Journal of Colloid and Interface Science 607 (2022) 89–99

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Journal of Colloid and Interface Science

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

Flexible and transparent silver nanowires/biopolymer film

for high-efficient electromagnetic interference shielding
Gehuan Wang, Lele Hao, Xindan Zhang, Shujuan Tan ⇑, Ming Zhou, Weihua Gu, Guangbin Ji ⇑
College of Materials Science and Technology, Nanjing University of Aeronautics and Astronautics, Nanjing 210016, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The flexible transparent silver Flexible and transparent silver nanowires/biopolymer films were prepared by rod-coating method.
nanowires/biopolymer films were Hydrogen bonds and swelling effect of gel enhance the adhesion between Ag NWs and biopolymer sub-
prepared by facile rod-coating state. It integrates high-efficient EMI shielding performance, reliable durability, antioxidation, and anti-
method. frozen functions, which exhibits great potential in next-generation flexible optoelectronic devices.

The adhesion between biopolymer
substrate Ag NWs was enhanced by
hydrogen bonds and swelling effect of
gel.

The EMI SE of the Ag NWs/
biopolymer films achieves 20.94 dB,
and the transmittance is ca. 80 %.

The Ag NWs/biopolymer films also
integrating reliable durability,
antioxidation and anti-frozen
functions.

a r t i c l e i n f o a b s t r a c t

Article history: Flexible and transparent conductive films are highly desirable in some optoelectronic devices, such as
Received 17 August 2021 smart windows, touch panels, as well as displays and electromagnetic protection field. Silver nanowire
Revised 27 August 2021 (Ag NW) has been considered as the best material to replace indium tin oxide (ITO) to fabricate flexible
Accepted 28 August 2021
transparent electromagnetic interference (EMI) shielding films due to its superior comprehensive perfor-
Available online 1 September 2021
mance. However, the common substrates supporting Ag NWs require surface modification to enhance the
adhesion with Ag NWs. In this work, a flexible and transparent Ag NWs EMI shielding film with sandwich
Keywords:
structure through a facile rod-coating method, wherein Ag NWs network were embedded between
Flexible and transparent
Silver nanowires
biodegradable gelatin-based substrate and cover layer. The interfacial adhesion between Ag NWs and
Biodegradable gel gelatin-based layers was enhanced by hydrogen-bonding interaction and swelling effect without any pre-
Sandwich structure treatment. The shielding effectiveness (SE) of the G/Ag NW/G (G represents gelatin-based layer) film
Electromagnetic interference shielding reaches 37.74 dB at X band with an optical transmittance of 72.0 %. What’s more, the flexible gelatin-
based layer and encapsulated structure endow the resultant G/Ag NW/G film integrating excellent
mechanical properties, reliable durability, antioxidation, as well as anti-freezing performance. This work
paves a new way for fabricating flexible transparent EMI shielding films.
Ó 2021 Elsevier Inc. All rights reserved.

1. Introduction

⇑ Corresponding authors at: 29# Yudao Street, Nanjing 210016, PR China. The flourishing development of communication facilities and
E-mail addresses: tanshujuan@nuaa.edu.cn (S. Tan), gbji@nuaa.edu.cn (G. Ji). electronic devices has aroused social concerns because the ensuing

