rapid self-healing performance for destructive crack damage. Herein, a novel supramolecular rubber
elastomer is prepared by introducing metal coordination between carboxyl-terminated polybutadiene
and polystyrene-vinylpyridine copolymer. Based on the metal coordination interaction, the elastomer
exhibits shape memory and self-healing properties. Moreover, a rapid closure-repair process of
destructive cracks is achieved by presetting temporary shapes. This shape memory-assisted self-
repair model is shown to be an effective means for rapid repair of severe cracks. An approach
to enhance the mechanical and self-healing properties of elastomer was demonstrated by adding
appropriate amounts of oxidized carbon nano-onions (O-CNO) into the system. The tensile strength
of the elastomer with an O-CNOs content of 0.5 wt% was restored to 83 ± 10% of the original sample
after being repaired at 85 ◦ C for 6 h. This study confirms that metal coordination interaction is an
effective method for designing shape memory self-healing rubber elastomer. The shape memory-
assisted self-healing effect provides a reference for the rapid self-repairing of severe cracks.
Keywords: self-healing; polybutadiene; metal coordination; shape memory; oxidized carbon nano-onions
1. Introduction
Rubber has been widely used in aerospace, automotive, smart devices and artificial
skin due to its excellent performance due to its high elasticity and high wear resistance. The
traditional rubber generally needed to undergo vulcanization is processed to cross-link the
raw rubber molecules to form a 3D network to optimize its performance. However, a stable
and an irreversible covalent cross-linked structure makes the rubber difficult to recycle once
it is aged. Therefore, developing a new elastomer molecular network construction approach
to manufacture rubber materials with excellent mechanical properties and self-healing
efficiency remains a challenge [1–3].
Supramolecular interactions include hydrogen bonding interaction, metal coordina-
tion interaction, π–π stacking interaction, host–guest interaction and other intermolecular
interactions [4,5]. Urban et al. [6] pointed out that supramolecular interactions have faster
polymer network reconstruction speed and sensitivity compared with covalent bonds.
Moreover, compared with other supramolecular interactions, such as hydrophobic inter-
action and hydrogen bond interaction, metal coordination has strong interaction forces,
strict directivity, abundant ligands and it is easy to modify, thus having broad designability
and diverse functions [7]. The supramolecular polymers based on metal coordination
can simultaneously obtain the excellent properties of polymers and metal complexes [8,9].
https://www.mdpi.com/journal/polymers
Polymers 2022, 14, 4879 2 of 13

Metal coordination will provide the possibility for the design of new self-healing shape
memory elastomers.
Liu et al. [10] combined hydrogen bonding and Zn(II)-triazole coordination to prepare
a high-performance elastomer with a dual dynamic network. The tensile strength of the
elastomer recovered to 74% of that of the original sample (15.5 MPa) after healing at 80 ◦ C for
24 h. Zhao et al. [11] developed dual-programmable shape-memory organohydrogels with
supramolecular heterogeneous networks by utilizing Fe(III)-carboxylate coordination. This
organohydrogels exhibits excellent self-healing properties and hierarchical shape morphing
performance. Li et al. [12] prepared an elastomer with high stretchability and self-healing
ability based on strong pyridine-Fe(III) and weak formamide-Fe(III) coordination. The
healing efficiency of this elastomer was 90 ± 3% after 48 h of healing at room temperature.
Wu et al. [13] introduced strong metal coordination bonds and weak hydrogen bonds
into the polymer network to prepare a supramolecular elastomer with good mechanical
properties and excellent self-healing ability, with a high self-healing efficiency of 90%.
However, the properties of these self-healing elastomers are relatively single, generally
showing good mechanical properties and self-healing properties. Here, we consider intro-
ducing metal coordination bonds into the block copolymer network, using the microphase
separation properties of block copolymers and the metal coordination of supramolecular
polymers to make the polymers form metal coordination block copolymer micelles [14–17].
Dynamic coordination interaction is used to ensure the spontaneous progress of self-healing
and the aggregated structure of micelles is used to provide the nodes and networks required
for shape memory polymers, while shape memory effect can assist self-healing behavior
and further improve self-repair efficiency or shorten the time in the same case.
Moreover, carbon nano-onions (CNOs) with unique structural properties are typical
0D nanomaterials with high porosity, high electrical conductivity, and electrochemical
stability [18–20]. Surface-functionalized CNOs not only possess good chemical/mechanical
stability, high electrical conductivity, and tunable surface structure [21–23] but also have
good dispersibility and barely agglomeration [24,25]. Compared with other widely studied
carbon materials, the functionalized CNOs exhibit higher reactivity and solubility. The
oxidized CNOs (O-CNOs) have abundant carboxyl groups, which may provide a strong
interfacial force between O-CNOs and polymer subjects so as to form composites with
better mechanical properties [26,27]. Additionally, O-CNOs with abundant carboxyl groups
can increase the content of hydrogen bonds in the complexes to form strong interfacial
interactions, strengthening the mechanical properties, while providing an extra interfacial
driving force for the repairing the broken interfaces [28]. For this study, O-CNOs are
prepared by referring to the previously reported method [29], and their effects on the
mechanical properties and self-healing properties of the system are investigated.
In this paper, a self-healing polybutadiene-polystyrene-vinylpyridine elastomer based
on metal coordination bond interaction [Zn(II)-carboxyl group and Zn(II)-pyridine] was
prepared using polybutadiene rubber as the base material. An appropriate amount of
O-CNOs was added to the elastomer to enhance its mechanical properties and self-healing
ability. The well-dispersed O-CNOs reduced the intermolecular chain interaction forces,
and the polymer chain mobility was enhanced, thus improving the self-healing ability.
Moreover, the functionalized O-CNOs provide more abundant carboxyl groups, which
enhanced the internal hydrogen bonding to improve the mechanical properties. The shape
memory-assisted self-repair model was proposed as an effective means for rapid repair of
large cracks. This multifunctional material integrating shape memory, self-healing, and
shape-memory-assisted self-repairing properties will play a unique role in artificial muscles,
artificial skin, intelligent control, sensing and other fields.

