Materials Today Communications 17 (2018) 419–426

Contents lists available at ScienceDirect

Materials Today Communications

journal homepage: www.elsevier.com/locate/mtcomm

Bioinspired poly(vinyl alcohol)-silk hybrids: Two-way water-sensitive T

shape-memory materials
⁎
Lin Gua,b, Yuanzhang Jiangb, Jinlian Hub,
a
Key Laboratory of Marine Materials and Related Technologies, Key Laboratory of Marine Materials and Protective Technologies of Zhejiang Province, Ningbo Institute of
Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, 315201, PR China
b
Institute of Textiles & Clothing, The Hong Kong Polytechnic University, Hong Kong, 999077, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Water-sensitive shape memory polymers have drawn significant attention because water is the safest stimulus for
Silk living organisms which is much easier to be performed in biological applications. Inspired by the water-sti-
Shape memory mulated shape memory behavior of supercontracted spider silks, silk fibroin with β-sheet structure is introduced
Two-way into poly(vinyl alcohol) (PVA) to develop a novel shape memory material. Bending test indicated that the ad-
Water-induced
dition of the silk fibroin favors good water-induced shape-memory effect (WSME) of the PVA/silk hybrids. More
Hybrids
importantly, the PVA/silk hybrids also display two-way WSME, which could mimic the behavior of pine cones to
close their scales in a wet state and open them again in a dry state. It is demonstrated that the asymmetric
laminated structure of the hybrids could attribute to the two-way shape-memory effect, whereas the competitive
hydrogen bonds between silk fibroin and PVA from water as “switch”, the β-sheet structure as “netpoint” and its
swelling plasticizing effect are main factors for the water-sensitive shape-memory behavior. These PVA/silk
hybrids not only possess biocompatibility and nontoxicity, but also have ease to be fabricated, which are pro-
mising in various potential applications such as biological, medical, textile, and toys.

1. Introduction poly(tetramethylene oxide) glycol-based network with tunable 2W-

Shape memory polymers (SMPs) as a branch of the significant smart
materials have drawn a great deal of attention owing to their out-
standing properties and wide potential applications such as actuators,
supercapacitors, high-performance textiles, and biomedical devices
[1–6]. Generally, the traditional SMPs always exhibit an ability to au-
tomatically recover to their permanent shape from the deformed shape
upon external stimuli, and this permanent shape remains unchanged
when an external reverse stimulus is applied [7–11]. This kind of shape
memory behavior is known to be one-way shape memory effect (1W-
SME) that is actually irreversible unless re-programming process has
been done [12,13]. On the contrary, two-way shape memory process is
fully reversible, meaning that the shape can vary between two dis-
tinguished shapes upon two external opposing stimuli [14,15]. Two-
way SMPs (2WSMPs) have become one of the hot spots of current re-
searches on smart materials because of their unique properties and
promising applications in actuators, sensors, and artificial muscles
[16–18]. Chen et al. reported a polymer laminate via layer technique
with the SMP and elastic polymer, which exhibited two-way shape
memory effect (2W-SME) [19]. Xie at al. prepared a semicrystalline
SWE via temperature-switched netpoints [12]. Recently, Wang et al.
designed a series of light-actuated 2W-SMPs by incorporating poly-
dopamine nanospheres into semicrystalline polymer networks based on
poly(ε-caprolactone) copolymers [20]. However, most of the widely
studied 2WSMPs by far are still limited by thermal, or light-triggered
[21].
In recent years, water-sensitive SMPs become promising candidates
to be performed in biological applications because water is the safest
stimulus for living organisms [22–24]. Since Huang et al. reported that
moisture can induce shape recovery in polyurethane SMPs [25], a
number of water-sensitive SMPs have been developed including cellu-
lose/elastomer nanocomposites, poly(ethylene glycol)-based copoly-
mers, and poly(vinyl alcohol) (PVA) nanocomposites [24,26–31]. Their
water-induced shape memory effect was based on the plasticizing effect
of water molecules and disruption of hydrogen bonds (HBs) in SMPs,
which thus increase the flexibility of the macromolecular chains and
lower the glass transition temperature [24,30,32]. In these SMPs, PVA
is known to be an attractive candidate because of its nontoxicity, bio-
compatibility, high hydrophilicity, easy processability and good me-
chanical properties [33,34]. Qi et al. designed a water-sensitive PVA-

⁎
Corresponding author.
E-mail address: jin-lian.hu@polyu.edu.hk (J. Hu).

https://doi.org/10.1016/j.mtcomm.2018.10.005
Received 6 September 2018; Received in revised form 7 October 2018; Accepted 8 October 2018
Available online 09 October 2018
2352-4928/ © 2018 Elsevier Ltd. All rights reserved.
L. Gu et al. Materials Today Communications 17 (2018) 419–426

Fig. 1. (a) Structural model of silk (spider silk, silkworm silk) and (b) proposed water-sensitive shape memory mechanical model of spider silk. (c) Cleavage and
reforming of hydrogen bonds between PVA and silk under effect of water.