https://doi.org/10.1016/j.jcis.2021.08.190
0021-9797/Ó 2021 Elsevier Inc. All rights reserved.
G. Wang, L. Hao, X. Zhang et al.
EMI poses a hazard to electronic equipment normal operation and
human being health. To realize effective electromagnetic protec-
tion, the development of high-performance EMI shielding materi-
als has become a cutting-edge topic [1–5]. Flexible transparent
EMI shielding films are a kind of the state-of-art materials for opto-
electronic and wearable devices, which have grabbed considerable
attention in recent years [6,7]. ITO, as a conventional transparent
EMI shielding materials, has been limited by intrinsic brittleness,
which is not applicable for flexible electronics [8,9]. Carbon mate-
rials, including carbon nanotubes (CNTs) and graphene, and two-
dimensional metal carbons/nitrides (MXene) as alternatives to
ITO have been widely developed as flexible transparent EMI shield-
ing films. However, these materials have a trade-off between trans-
mittance and EMI shielding performance. For instance, the
monolayer graphene prepared by chemical vapor deposition
method has an ultrahigh transmittance of 97.7 %, while the sheet
resistance (Rs) is up to 635 X.sq-1, which exhibits a limited EMI
shielding performance of 2.27 dB [10]. Although the EMI shielding
performance of graphene can be enhanced by stacking and doping,
the procedures are complicated and the Rs value is still too high
[11]. Based on rayleigh–bénard convection and Marangoni force,
Yun et. al. fabricated self-assembled MXene films. The transmit-
tance of the resultant film with 9 layers is 45 % and EMI SE value
is 10 dB [12]. Weng’s group has reported a MXene/SWCNT compos-
ite film via a spin spay layer-by-layer assembly technology while
the EMI SE is only 3.3 dB at transmittance of 41% [13].
Metal nanowires, especially Ag NW, outperform than other con-
ductive materials due to outstanding conductivity and good flexi-
bility [14,15]. Moreover, the dilemma between transmittance and
EMI shielding properties can be alleviated to some extent [16].
Therefore, Ag NW has been considered as a promising candidate
for fabricating flexible transparent EMI shielding film. However,
the weak adhesion between Ag NW and substrate makes Ag NW
easily slide or fall off, which impacts the EMI shielding perfor-
mance [17,18]. This drawback can be solved by modifying the sur-
face of substrate. For example, Wang et. al. reported a transparent
Fe3O4-modified Ag NWs film on an UV-ozone atmosphere-treated
polyethylene terephthalate (PET) substrate, which exhibits great
EMI shielding performance of 24.9 dB at X band [19]. Recently, a
flexible transparent EMI shielding film was fabricated by spaying
Ag NWs and MXene on air-plasma-treated polycarbonate (PC) film.
The EMI SE value of the MXene/Ag NW composite film reaches
32 dB with optical transmittance of 52.3 % [20]. The sophisticated
pretreatment of substrate is used to introduce polar groups to
enhance adhesion [21,22]. Therefore, it is a sensible strategy to
deposit Ag NWs on a substrate with inherent functional groups.
Gelatin, a kind of renewable and abundant biopolymer, is avail-
able from the partial hydrolysis of collagen derived from animals’
skin and bone [23,24]. It has been widely explored in e-skin and
edible films for its eco-friendly, biodegradable and good filmogenic
property [25,26]. Naturally derived gelatin has abundant hydroxyl,
carboxyl, amino and other functional groups, and it forms a stable
three-dimensional network in the blend system [27]. Besides, it
also possesses oxygen barrier properties [28,29]. Based on the
advantages above, gelatin was selected as film forming materials
in this work. Glycerol was used as plasticizer to improve the
mechanical property of gelatin-based layer. As-synthesized Ag
NWs were deposited on gelatin-based substrate via rod-coating
method. Ag NWs were adhered to gelatin-based substrate through
hydrogen-bonding interaction and swelling behavior of water-
soluble gelatin. Then, Ag NWs network was coated by another
gelatin-based layer to avoid oxidation. The optical transmittance
is ca. 80 % with EMI SE value of 20.94 dB, which can shield electro-
magnetic wave more than 99 %. When the Ag NWs area density is
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Journal of Colloid and Interface Science 607 (2022) 89–99
250 mg.m2, the superior EMI SE achieves 37.74 dB at X band with
transmittance of 72.0 %. Furthermore, Ag NWs were embedded
between gelatin-based layers that endow the sandwiched film
integrating multiple fascinating qualities, including excellent