2. Materials and Methods

2.1. Materials
Carboxyl-terminated polybutadiene (PB-COOH, average molecular weight of 4200 g/mol)
was purchased from Tianjin Xiens Biochemical Technology Co., Ltd. (Tianjin, China). The
 Polymers 2022, 14, 4879 3 of 13

polystyrene-vinylpyridine (PS-b-P4VP) was purchased from Scientific Polymer Products;

molecular weight was 400,000, and the content of pyridine functional group was 50 mol%.
Toluene, ethanol and zinc acetate dihydrate were purchased from Aladdin Chemical
Reagent Company. Carbon nano-onions (CNOs, diameters: 5–7 nm) were purchased from
Nanjing Mingchang New Material Technology Co., Ltd. (Nanjing, China). All chemicals
were commercially available and used as received.

2.2. Preparation of Polybutadiene-Polystyrene-Vinylpyridine Elastomer

The compositions of all samples are listed in Table 1, and the samples were prepared
according to the following procedure (Figure 1). Firstly, zinc acetate was dissolved in
deionized water and methanol mixture with volume ratio of 1:1, and PB-COOH was
dissolved in toluene. The above two solutions were mixed and stirred for 48 h and then
vacuum-dried at 50 ◦ C for 24 h to remove small molecular solvents, such as water, methanol,
acetic acid and toluene, to obtain zinc ionized carboxyl-terminated polybutadiene (PB-
COOZn). PB-COOZn and PS-b-P4VP were respectively dissolved in toluene solution; the
two solutions were mixed and magnetically stirred for 48 h. The mixture was dried in an
oven at 50 ◦ C for 72 h to remove most of the solvent and then dried in a vacuum drying
oven at 50 ◦ C for 24 h to remove all solvents to obtain the metal ion complex of PB-COOZn
and PS-b-P4VP. The samples with the molar ratios of Zn2+ , COO- and VP of 1:2:2, 1:2:4 and
1:2:8 were denoted as R1, R2 and R3, respectively.

Table 1. Component polymers ratio table.

Samples PB-COOH PS-b-P4VP Zn(AC)2 Zn2+ :COO− :VP mO-CNOs mO-CNOs /mtotal
Polymers 2022,
R114, 4879 5g 0.46 g 0.24 g 1:2:2 - - 4
R2 5g 0.92 g 0.24 g 1:2:4 - -
R3 5g 1.84 g 0.24 g 1:2:8 - -
R2-0.5% 5g R2-0.5%0.92 g 5g 0.24 g 0.92 g 1:2:4
0.24 g 30.8 1:2:4
mg 0.5% mg
30.8 0.5%
R2-1% 5g R2-1%0.92 g 5g 0.24 g 0.92 g 1:2:4
0.24 g 61.6 1:2:4
mg 1% mg
61.6 1%
R2-2% 5g R2-2%0.92 g 5g 0.24 g 0.92 g 1:2:4
0.24 g 123.21:2:4
mg 2% mg
123.2 2%

Figure1. 1.
Figure Schematic
Schematic diagram
diagram of the preparation
of the preparation process ofpolybutadiene
process of self-healing self-healingrubber
polybutadiene
com- ru
posite without
composite or with or
without O-CNOs.
with O-CNOs.

2.3. Characterization
Chemical bonds and functional groups of the samples were detected by Fou
Transform Infrared Spectroscopy (FT-IR) instrument (Nicolet 380, Thermal Elect
Waltham, MA, USA). The number of scans was 32 times/s. The test range was 400–
Polymers 2022, 14, 4879 4 of 13

The CNOs and concentrated sulfuric acid were mixed to prepare a suspension; under
the condition of constant stirring, concentrated sulfuric acid and concentrated nitric acid
mixture with volume ratio of 3:5 was added to the above suspension and then cooled in
an ice-water bath for 30 min. The mixture was then heated at 80 ◦ C for 30 min to obtain a
dispersion. Distilled water was added to the dispersion to dilute the dispersion; the dilution
was centrifuged at 7500 rpm after standing for 12 h, and the dilution and centrifugation
process was repeated twice. The black solid was collected to obtain O-CNOs powder.
O-CNOs powder and zinc acetate were dispersed in water/ethanol solution. PB-
COOH and zinc acetate were dissolved in toluene solution. Mix the above two solutions
well and let stand. After the solution was separated, PS-b-P4VP/toluene solution was
added to it, and finally a gray mixed solution was formed. Use a rotary evaporator to re-
move most of the solvent from the grey mixed solution. The mixture was dried in a vacuum
oven for 24 h to remove residual solvent, and a gray-brown translucent composite material
was obtained. The molar ratio of Zn2+ , COO− and VP in the prepared composite samples
was 1:2:4, which were denoted as R2-0.5%, R2-1% and R2-2%, respectively, according to the
mass ratio of their O-CNOs.

2.3. Characterization
Chemical bonds and functional groups of the samples were detected by Fourier Trans-
form Infrared Spectroscopy (FT-IR) instrument (Nicolet 380, Thermal Electron, Waltham,
MA, USA). The number of scans was 32 times/s. The test range was 400–4000 cm−1 , and
the transmission mode was used.
The molecular structure of the material was characterized by the laser microscope
Raman spectrometer (Renishaw inVia, British). The wavelength was 532 nm, and the light
intensity was 10%.
The thermal properties of the samples were measured with a Netzsch Instruments
FTA449F5 differential scanning calorimetry (DSC) from 40 to 240 ◦ C using a heating
and cooling rate of 10 ◦ C min−1 and an argon atmosphere. The data reported are from
measurements made after first preheating the samples to 320 ◦ C and then cooling them to
40 ◦ C to eliminate the influence of the prior thermal history.
The quasi-static tensile test was performed on a Instron 5967 universal tensile testing
machine with a stretching rate of 10 mm min−1 . The tensile test uses dumbbell-shaped
standard samples, and each specimen is tested more than five times in the same test
environment to obtain the average value.
Cyclic tensile tests were performed on the samples at room temperature, the specimens
were stretched to 50% strain, fully unloaded, and so on, and the hysteresis curves were
measured at different cycles. The dissipated energy ∆W of the elastic body is obtained by
calculating the integral area enclosed by the hysteresis curve by the following formula:
Z Z
∆W = σdε − σdε (1)
load unload