Fig. 2. Characterization of PVA/silk hybrids with different silk contents. (a) FTIR and (b) Raman spectra. (c) Storage modulus and (d) tan δ curves.

420
L. Gu et al.
Fig. 3. Digital images illustrating the shape recovery behaviors of PVA/silk hybrids immersed in water.
based SMP material by introducing graphene oxide (GO) [30]. The
introduction of GO largely improved the shape memory properties of
PVA derived from the strong hydrogen bonding interactions between
GO and PVA. Yang et al. developed a luminescent water-induced SMP
composite by blending PVA and carbon quantum dots [24]. This com-
posite presents the advantages of excellent luminescent property and
water-induced tunable shape recovery performance. Nevertheless, these
studies of water-induced SMPs mainly focused on 1W-SME that limits
their wide applications. Consequently, it is expecting and of consider-
able significance to develop water-sensitive 2WSMPs that remain less
investigated.
Spider silks have been brought into the focus of research for decades
due to its perfect balance of strength and toughness [35]. Besides the
amazing mechanical properties, spider silks have another remarkable
feature called supercontraction, which describes their dramatic
shrinkage at high humidity [36]. Moreover, supercontracted spider
silks exhibit typical water-sensitive shape memory behavior, and the
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Materials Today Communications 17 (2018) 419–426
Fig. 4. Photography showing water-sensitive
two-way shape-memory effect of PVA/10% silk
hybrid.
Fig. 5. (a) the appearance of a pine cone in
simulation and (b) shape change of PVA/silk
hybrids in the wet and dry state.
mechanism can be explained by a switch-netpoint model as reported in
our previous work (Fig. 1) [37]. In the model, hydrogen bonding among
the amorphous regions of spider silk can act as a switch unit responsible
for temporary shapes, while β-sheet crystals play a netpoint role in
determining permanent shapes. Inspired by spider silks, we previously
designed shape memory biopolymers based on β-sheet crystals of
polyalanine segments [38]. The β-sheet crystals act as netpoints that are
responsible for the achievement of high shape fixity and excellent shape
recovery ability. However, spider silks are difficult to acquire on a
commercial scale, and the fabrication of the above-mentioned biopo-
lymers with β-sheet structure is complicated. Compared to spider silks,
silkworm silks also have β-sheet structure, and could be easily obtained
in large amounts, but could not display water-sensitive shape memory
effect [39,40].
In this work, inspired by spider silks, biocompatible PVA/silkworm
silk hybrids were prepared to develop a novel shape memory material.
In the proposed model, the reversible cleavage and reforming of
L. Gu et al.
Fig. 6. Characterization of PVA/5% silk immersed in water for different times.
(a) Storage modulus and (b) tanδ curves. (c, d) FTIR spectra. (e) WAXD profiles. (f) Weight swelling degree and volume swelling degree as a function of immersion
time.
hydrogen bonds between PVA and silk could act as switches to trigger
the shape deformation (Fig. 1). Interestingly, the hybrids reveal two-
layer structure, where the silk fibroin is enriched in one layer. More
importantly, these hybrids exhibit water-induced two-way shape-
memory effect (2WSME) due to asymmetric laminated structure, which
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Materials Today Communications 17 (2018) 419–426
could mimic the behavior of pine cones to close their scales in a wet
state and open them again in a dry state. It should be pointed that these
hybrids are biocompatible and nontoxic, and are easy to be prepared,
which possess great potential in biological, medical, textile, and toys
applications. We believe this work will offer new insight for developing
L. Gu et al.
Fig. 7. SEM images of the cross-section of PVA/silk hybrid.
Fig. 8. Schematic illustration of the two-way shape-memory behavior of PVA/silk hybrids actuated with water.
intelligent water-induced 2WSMPs materials.
2. Experimental section
2.1. Materials
Poly(vinyl alcohol) (PVA, Mw 89,000–98,000, 99+% hydrolyzed)
was purchased from Sigma-Aldrich and used as received.
Hexafluoroisopropanol (HFIP) was provided by J & K Scientific Ltd and
used as received. Degummed silk fibroin was obtained from Bombyx
mori cocoons according to the literature [41].
2.2. Fabrication of PVA/silk hybrids
PVA and degummed silk fibroin were completely dissolved in HFIP