mechanical properties, fatigue-resistant, antioxidation and anti-
freeze, which satisfies requirements for next-generation electron-
ics and wearable devices.
2. Experimental section
2.1. Materials
Poly(vinylpyrrolidone) (PVP, Mw = 1300000) was purchased
from Sigma-Aldrich Co., Ltd. Acetone was purchased form Nanjing
Chemical Reagent Co., Ltd. Absolute ethanol, ethylene glycol (EG),
gelatin (260 bloom), and glycerol were obtained from Macklin
Co., Ltd. Sodium chloride (NaCl) and silver nitrate (AgNO3) were
supplied by Sinopharm Chemical Reagent Co., Ltd. The deionized
water was homemade in laboratory. All of the chemicals were ana-
lytically pure and used without any further purification.
2.2. Synthesis of Ag NWs
Ag NWs were synthesized by polyol method. Briefly, 1.6 g PVP
was dissolved into 50 mL EG under magnetically stirring followed
by injecting 1.6 mL NaCl solution (1.2 mg mL1 in deionized
water), forming a homogeneous solution A. Subsequently, 0.54 g
AgNO3 was completely mixed with 30 mL EG to obtain the solution
B. Afterward, the solution A was mixed with solution B dropwise
for several minutes, and then transferred the mixture into Teflon
autoclave for hydrothermal treatment at 160 °C for 7 h. Finally,
the reaction mixture was washed by deionized water, acetone
and absolute ethanol along with centrifugation of 3000 rpm for
5 min. The purify process was repeated for several times. The resul-
tant Ag NWs were re-dispersed in deionized water with concentra-
tion of 0.4–0.9 mg. mL1.
2.3. Synthesis of biodegradable sol
The homogeneous biodegradable sol was obtained by blending
1.0 g gelatin and 0.2 g glycerol in 10 mL deionized water at 60 °C
water bath.
2.4. Fabrication of G/Ag NW/G film
Prior to all steps, the surface of glass substrate was cleaned by
deionized water and ethanol, and dried in air at room temperature.
Afterward, biodegradable sol used as film forming solution was
rod-coated on glass substrate followed by air-drying at room tem-
perature for 24 h. During this process, the sol was cooled into gel
and further dried to form a transparent film. The Ag NWs suspen-
sion with different concentration were uniformly distributed on
the surface of gelatin-based substrate (6  6 cm2) via rod-coating
method. After drying, another gelatin-based biogel layer was over
coated on the surface of Ag NWs network and dried at room tem-
perature for 24 h. Finally, a flexible and transparent film with sand-
wich structure was peeled from glass substrate. The samples were
denoted as G/Ag NWx/G film, where G and x represent gelatin-
based layer and the area density of Ag NWs respectively. The area
density of Ag NWs was related to the amount of Ag NWs and the
area of gelatin-based substrate, which can be expressed by the fol-
lowing equation [20]:
CA  V A
rA ¼ ð1Þ
SG
G. Wang, L. Hao, X. Zhang et al.
Where rA represents the area density of Ag NWs, CA and VA are
the concentration and volume of Ag NWs, and the SG is the area of
gelatin-based substrate. The calculated result of Ag NWs area den-
sity was 111.1, 138.9, 166.7, 194.4, 222.2 and 250.0 mg m2.
2.5. Characterization
The morphologies and structure of the specimens were
recorded by Scanning Electron Microscope (SEM, Hitachi S4800).
The elemental composition of Ag NW was examined by energy dis-
persive spectrometer (EDS). The X-ray diffraction (XRD, Bruker D8
ADVANCE) was carried out to observe crystal phases. Fourier trans-
form infrared spectroscopy (FT-IR, PerkinElmer IR-843) was carried
out to analyze the surface functional groups. The X-ray photoelec-
tron spectrometer (XPS, PHI 5000 VersaProbe) was used to analyze
the binding energy of the samples. The gelatin-based film was used
as baseline, and the transmittance spectra of films was obtained by
UV–visible spectrophotometer (UV-3600) in the visible light
region. The sheet resistance was obtained by using four-point
probes resistivity measurement system (RTS-8). The mechanical
properties of films were measured by the Universal Testing
Machine (CMT-5105) at the crosshead speed of 10 mmmin1.
The cyclic bending test was performed by a homemade equipment.
Typically, both sides of the film were clamped with binder clips,
bending with a radius of curvature (RoC) of 2 mm. A vector net-
work analyzer (Agilent PNA N5244A) was used to record reflection
(S11) and transmission (S12) parameters at X band (8.2–12.4 GHz)
with sample size of 22.86  10.16 mm2. The power coefficients,
including reflection (R), absorption (A), and transmission (T), can
be calculated by the Eqs. (2)–(7) [30]:
R ¼ jS11 j2 ð2Þ
T ¼ jS21 j2 ð3Þ
RþAþT ¼1 ð4Þ
SET ¼ SER þ SEA ð5Þ
SER ¼ 10logð1  RÞ ð6Þ