Analysis of self-healing performance: The wafer sample was cut into two semicircles
with a blade and then healed at a certain temperature. The morphology of the sample
before and after repair was observed by an optical digital microscope (DSX510, OLYMPUS,
Tokyo, Japan).
Dumbbell-shaped elastomer samples were cut in half from the middle with a blade; the
sections were aligned at room temperature, pressed gently for 1 min and then placed in a
vacuum drying oven at room temperature and 85 ◦ C for healing. After the repaired samples
were taken out from the vacuum drying box, they were cooled to room temperature and
then subjected to stress–strain testing at a tensile rate of 10 mm × min−1 . The self-healing
efficiency was quantitatively evaluated according to the ratio of the tensile strength and
elongation at break of the healed material to the original material, respectively.
 tensile strength and elongation at break of the healed material to the original mate
respectively.

3. Results and Discussion

Polymers 2022, 14, 4879 5 of 13
3.1. Molecular Structure of the Composite
The Raman spectras of CNOs and O-CNOs obtained at oxidation time of 0.5 h
3. Resultsinand
shown Figure 2. The D band and G band of the oxidized CNOs shifted to hi
Discussion
wavenumbers
3.1. from of
Molecular Structure 1350 cm−1, 1599 cm−1 to 1358 cm−1, 1608 cm−1, respectively. The rat
the Composite
intensities of the
The Raman D andofGCNOs
spectras bandsand (R O-CNOs
= ID/IG) directly
obtainedwere relatedtime
at oxidation to theof oxidation
0.5 h are degr
shown
the CNOs [28]. R of the pristine CNO was higher than that of O-CNO, higher
in Figure 2. The D band and G band of the oxidized CNOs shifted to which confir
wavenumbers
that CNOs had from cm−1 , 1599 cm
1350successfully
been
−1 to 1358 cm−1 , 1608 cm−1 , respectively. The
oxidized to O-CNOs. XPS results indicated that t
ratio of intensities of the D and G bands (R = ID /IG ) directly were related to the oxidation
were oxygen-containing functional groups on the surface of O-CNOs. The survey
degree of the CNOs [28]. R of the pristine CNO was higher than that of O-CNO, which
spectra ofthat
confirmed theCNOs
two samples
had been (Figure 2b) oxidized
successfully revealedtothat thereXPS
O-CNOs. wasresults
a strong O 1S peak i
indicated
CNOs compared with the original CNOs. This peak was largely
that there were oxygen-containing functional groups on the surface of O-CNOs. The survey attributed to
production
XPS spectra ofofthe
a large number(Figure
two samples of oxygen-containing functional
2b) revealed that there groups
was a strong O on the acidifie
1S peak
in O-CNOs compared with the original CNOs. This peak was
CNOs. Further analysis of the high-resolution C 1s peak (Figure 2c) showedlargely attributed to the that
production of a large number of oxygen-containing functional groups
surface of O-CNOs contains a mixture of carboxyl group (COOR), hydroxyl group ( on the acidified
O-CNOs. Further analysis of the high-resolution C 1s peak (Figure 2c) showed that the
and carbonyl (C=O). Note that the weak carbonyl peak observed in the C 1s spectru
surface of O-CNOs contains a mixture of carboxyl group (COOR), hydroxyl group (CO)
CNOs
and can be
carbonyl attributed
(C=O). to the
Note that adsorption
the weak carbonyl ofpeak
CO2observed
by the powder sample.
in the C 1s spectrum Theofcrystall
of the CNOs and O-CNOs were studied by XRD (Figure 2d). The
CNOs can be attributed to the adsorption of CO2 by the powder sample. The crystallinity peaks at 2θ = 26°
◦ and 44◦
44°
of thecan
CNOs beand
associated
O-CNOs werewithstudied
the (002)
by XRD and (100)2d).
(Figure diffractions
The peaks atof2θthe
= 26hexagonal grap
can be associated with the (002) and (100) diffractions of the hexagonal graphite
structure. For O-CNOs, the peak intensity at 2θ = 44° was decreased slightly, which structure.
For O-CNOs, the peak intensity at 2θ = 44◦ was decreased slightly, which may be due to
be due to the increase of lattice defects after oxidation.
the increase of lattice defects after oxidation.