to form a 4 w/v% solution, respectively. The resultant solutions were
then mixed at various weight ratios of PVA/silk (95/5, 90/10, 80/20).
The PVA/silk solutions were poured into Teflon molds and dried at
room temperature overnight, and then further dried in vacuum at 60 °C
for 24 h. Finally, the PVA/silk films with a thickness of ∼0.15 mm were
obtained. The pure PVA film was also prepared as a control using the
same procedure.
2.3. Characterization and measurements
Fourier transform infrared (FTIR) spectra were performed on a
PerkinElmer Spectrum 100 FTIR spectrometer. Raman spectra were
obtained on a BaySpec 3 in 1 Nomadic Raman Microscope using the
wavelength of 532 nm. Dynamic mechanical analysis (DMA) was car-
ried out using a METTLER TOLEDO DMA1 at a heating rate of 10 °C/
min and a frequency of 1 Hz from −50 °C to 150 °C. Wide angle X-ray
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Materials Today Communications 17 (2018) 419–426
diffraction (WAXD) patterns were collected on a Rigaku SmartLab X-ray
diffractometer using Cu Kα radiation (1.54 Å). Samples were scanned
from a diffraction angle 2θ = 5° to 45° at a scan speed of 10°/min.
Differential scanning calorimetry (DSC) analysis was conducted on a
PerkinElmer DSC 8000 instrument under a N2 flow from −30 °C to
250 °C at a rate of 10 °C/min. Thermogravimetric analysis (TGA) was
performed on a METTLER TOLEDO thermal analyzer under a N2 flow at
a heating rate of 10 °C/min from 50 °C to 600 °C. Tensile test was car-
ried out on an Instron 5566 instrument with a tensile rate of 10 mm/
min at room temperature (22 °C). Scanning electron microscope (SEM)
images were obtained on a JEOL JSM-6490 SEM instrument under a
20 kV acceleration voltage.
The weight and volume swell degrees of the PVA/silk films were
defined as (Wwet―Wdry)/Wdry ×100% and (Vwet―Vdry)/Vdry ×100%,
respectively, where Wdry and Vdry were the weight and volume before
immersed in water and Wwet and Vwet the weight and volume after
immersed in water at different time intervals, respectively. Before test,
all the samples were dried in vacuum at 80 °C for 24 h. Samples with a
rectangle size of 5 mm × 10 mm and 5 mm × 35 mm were prepared for
DMA and tensile test, respectively.
The bending test was employed to evaluate the water-induced shape
memory behavior of the PVA/silk films [42]. Firstly, a straight spe-
cimen (3 mm × 20 mm) was bent to an angle at 80 °C. Subsequently, it
was cooled down to room temperature (22 °C) with an external force to
maintain the deformation. Then the deformed specimen was immersed
in water for free recovery at room temperature.
3. Results and discussion
3.1. Characterization of PVA/silk hybrids
Biocompatible PVA/silk hybrids were fabricated by a solvent
L. Gu et al.
casting method, where the hybrids containing 5%, 10%, and 20% silk
fibroins are nominated as PVA/5% silk, PVA/10% silk, and PVA/20%
silk, respectively. Silk fibroins have a highly repetitive amino acid se-
quence that could generate strong hydrogen bonding interactions with
PVA. FTIR and Raman spectroscopy were used to confirm the interac-
tions between the silk fibroin and PVA (Fig. 2a and b). Fig. 2a shows the
FTIR spectra of the obtained PVA/silk hybrids with different silk con-
tents. The silk film exhibits an absorption peak at 1625 cm−1 as the key
characteristic of the antiparallel β-sheet structure [10,43], and it is
different from the silk film prepared using aqueous solution (random
coil conformation) [44]. It should be pointed out that the β-sheet
conformation of the silk fibroin does not be changed by blending with
PVA. As for PVA, the broad absorption band at 3253 cm-1 is associated
with the eOH stretching vibration, which is generally sensitive to hy-
drogen bonds (HBs) [30]. In comparison, this stretching peak for eOH
groups shifts to ca. 3280 cm−1 in the case of PVA/silk hybrids, in-
dicating the existence of hydrogen bonding interactions between the
silk fibroin and PVA [24,30,45].
Fig. 2b shows the Raman spectra of the obtained PVA/silk hybrids.
The spectrum of pure PVA reveals the CeO stretching band at
1095 cm−1, whereas a lower wavenumber (ca. 1040 cm−1) is found for
the PVA/silk hybrids. This result implies the presence of HBs between
the silk fibroin and PVA [24]. Furthermore, the emerging absorption
peak at ca.1243 cm−1 also corresponds to the β-sheet conformation of
PVA/silk hybrids [46].
Fig. 2c and d show the thermomechanical properties of the obtained