T between gelatin-based layers. The adhesion between the Ag NWs
SEA ¼ 10logð Þ ð7Þ
1R
3. Results and discussion
The composition of biodegradable sol is shown in Fig. 1a, gela-
tin, glycerol and water were blended together to prepare a homo-
geneous film forming solution. The fabrication process of the G/Ag
NW/G film is illustrated in Fig. 1b. Briefly, biodegradable sol was
spread on the glass substrate via facile rod-coating method. During
the cooling and drying process, the sol was turn into gel, and finally
formed a transparent gelatin-based film (Fig. 1c). Subsequently,
the Ag NWs suspension was coated on the gelatin-based substrate
through the same way, followed by encapsulating another gelatin-
based layer. It is noteworthy that ethanol and isopropyl alcohol are
poor solvents for gelatin, which results in the coacervation of gela-
tin [31]. Therefore, this preparation method is not applicable to Ag
NWs dispersed in ethanol and isopropyl alcohol. After completely
drying, sandwich structured G/Ag NW/G film can be peeled from
glass substrate. The digital photographs of G/Ag NW/G film are pre-
sented in Fig. 1d and e. The G/Ag NW/G film was suspended on the
flower, showing high transparency. Besides, it also exhibits excel-
lent flexibility.
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Journal of Colloid and Interface Science 607 (2022) 89–99
The micromorphology of Ag NWs synthesized by polyol method
are shown in Fig. 2a and b. It can be found that as-prepared nano-
wires with diameter of 70–90 nm and length of 20–40 lm. EDS
spectra confirmed that the main component of nanowires was sil-
ver (Fig. 2c). The XRD spectra of Ag NWs is presented in Fig. 2f.
There are five characteristic diffraction peaks located at 38.1,
44.3, 64.4, 77.5, and 81.5°, corresponding to the pure face-
centered cubic silver crystals plane of (1 1 1), (2 0 0), (2 2 0), (3 1 1),
and (2 2 2). These results are accordance with Ag PDF#04–0783.
As shown in Fig. S1a, the water contact angle of as-synthesized
Ag NWs is 47.19°. The hydrophilic characteristic was originated
from the PVP on the surface of Ag NWs. As shown in Fig. 2d, the
gelatin-based substrate formed by biogel have a relative smooth
surface and have no cracks. It also exhibits hydrophilicity with a
contact angle of 68.86°, which is favorable for the uniform distribu-
tion of Ag NWs (Fig. S1b). To the best of our knowledge, the high
contact resistance of Ag NWs impairs the conductivity due to insu-
lating PVP on the nanowire surface and the loose contact of wire
junctions [32]. In Fig. 2e, Ag NWs were dispersed randomly on
the gelatin-based substrate. It is worth noting that the crossed
Ag NWs exhibit obvious shape deformation, suggesting the wire-
wire junctions were well welded. This phenomenon can be
explained by the water evaporation induced capillary force during
drying process, which is beneficial to reduce the contact resistance
of Ag NWs (Fig. 3b) [33]. Interestingly, Ag NWs at bottom were
partially embedded in the substrate, which enhances the adhesion
between Ag NWs and substrate (Fig. S2a). For ease of comparison,
the Ag NW/PET film was prepared via the same method. One can
found that there have small spaces between substrate and crossed
Ag NWs, which shows a weak adhesion (Fig. S2b). This phe-
nomenon can be explained by the swelling effect of hydrogel,
and the schematic of the is shown in Fig. 3c. When the water-
borne Ag NWs suspension approaches the surface of gelatin-
based substrate, the substrate transforms to hydrogel by absorbing
water. The volume of the gelatin-based substrate becomes larger
and soft. Then the bottom of the Ag NWs was partially embedded
into the substrate due to their own gravity during the swelling-
drying process. According to the design principle demonstrated
in Introduction, the G/Ag NW/G film with sandwich structure
was constructed. Fig. 2g and h exhibits the cross-sectional SEM
images of the G/Ag NW/G film. The film forming solution fills the
hole of Ag NWs network, and the Ag NWs were tightly fixed
and gelatin-based layers can further enhance the hydrogen bond-
ing interactions, which can be proved by FT-IR spectra (Fig. 2i).
For pure gelatin film, one can observe 5 characteristic bands. The
typical Amide A band located at 3284.6 cm1, which is caused by
the stretching vibration of hydrogen bonded NAH groups. The
Amide B band around 2939.9 cm1 is arose from the stretching
vibration of CAH groups. The band situated at 1628.1 cm1 is the
characteristic band of Amide I, corresponding to C@O stretching
vibration and hydrogen bonded –COO groups. Amide II centered