Figure2.2.(a)(a)
Figure Raman spectra
Raman of CNOs
spectra and O-CNOs
of CNOs obtainedobtained
and O-CNOs at oxidation time of 0.5 h.
at oxidation XPSof
time analysis
0.5 h. XPS ana
of all tested samples (b) and peak fitting of C 1s at high resolution (c). (d) XRD spectra of
of all tested samples (b) and peak fitting of C 1s at high resolution (c). (d) XRD spectra of CNOsCNOs
and O-CNOs.
O-CNOs.
As shown in Figure 3a, FTIR spectra was used to elucidate the successful construction
of theAs shownnetwork
dynamic in Figure 3a, FTIR
structure of spectra was used
polybutadiene to elucidate
composite rubberthe successful
based on metalconstruc
of the dynamic
coordination. network structure
The comparison of the FTIRof polybutadiene
spectra of the originalcomposite rubber
material and based on m
the sample
is shown in Figure −1 , 1713 cm−1 and 1740 cm−1
coordination. The3.comparison
The peaks ofof PB-COOH
the FTIRatspectra
1639 cmof the original material and the sam
corresponded
is shown in toFigure
the olefin C=C stretching
3. The peaks of vibration,
PB-COOH the at
hydrogen
1639 cm bond
−1, dimer,
1713 cmcarboxyl
−1 and 1740
groups and the carbonyl group (C=O) of free carboxyl groups, respectively. It can be seen
corresponded to the olefin C=C stretching vibration, the hydrogen bond dimer, carb
that the peak of PB-COOZn at 1740 cm−1 disappeared, instead, a broader peak appeared
groups
at 1580 cmand
−1 , the carbonyl
which group
confirmed (C=O) of free
the successful carboxyl
bonding groups,torespectively.
of PB-COOH It can be
Zn2+ . For PS-b-
P4VP, the peaks at 1413 cm−1 , 1491 cm−1 , 1556 cm−1 , and 1595 cm−1 corresponded to the
aromatic vibration of the pyridine ring, and the peak at 1595 cm−1 corresponded to the
 aromatic vibration of the pyridine ring,−1and the peak at 1595 cm−1 corresponded to
that the peak of PB-COOZn at 1740 cm disappeared, instead, a broader peak appea
carbon-nitrogen bond (C-N) vibration. The peak of R2 and R2-0.5% appear at 1617 c
at 1580 cm−1, which confirmed the successful bonding of PB-COOH to Zn2+. For P
next to 1595 cm−1, revealing the complexation of Zn 2+ with the N atom of pyridine on
P4VP, the peaks at 1413 cm−1, 1491 cm−1, 1556 cm−1, and 1595 cm−1 corresponded to
Polymers 2022, 14, 4879
b-P4VP [30]. The broad peak near 1580 cm−1 still existed, indicating −1that the complexat
6 of 13
aromatic vibration of the pyridine ring, and the peak at 1595 cm corresponded to
of Zn with the carboxyl groups on the carboxyl-terminated polybutadiene was
2+
carbon-nitrogen bond (C-N) vibration. The peak of R2 and R2-0.5% appear at 1617 c
disrupted. There−1was a clear relationship between the vasym(COO−) and vsym(COO−) bands in
next to 1595 cm , revealing the complexation of Zn 2+ with the N atom of pyridine on
FTIR spectra (region
carbon-nitrogen bond (C-N)of 1300–1750
vibration.cm The )peak
−1 and the metal-carboxylate coordination
R2 and R2-0.5% appear at 1617 cm−1 type.
b-P4VP [30]. The
− 1 broad peak near 1580 cm−1ofstill
2+ existed, indicating that the complexa
separation
next to 1595 of
cmthe bands (Δv
, revealing thea-s = vasym − vof
complexation ) canwith
symZn indicate of the
the N atom of structure
pyridine onof PS-carboxy
of Zn [30].
b-P4VP
2+ with Thethe
broad carboxyl
peak groups on the existed,
−1 still carboxyl-terminated thepolybutadiene was
[31]. The value for Δv a-s near
for 1580
Zn2+cmwas almost equal indicating
thanthat
that complexation
of Na +, revealing t
disrupted.
of Zn withThere
2+ the was a clear
carboxyl groupsrelationship
on was between the vasym(COO
the carboxyl-terminated
−) and vsym(COO
polybutadiene was not
− ) bands in
coordination mode in PB-COOZn bidentate bridging (Figure 3b) [32].
− and v − bands type.
FTIR spectra
disrupted. There(region of 1300–1750
was a clear relationship cmbetween
−1) and thethevmetal-carboxylate
asym(COO ) coordination
sym(COO )
separation of the (region
in the FTIR spectra bands of (Δv a-s = vasym
1300–1750 cm− −v1sym ) can
) and the indicate of the structure
metal-carboxylate coordinationof carboxy
type. The separation of the bands (∆v = v − v ) can
[31]. The value for Δva-s for Zn was almost equal than that of Na , revealing
2+
a-s asym sym indicate of the structure
+ of
carboxylate [31]. The value for ∆v a-s for Zn 2+ was almost equal than that of Na+ , revealing
coordination mode in PB-COOZn was bidentate bridging (Figure 3b) [32].
that coordination mode in PB-COOZn was bidentate bridging (Figure 3b) [32].

Figure 3. (a) FTIR spectra for component polymers and their blends. (b) The frequency separat
(Δva-s) between the symmetric and asymmetric stretching modes of COO− in R2 and PBCOOZn

3.2. Thermodynamic Property

Figure 3.3.(a)
Figure (a)FTIR
FTIR spectra for component
spectra polymers
for component and their
polymers blends.
and their(b) The frequency
blends. (b) Theseparations
frequency separat
(∆va-sAs shown in Figure and4 and Table 2, the DSC curves
− in R2were used to reveal
(Δv a-s)) between
betweenthe symmetric
the symmetric asymmetric
and stretching
asymmetric modes
stretching ofmodes
COO of COO and PBCOOZn.
− in R2 and PBCOOZn
thermodynamic properties of the samples. The Tg values of R1, R2 and R3 were 87 °C
3.2. Thermodynamic Property
°C
3.2.and 100 °C, respectively,
Thermodynamic Property indicating that more effective metal coordination bonds w
As shown in Figure
formed with the increase of PS-b-P4VP4 and Table 2, the DSC curves were used
content in theto reveal
system,the thermody-
which led to
namicAs shown ofintheFigure
properties samples. 4 The
andTgTablevalues2, the R2
of R1, DSCand R3curves
were 87 ◦ C, 92
were used◦ C andto reveal
thermodynamic transformation tending to a higher temperature. However, the Tg val
100 ◦ C, respectively,properties
thermodynamic indicating that more
of the effectiveThe
samples. metal Tgcoordination
values of R1, bondsR2 were
and formed
R3 were 87 °C
of
withthe samples
the increase gradually
of PS-b-P4VP decreased
content as
in thesystem,
the contentwhich of O-CNOs
led to increased.
the thermodynamic This may be
°C and 100 °C, respectively, indicating that more effective metal coordination bonds w
to the poor interfacial
transformation tending interaction between PS-b-P4VP
to a higher temperature. However, the andTO-CNOs
g values ofin the
the system result
samples
formed with the increase of PS-b-P4VP content in the system, which led to
in the formation of extra free volume between filler and matrix. The polymer
gradually decreased as the content of O-CNOs increased. This may be due to the poor inter-chains n
thermodynamic
facial interaction transformation
between PS-b-P4VP tending
andthis
O-CNOs to a higher
in the systemtemperature.
resulting However, the Tg va
the interface optionally transfer into free volume, resulting inin the formation
increased chain mobi
of the
of extra samples gradually
free volumeTbetween filler and matrix. The polymer chains near the interface option-may be
decreased as the content of O-CNOs increased. This
and decreased g value. Previous studies by BalajiKrishnakumar et al. [33]
to
allythe poor into
transfer interfacial
this freeinteraction between
volume, resulting PS-b-P4VP
in increased chain and O-CNOs
mobility in the system
and decreased Tg resul
GaniuB.Olowojoba
value. Previous studies
etbyal. [34] showed that
BalajiKrishnakumar et
the
al. [33]
Tand
g value gradually decreased with
GaniuB.Olowojoba et al. [34]
in the formation of extra free volume between filler and matrix. The polymer chains n
increase
showed of graphene
that the Tg valueoxidegraduallyadded to thewith epoxy resin system, and oxide
the same mechan
the interface optionally transfer decreased
into this free volume, the increase of graphene
resulting in increased addedchain mob
may
to theplayepoxy a resin
role system,
here. Meanwhile,
and the same sincemechanismthe self-healing
may play a role performance
here. Meanwhile, of the material w
since
and decreased Tg value. Previous studies by BalajiKrishnakumar et al. [33]
closely related to the dynamic reversibility of metal coordination bonds, the reduction
the self-healing performance of the material was closely related to the dynamic reversibility
GaniuB.Olowojoba et al.the [34] showed of Tthat the Tg valueto thegradually
self-healingdecreased
property with
Tofg was
metalbeneficial
coordination tobonds,
the self-healingreduction property g wasat beneficial
low temperature.
increase of
at low temperature. graphene oxide added to the epoxy resin system, and the same mechan
may play a role here. Meanwhile, since the self-healing performance of the material
closely related to the dynamic reversibility of metal coordination bonds, the reductio
Tg was beneficial to the self-healing property at low temperature.