PVA/silk hybrids with different silk contents. The storage modulus of
PVA/silk hybrids significantly increases with the increase of the silk
content, and the glass transition temperature (Tg, determined from tanδ
curves) increases from 47 °C (for PVA) to 57 °C (for PVA/20% silk). In
addition, the effect of silk content on the crystallinity of PVA was also
investigated by DSC and WAXD (see Figs. S2-3 and Table S1). A decline
in crystallinity degree and the slight increase in the melting tempera-
ture can be seen for the PVA in the obtained hybrids. These results
further demonstrate the strong interactions formed in the hybrids
[24,30].
3.2. Water-sensitive two-way shape memory effect of PVA/silk hybrids
Classical bending test was used to observe the water-induced shape
recovery behavior of the PVA/silk hybrids. Straight specimens were
bent to an angle at 80 °C and maintained the deformation with an ex-
ternal force during cooled down to room temperature. After that, the
deformed specimens were immersed in water and their shape recovery
processes were recorded with time, as shown in Fig. 3. It is clear that
pure PVA sample cannot recover to its original straight shape even after
300 s, while the PVA/silk hybrids can return to their original shapes
quickly within 190 s when they were immersed in water. This result
clearly demonstrates that the PVA/silk hybrids exhibit a better shape
recovery than pure PVA.
More importantly, the PVA/silk hybrids still present water-sensitive
reversible shape memory behavior without any shape memory pro-
gramming, which is called two-way water-sensitive shape-memory ef-
fect (2W-WSME). The PVA/10% silk hybrid was selected as a re-
presentative sample to display 2W-WSME, as shown in Fig. 4. The
straight strip was immersed in water and spontaneously cuddled up in a
heap. After dry at air, the deformed sample could regain its initial
straight shape. The entire process can be repeated many times. The two-
way water-sensitive shape-memory PVA/silk hybrids are of great po-
tential in various applications such as textiles, artificial muscle, actua-
tors, and sensors [14]. To our best knowledge, this is the first time
obtaining a hybrid with 2W-WSME via one-step preparation method.
Furthermore, this PVA/silk hybrids could mimic the behavior of pine
cones to close their scales in a wet state and open them again in a dry
state (Fig. 5) [47].
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Materials Today Communications 17 (2018) 419–426
3.3. Mechanism of two-way water-sensitive shape memory in PVA/silk
hybrids
To investigate the water-sensitive shape memory mechanism of
PVA/silk hybrids, the dynamic mechanical properties of PVA/5% silk
hybrids with different immersion times (0–3 min) were measured by
DMA. As can be seen in Fig. 6a, the storage modulus of PVA/5% silk
hybrids significantly decreases from 4695 MPa to 1415 MPa with the
increase of immersion times from 0 to 3 min. Correspondingly, the Tg
(determined from tanδ peak position at the lower temperature) reduces
from 49.5 °C to-24.1 °C (see Fig. 6b and Table S3). These results de-
monstrate that the absorbed water molecules act as plasticizers, re-
sulting in a decline of the switching temperature and the stiffness of
PVA/5% silk hybrid [24,30]. Thus, water is recognized as a stimulus to
induce the shape change of PVA/silk hybrids.
The structural variations of PVA/silk hybrids immersed in water for
different time have been further evaluated by WAXD and FTIR. Fig. 6e
shows the WAXD profiles of PVA/5% silk hybrid with different im-
mersion time. The relative sharp peaks at 2θ = 19.2° for PVA become
obviously weak as the immersion time prolongs to 3 min. Moreover, a
clear peak at 2θ = 19.6° representing the diffraction of (020) plane of
silk fibroin appears after immersed in water for 3 min that reveals a
typical β-sheet crystalline structure [48]. It can be concluded that the β-
sheet crystalline phase can play a netpoint role in the shape memory
behaviors of PVA/silk hybrids. On the other hand, the FTIR spectra of
PVA/5% silk hybrid display that the broad absorption peak of eOH
stretching (3280 cm−1) shifts to a higher wavenumber (ca. 3290 cm−1)
after immersed in water (Fig. 6c). It is an essential evidence indicating
that the absorbed water is bound to eOH groups. [30] In particular, the
characteristic peaks of C]O stretching (amide I) and NeH bending
(amide II) vibrations in the silk fibroin also shift from 1625 cm−1 to
1637 cm−1 and 1517 cm−1 to 1537 cm−1, respectively (Fig. 6d)
[49,50]. This result implies that the absorbed aqueous molecules form
HBs with PVA and silk fibroin, and meanwhile significantly disrupt the
primary HBs in the PVA/silk hybrids (PVA and PVA, PVA and silk fi-
broin) [24]. Furthermore, these peaks of eOH stretching, C]O
stretching and NeH bending vibrations could reversibly shift to lower
wavenumbers when PVA/silk hybrids are switched from wet to dry
state. Therefore, it is proved that the HBs in the PVA/silk hybrids can
act as switches for their water-induced shape memory behavior
[26,49,50].
To further understand the water-induced shape memory mechanism
in the PVA/silk hybrids, the weight and volume swelling degrees of
PVA/5% were assessed as a function of the water immersion time
(Fig. 6f). It clearly reveals that the weight and volume of PVA/5% silk
increase obviously as the immersion time extends to 3 min. Meanwhile,
its weight and volume swelling degrees correspondingly increase from
0 to 102.4%, 75.5%, respectively (See Table S3). However, it should be
mentioned that these values for PVA/5% silk are lower than those for
PVA under the same immersion time (see Fig. S6). This result reveals
that the swelling effect cannot be the single factor accounting for the
water-induced shape memory effect of the PVA/silk hybrids [24].
Moreover, the cross-section of PVA/silk hybrid was also observed by
SEM. As shown in Fig. 7, the PVA/silk hybrid possesses a two-layer
structure, which was also proved by WXRD (see Fig. S7). The silk fi-
broin is enriched in one layer (faced mold, bottom surface) and well-
dispersed in the PVA matrix. The other layer (faced air, top surface) is
relatively smooth, and mainly for PVA. Such kind of asymmetric la-
minated structure in the hybrids plays a key role in two-way shape-
memory behavior [19,51].
A schematic model is proposed through the above discussion to
better understand the water-induced two-way shape-memory me-
chanism of PVA/silk hybrids, as shown in Fig. 8. The model indicates
that the PVA/silk hybrids have a two-layer structure (i.e. PVA/silk and
PVA layer), where HBs are the same switch units in water-sensitive
shape memory effect. In the PVA/silk layer, β-sheet crystals act as
L. Gu et al.
netpoints. The wetting process of the PVA/silk hybrids makes the HBs
destructed in the PVA/silk and PVA layers, resulting in these two layers
with different swellings and improved flexibility of PVA chains by polar
aqueous molecules (see Fig. 6a and b). In water, the hybrids can be
deformed due to the stress from different swelling degrees of those two
layers. The elastic strain is stored in the PVA/silk layer due to the ex-
istence of netpoints. The drying process removes the aqueous molecules
from the hybrids, forming new HBs on the neighboring macromolecular
chains, where the elastic strain stored in the PVA/silk layer is released
for recovering the deformed shape [19]. From the macroscopic view-
point, the PVA/silk hybrids display reversible shape change in water
without any shape memory programming.
4. Conclusions
A novel spider silk-inspired 2WSMPs material has been developed
via simple solvent casting of silk fibroin and PVA. The silk proteins in
the hybrids exhibit antiparallel β-sheet conformation, and significantly
improve the storage modulus of PVA due to the strong hydrogen
bonding interactions. Meanwhile, the obtained PVA/silk hybrids pos-
sess a two-layer structure, where the silk fibroin is enriched in one layer
and well-dispersed in PVA. The hybrids display a water-sensitive two-
way shape-memory performance, where HBs and β-sheet crystals can
act as switch units and netpoints, respectively. The laminated structure
in the hybrids plays a key role in exhibiting two-way shape-memory
effect. The competitive HBs from water and its swelling plasticizing
effect are main factors for water-induced shape-memory behavior. This
work will offer new insight for developing intelligent water-induced
shape-memory materials and have great potential in various applica-
tions such as textiles, artificial muscle, actuators, and sensors.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time due to legal or ethical reasons.
Acknowledgments
This work was financially supported by the National Natural Science
Foundation of China (51673162), Research Grants Council, University
Grants Committee (PolyU 5158/13E), and Hong Kong Scholars
Program (XJ2016052).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.mtcomm.2018.10.005.
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