Figure 4. DSC curves of component polymers.

Polymers 2022, 14, 4879 7 of 13

Table 2. Tg value of different samples.

Samples R1 R2 R3 R2-0.5% R2-1% R2-2%

Tg 87 ◦C 92 ◦C 100 ◦C 85 ◦C 81 ◦C 74 ◦ C

3.3. Mechanical Property

Figure 5 shows the mechanical properties of various samples. With the increase of VP
content, the tensile strength of the samples gradually increased from 0.76 MPa ± 0.09 MPa
(R1) to 2.41 MPa ± 0.02 MPa (R3), and the elongation at break decreased gradually from
2009 ± 36% (R1) to 674 ± 50% (R3) (Figure 5a,d,e). Since the coordination number of Zn2+
was 4 [35,36], when the molar ratio of Zn2+ :COO− :VP was 1:2:2, the molar ratio of Zn2+ to
ligand reached the stoichiometric equivalent, and the tensile strength should reach the the-
oretical maximum value at this time. However, there will be uncoordinated free ligands in
the system due to the steric hindrance and high viscosity of rubber. Therefore, higher molar
ratios were required to ensure complete complexation and better mechanical properties.

Figure 5. Mechanical properties of the samples. (a,b) Stress–strain curves for samples. (c) Continuous
cyclic tensile loading–unloading curves at 50% strain without resting time between each cycle.
(d,e) Elongation at break and Tensile strength of the samples.

With the increase of O-CNOs content, the tensile strength of the composites gradually
decreased from 1.28 ± 0.01 MPa (R2-0.5%) to 0.83 ± 0.01 MPa (R2-2%) (Figure 5b,d,e).
However, the tensile strengths of the samples added with O-CNOs (R2-0.5%, R2-1% and
R2-2%) were consistently higher than the original samples (R2). However, the mechanical
properties of R2-0.25% decreased sharply and were even lower than the R2. This appearance
could be attributed to the formation of inhomogeneous defect sites in the composite due to
the low content of OCNOs, which led to the decrease of the overall mechanical properties.
This indicated that appropriate doping of O-CNOs can improve the mechanical properties
of the composites through the interaction between O-CNOs and polymer segments, while
excessive doping of O-CNOs may aggregate, which can create defects in the system,
resulting in the poor mechanical properties of the composites.
The scanning electron microscope (SEM) was used to study the dispersion of O-CNOs
in composite to illustrate the good mechanical properties. As shown in Figure 6, compared
with R2, the uniformly dispersed O-CNOs in the surface and cross-section can be clearly
observed in SEM images of R2-0.5. The uniform dispersion of O-CNOs was the guarantee
to improve the mechanical properties of the composites.
4, 4879 8 of 13

14, 4879 Polymers 2022, 14, 4879 8 of 138 of 13

Figure 6. SEM images of R2-0.5 and R2 in surface and cross section mode.

Figure 5c shows the cyclic tensile loading–unloading curves of R2-0.5% at room

temperature.
Figure 6. SEM The
images gradual reduction
Figureof6. R2-0.5 and R2
SEM images in of the
surface
of R2-0.5 and R2
hysteresis
and loop mode.
cross section
in surface
with
and cross
the progress of cyclic
section mode.
stretching proved the dynamic properties of metal coordination bonds. The bond energy
of theFigure
coordination
5c shows Figure
bond 5c showstensile
thebetween
cyclic the carboxyl
the cyclic tensile
grouploading–unloading
loading–unloading and Zncurves curves
2+ was 104–134
of R2-0.5% ofkJ/mol
R2-0.5% at room
[37],
at room
and temperature.
that of between pyridine The gradual
and Zn2+ reduction of the hysteresis loop with the progress of cyclic
temperature. The gradual reduction ofwasthe approximately
hysteresis loop250 with kJ/mol [38]. TheofZn(Ⅱ)-
the progress cyclic
stretching proved the dynamic properties of metal coordination bonds. The bond energy of
carboxy coordination
stretching provedthe the
bond
dynamic
coordination
with lower
properties
bond
energy
between of
was coordination
themetal
carboxyl
broken first, and
group and Znbonds.
2+ wasthe104–134
TheZn(Ⅱ)-pyridine
bond energy
kJ/mol [37], and
coordination bond
of the coordination
that ofwith
bond higher
between
between energy
theand
pyridine was
carboxyl broken
Zn wasgroup
2+ later (Figure
and Zn 250was
approximately 2+ 7).
104–134
kJ/mol The dynamic
kJ/mol
[38]. The [37],
Zn(II)-carboxy
reversibility of coordination
and that of betweenthe metal
pyridinecoordination
bond and
with Zn bonds
2+ was
lower energy enabled
approximately
was the 250
broken first, continuous
and kJ/mol breaking
[38]. and
The coordination
the Zn(II)-pyridine Zn(Ⅱ)-
reformation of the
bond twowithcoordination
higher energy bonds
was (Zn(Ⅱ)-carboxyl
broken later (Figure and
7).
carboxy coordination bond with lower energy was broken first, and the Zn(Ⅱ)-pyridine Zn(Ⅱ)-pyridine)
The dynamic during
reversibility of the
the metal
stretching bond coordination
processwith and higher bonds
led to the enabled
folding the continuous breaking and reformation which two
of the
coordination energy wasand sliding
broken of the
later polymer
(Figure 7). Thechain,dynamic
coordination bonds (Zn(II)-carboxyl and Zn(II)-pyridine) during the stretching process and
dissipated a mass
reversibility of ledof energy,
the resulting in the
metal coordination composite
bonds enabled withthesuperior tensilebreaking
continuous strength andand
to the folding and sliding of the polymer chain, which dissipated a mass of energy,
toughness.
reformation of the two in
resulting coordination
the compositebonds (Zn(Ⅱ)-carboxyl
with superior andand
tensile strength Zn(Ⅱ)-pyridine)
toughness. during
the stretching process and led to the folding and sliding of the polymer chain, which
dissipated a mass of energy, resulting in the composite with superior tensile strength and
toughness.

Figure
Figure 7. Schematic 7. Schematic
illustration illustration
of the of themechanism.
self-healing self-healing mechanism.

3.4. Self-Healing Ability

3.4. Self-Healing Ability
To investigate the self-healing properties of the R2-0.5%, the original composite was cut
intoillustration
To7.investigate
Figure Schematic two self-healing
the separate
ofsamples using a blade.
properties
the self-healing of theThe two sections
R2-0.5%,
mechanism. theformed
originalafter cutting were
composite wasaligned
◦
cut into two separate samples using a blade. The two sections formed after cutting were C for
and pressed gently for 1 min, which were transferred to a vacuum drying oven at 85
3.4. Self-Healinghealing.
Ability It can be seen that the fracture interface of the composite was completely healed
aligned and pressed gently for 1 min, which were transferred to a vacuum drying oven at
and the crack disappeared (Figure 8a,b). Likewise, the same cutting-aligning-heat treatment
85 °C To
forinvestigate
healing.was
It can
the be seenonthat
self-healing
performed the fractureof
properties
dumbbell-shaped interface ofto
the R2-0.5%,
elastomer the composite
the
achieveoriginal was completely
composite
self-repairing was The
behavior.
healed
cut intoand
twothe crack disappeared
separate samples using(Figure 8a,b).
a blade. TheLikewise, the same
two sections cutting-aligning-heat
formed after cutting were
treatment
aligned and was performed
pressed on 1 dumbbell-shaped
gently for elastomer totoa vacuum
min, which were transferred achieve drying
self-repairing
oven at
behavior. The self-healed
85 °C for healing. It can bedumbbell-shaped composite
seen that the fracture was
interface of taken out and cooled
the composite to room
was completely
temperature, and then subjected to stress–strain testing at a tensile rate of 10 mm
healed and the crack disappeared (Figure 8a,b). Likewise, the same cutting-aligning-heat min−1.
4, 4879 9 of 13
Polymers 2022, 14, 4879 9 of 13

Figure 8c shows the stress–strain curves and self-repairing efficiency of the composite
self-healed dumbbell-shaped composite was taken out and cooled to room temperature,
after heat treatment at 85 °C for 1 h, 2 h, 4 h and 6 h, respectively. The results showed that
and then subjected to stress–strain testing at a tensile rate of 10 mm min−1 . Figure 8c
the tensile strength andthe
shows elongation at break
stress–strain curvesof theself-repairing
and composite gradually
efficiency ofincreased withafter
the composite the heat
extension of heattreatment
treatment time
at 85 ◦ and1 h,
C for were
2 h, more
4 h andand
6 h,more close to
respectively. Thethe original
results state.
showed thatNote
the tensile
that the self-healing efficiency
strength of theatcomposite
and elongation break of the can reachgradually
composite 83 ± 10% after 6with
increased h of theheat
extension
of heat treatment time and were more and more close to the
treatment (Figure 8d). Compared with other advanced self-healing materials reported so original state. Note that the
self-healing efficiency
far, the metal-ligand-based of the
self-healing composite
R2-0.5% has can reach
better 83 ± 10% after
self-healing 6 h of heat
properties treatment
(Figure
(Figure 8d). Compared with other advanced self-healing materials reported so far, the
8e).
metal-ligand-based self-healing R2-0.5% has better self-healing properties (Figure 8e).

Figure
Figure 8. (a) Optical 8. (a) of
images Optical
cut, images
healedofandcut,stretching
healed and R2/R2-0.5%
stretching R2/R2-0.5%
specimen. specimen. (b) Microscope
(b) Microscope
image of the surface of the sample. (c) Typical stress–strain curves with
image of the surface of the sample. (c) Typical stress–strain curves with different healing times. different healing
(d) times.
(d) Corresponding
Corresponding healing efficiency ofhealing efficiency
the R2-0.5% of the R2-0.5%
at different times.at(e)different times. of
Comparison (e)self-repairing
Comparison of self-
performance using this work with previous reports [39,40,41,42,43,44,45]. (f) The proposed self-healing
repairing performance using this work with previous reports [39–45]. (f) The proposed self-
healing mechanism mechanism
of R2-0.5%.of R2-0.5%.

The essence of the excellent self-healing ability of composite was further explained
The essenceby
ofthe
thesupramolecular
excellent self-healing
interaction.ability
Figureof8f composite was further
shows the mechanism explainedeffect.
of self-healing
by the supramolecular
When theinteraction. Figure
composite was 8f shows
damaged, themetal
the two mechanism of self-healing
coordination effect. and
bonds [Zn(II)-carboxyl
When the composite was damaged, the two metal coordination bonds [Zn(Ⅱ)-carboxyl
and Zn(Ⅱ)-pyridine] at the fractured interface were broken. The mobility of the polymer
chains was greatly enhanced and accompanied by a reversible decrease in viscosity
during the heat treatment at 85 °C, which promoted the rearrangement of the chains.
 Polymers 2022, 14, 4879 10 of 13

Zn(II)-pyridine] at the fractured interface were broken. The mobility of the polymer chains
Polymers 2022, 14, 4879 10 of 13
was greatly enhanced and accompanied by a reversible decrease in viscosity during the heat
treatment at 85 ◦ C, which promoted the rearrangement of the chains. Meanwhile, when the
fractured interfaces were in contact with each other, the polymer chains diffused into each
other
higher and were
healing accompanied and
temperature by thelonger
reformation of two
healing timemetal coordination
endowed the bonds,
polymerresulting
chains with
in the healing of the fractured interfaces. Additionally, both higher healing temperature and
better fluidity, resulting in superior self-healing ability and mechanical properties. Note
longer healing time endowed the polymer chains with better fluidity, resulting in superior
thatself-healing
the O-CNOs as fillers reduced the Tg value of the R2 and thus enhanced the mobility
ability and mechanical properties. Note that the O-CNOs as fillers reduced the
of the
Tg polymer
value of the chains,
R2 andwhich improved
thus enhanced the self-healing
the mobility properties
of the polymer chains, of composite.
which improved
Note
the that theproperties
self-healing self-healing effect of R2 and R2-0.5 can also occur at room temperature
of composite.
As shown Note inthat the self-healing
Figure 9, after 48effect
h ofofhealing
R2 and R2-0.5
process canatalso
roomoccurtemperature,
at room temperature.
the scratched
As shown in Figure 9, after 48 h of healing process at room temperature,
incision on the both sample surfaces were bonded and only minor cracks were observed the scratched
incision on the both sample surfaces were bonded and only minor cracks were observed,
demonstrating the great potential of metal coordination bonds with dynamic reversibility
demonstrating the great potential of metal coordination bonds with dynamic reversibility
in room
in room temperature self-repairing
temperature self-repairing (Figure
(Figure S1, Supporting
S1, Supporting Information).
Information). Moreover, Moreover,
R2-0.5% R2-
0.5%had
had a faster healing rate, which can be attributed to the addition
a faster healing rate, which can be attributed to the addition of O-CNOs that reduced of O-CNOs that
reduced
the Tgthe Tg composite
of the of the composite and enhanced
and enhanced the polymerthe polymer
chain chain flowability.
flowability.

Figure 9. Self-healing
Figure 9. Self-healingeffect
effectoccurred
occurred atatroom
room temperature
temperature (R.T.).
(R.T.).

Healing of polymeric materials included crack closure and crack healing. Crack closure
Healing of polymeric materials included crack closure and crack healing. Crack
was essential for subsequent crack healing. The damage of materials was often accompanied
closure was essential for subsequent crack healing. The damage of materials was often
by large deformations or cracks inside the materials in practical applications, which made
Polymers 2022, 14, 4879 accompanied 11 of
it difficult forby large deformations
the material or external
to self-repair without cracks force
inside the materials
intervention. To addressinthispractica
applications,
challenge, thewhich
shapemade it difficult
memory forproposed
effect was the material to self-repair
to rapidly without
close the crack external force
to facilitate
the self-healing
intervention. process this
To address (Figure 10). Herein,
challenge, theashape
series of novel supramolecular
memory elastomers
effect was proposed to rapidly
were
close prepared
memory-assisted by introducing
the crack to facilitate metal coordination
the performance
self-healing self-healing process between
of R2-0.5 carboxyl-terminated
(Figure 10). Herein,
was studied polybu-
a series above.
as mentioned of noveA
tadiene and polystyrene-vinylpyridine copolymer. Under the synergistic effect of metal
supramolecular
shown in Figure elastomers
S2, U shapedwereR2-0.5
prepared by introducing
showed a good shape metal coordination self-repa
memory-assisted between
coordination and microphase separation of supramolecular polymers, the polystyrene-
carboxyl-terminated
performance,
vinylpyridinewhich polybutadiene
indicated
aggregates can act that and polystyrene-vinylpyridine
addingofO-CNOs
as a network nodes thatnot only
define copolymer.
theenhanced
permanentthe Under
mechanic
shape, the
synergistic
properties effect of metal
and self-healing
the carboxyl-terminated coordination
properties
polybutadiene andalso
but
aggregates microphase
canmaintained separation of supramolecular
thesegments
act as switching shape memory-assiste
for fixing
polymers,
self-repairing
the temporary performance. 2+
the polystyrene-vinylpyridine
shape, and the Zn acted asaggregates can act
bridges to connect as awhich
them, network
allowedof nodes
the that
system to generate shape memory effect.
define the permanent shape, the carboxyl-terminated polybutadiene aggregates can act as
switching segments for fixing the temporary shape, and the Zn2+ acted as bridges to
connect them, which allowed the system to generate shape memory effect.
Before that, the shape fixation rate and recovery rate before and after the addition of
O-CNOs were calculated by testing the length of the original sample, the sample stretched
toFigure
the elongation
Figure state,
Schematic
10.10.Schematic and the
illustration
illustration ofsample
of the with
shape memory
the shape shape
memoryassistedrecovery.
self-healingThe
assisted shape
process.
self-healing fixation rates of
process.
R2 and R2-0.5 were ~96% and ~93%, respectively, while their shape recovery rates were
Before that, the shape fixation rate and recovery rate before and after the addition of
~75% and ~64%,
O-CNOs were respectively. The addition
calculated by testing the lengthofofO-CNOs slightly
the original sample,led
thetosample
the decrease
stretchedof shape
fixation
to theand recovery
elongation state,rate
andofthethe
samplecomposites,
with shapewhich
recovery.may Thebe attributed
shape to the
fixation rates of friction
resistance
R2 and produced
R2-0.5 wereby O-CNOs.
~96% and ~93%, respectively, while their shape recovery rates were
~75% and ~64%,two
Specifically, respectively.
samples The withaddition
the sameof O-CNOs
ratio asslightly
R2 were led to the decrease
casted of
as U-shape and
shape fixation and recovery rate of the composites, which may be attributed
rectangular strip, and denoted as R2U and R2S, respectively. The rectangular strip sample to the friction
resistance produced by O-CNOs.
R2S would endure a shape change and recovery process during which R2S was firstly
bent into U-shape after being thoroughly heated at 60 °C and then cooled to fix the
temporary U-shape. R2U and R2S, both in the U-shape state, were then scratched with a
blade and simultaneously placed in a temperature environment of 60 °C (Figure 11a). As
shown in Figure 11b–i, the incision on the sample R2S was quickly closed within 30 s, and
 Polymers 2022, 14, 4879 11 of 13

Specifically, two samples with the same ratio as R2 were casted as U-shape and
4, 4879 11 of 13
rectangular strip, and denoted as R2U and R2S, respectively. The rectangular strip sample
R2S would endure a shape change and recovery process during which R2S was firstly bent
into U-shape after being thoroughly heated at 60 ◦ C and then cooled to fix the temporary
U-shape. R2U and R2S, both in the U-shape state, were then scratched with a blade and
memory-assisted self-healing performance of R2-0.5 was studied as mentioned above. As
simultaneously placed in a temperature environment of 60 ◦ C (Figure 11a). As shown in
shown in Figure Figure
S2, U11b–i,
shaped R2-0.5 showed a good shape memory-assisted self-repair
the incision on the sample R2S was quickly closed within 30 s, and the incision
performance, which indicated healed
was completely that adding
within 80O-CNOs notincision
s, while the only enhanced
of the R2U the
was mechanical
not closed without
properties and self-healing
external force properties
intervention,but also
and it wasmaintained the
difficult to start its shape memory-assisted
self-healing process. These results
show that the prepared samples have outstanding shape memory assisted self-healing
self-repairing performance.
behavior. The energy stored by the temporarily state of shape memory process can quickly
drive the crack closure, promote the start of self-healing process. This shape memory
assisted self-healing performance can generally shorten the time required for self-healing
and improve the self-repair efficiency. The similar shape memory-assisted self-healing
performance of R2-0.5 was studied as mentioned above. As shown in Figure S2, U shaped
R2-0.5 showed a good shape memory-assisted self-repair performance, which indicated that
adding O-CNOs not only enhanced the mechanical properties and self-healing properties
Figure 10. Schematic illustration of the shape memory assisted self-healing process.
but also maintained the shape memory-assisted self-repairing performance.

Figure 11. Snapshots of the

Figure shape memory
11. Snapshots assisted
of the shape self-healing
memory process. (a)
assisted self-healing 0s, (b)10s,
process. (c) 20s,
(a) 0s, (b)10s, (c)(d)
20s, (d) 30s,
30s, (e) 40s, (f) 50s,(e)
(g)40s,
60s, (h) 70s, (i) 80s.
(f) 50s, (g) 60s, (h) 70s, (i) 80s.

4. Conclusions 4. Conclusions
In this paper, the elastomer with good shape memory effect, self-healing ability and
In this paper, the elastomer with good shape memory effect, self-healing ability and
mechanical properties was designed by introducing metal coordination and nano-filler
mechanical properties
into thewas designedrubber/polystyrene-vinylpyridine
polybutadiene by introducing metal coordination andThe
copolymer. nano-filler
result indicated
into the polybutadiene rubber/polystyrene-vinylpyridine ◦ copolymer. The result indicated
that the elastomer can be self-repaired at 85 C for 6 h, and its repair efficiency can reach
that the elastomer ± 10%.
83can be self-repaired at 85O-CNOs
The well-dispersed °C for reduced
6 h, andtheitsintermolecular
repair efficiency can reachforces,
chain interaction
83 ± 10%. The well-dispersed O-CNOs reduced the intermolecular chain interaction forces,ability.
and the polymer chain mobility was enhanced, thus improving the self-healing
and the polymerMoreover, the functionalized O-CNOs provide more abundant carboxyl groups, which
chain mobility was enhanced, thus improving the self-healing ability.
enhanced the internal hydrogen bonding to improve the mechanical properties. The as-
Moreover, the functionalized
prepared polymer O-CNOs
also showsprovide morememory
good shape abundant carboxyl
assisted groups,
self-healing which This
performance.
enhanced the internal
uniquehydrogen bonding
molecular network to improve
design the mechanical
not only provided properties.
a new network The approach
construction as-
prepared polymer foralso
the shows good of
development shape
new memory
rubbers toassisted self-healingbut
replace vulcanization performance. This
also blazed the way for
unique molecular the network
manufacturing
designof advanced
not onlyelastomers
providedwith a
bothnew excellent mechanical
network properties and
construction
self-healing ability.
approach for the development of new rubbers to replace vulcanization but also blazed the
way for the manufacturing of advanced elastomers with both excellent mechanical
properties and self-healing ability.

Supplementary Materials: The following supporting information can be downloaded at:

Polymers 2022, 14, 4879 12 of 13

Supplementary Materials: The following supporting information can be downloaded at:

https://www.mdpi.com/article/10.3390/polym14224879/s1, Figure S1: Self-healing effect of a
rectangular R2-0.5 occurred at room temperature (R.T.); Figure S2: Self-healing effect of a U-shaped
R2-0.5 occurred at room temperature (R.T.).
Author Contributions: Conceptualization, F.X. and X.G.; methodology, W.X. and L.L.; software,
Z.P.; validation, Y.D., F.Z. and C.Z.; investigation, L.L. and Z.P.; data curation, L.L. and Z.P.;
writing—original draft preparation, Z.P. and F.X.; writing—review and editing, F.X. and Z.P.; funding
acquisition, F.X. and X.G. All authors have read and agreed to the published version of the manuscript.
Funding: This research is supported by the National Natural Science Foundation of China (Grant
No. 11902099 and No. 11902100) and the Science Foundation of National Key Laboratory of Science
and Technology on Advanced Composites in Special Environments (Grant Nos. JCKYS2022603C018
and JCKYS2022603C019).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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