at 1539.4 cm1 stands for the NAH bending vibration and CAN
stretching vibration. The band at 1237.1 cm1 is corresponded to
the in-plane vibration of CAN and NAH groups or –CH2 groups
from glycerol and the side chain of hydroxyproline [34–36]. After
mixing with glycerol, the gelatin structure was preserved in the
blend system. The peak around 1040 cm1 is designated to the
CAO stretching vibration, which was mainly originated from glyc-
erol [27]. It is well established that the capping agent PVP and the
Ag NWs were connected by chemisorption during the synthesis
process. The FT-IR of the Ag NWs shows a band centered at
1630.5 cm1, which is related to the C@O stretching vibration from
PVP. Compared with gelatin-based film, the characteristic bands of
C@O and NAH in G/Ag NW/G film show a shift to lower band
(1629.0 to 1628.6 cm1, 3285.6 to 3284.2 cm1 respectively).
G. Wang, L. Hao, X. Zhang et al.
Fig. 1. (a) The ingredients of the biodegradable sol, enable a flexible and transparent, but fully degradable substrate and cover layer. (b) Schematic the fabrication procedure
of the G/Ag NW/G film. (c) Digital photographs of the gelatin-based substrate lying on the paper, showing high transparency. (d) Digital image of the G/Ag NW/G film. The G/
Ag NW/ G was suspended on Eustoma grandiflorum. (e) Photograph shows the mechanical flexibility of the G/Ag NW/G film.
These results indicate the formation of hydrogen bond between
carbonyl groups originated from PVP on Ag NWs and amino groups
of gelatin-based layers [37]. Thus, the Ag NWs were interconnected
with gelatin-based layers via hydrogen-bonding interaction,
wherein PVP acts as intermediate mediator (Fig. 3d).
The optical transmittance and electrical conductivity are two
key indicators for transparent EMI shielding films, and these indi-
cators can be adjusted by Ag NWs loading density. The digital
images of gelatin-based film and series G/Ag NW/G films with dif-
ferent Ag NWs loading density is presented in Fig. 4a. The letters
underneath G/Ag NW/G films are visible. The color of the film
become grey with the variation of Ag NWs density from 0 to
250.0 mg.m2, which can be attributed to enhanced photons scat-
tering and reflection [38]. The gelatin-based film was chosen as the
baseline and the transmittance of it was eliminated during the test.
It can be observed that the optical transmittance of as-prepared Ag
NW/G presents a downward trend with the increase of Ag NWs
density (Fig. S3). As shown in Fig. 4b, the G/Ag NW0/G film shows
the transmittance of 99.49 %, indicating that the cover layer has a
little influence on transparency. The corresponding transmittance
of G/Ag NW/G films shows similar trend, decreasing from 89.26
to 71.98 % at 550 nm as the increase of Ag NWs area density.
The gelatin-based substrate is an electrical insulating film, thus,
the conductivity depends on the area density of Ag NWs. As shown
in Fig. 4c, the sheet resistance also presents a decline trend with
the increase of Ag NW area density. For the G/Ag NW111.1/G film,
the Rs value is 109.9 Xsq-1, and that of the G/Ag NW250.0/G film
reaches 2.9 Xsq-1. The improvement of conductivity is attributes
to the dense conductive network constructed by more Ag NWs,
which facilitates to the transport of carrier.
The total EMI SE (SET) of G/Ag NW/G is shown in Fig. 5a. Obvi-
ously, the electrically insulating gelatin-based film is an electro-
magnetic wave transparent material, which has no contribution
92
Journal of Colloid and Interface Science 607 (2022) 89–99
to EMI shielding. With the increasing of Ag NWs content, the G/
Ag NW/G film exhibits stronger EMI shielding ability. The resula-
tent film satisfies the requirement of practical application
(SE greater than 20 dB) when the Ag NWs area density is
194.4 mg.m2 [39]. The superior EMI SE value reaches 37.74 dB
with the Ag NWs area density of 250.0 mg.m2, which means that
99.98 % of electromagnetic wave can be blocked. It is well-
established that the EMI shielding performance is related to the
sheet resistance. The improvement of EMI shielding performance
is attributed to high Ag NW loadings form a perfect conductive net-
work, reducing the sheet resistance. The equation (8) was used to
reveal the relationship between EMI SE and sheet resistance in the-
oretically [40]:
Z0
SET ¼ 20logð1 þ Þ ð8Þ
2Rs
Where Z0 (377 X) represents the free air impedance. The theo-
retical calculated and experimental SE value are presented in
Fig. 5b. Both of them are decreased with the increase of RS, and
the experimental results are match well with the calculated value.
Generally, the EMI shielding mechanisms are mainly reflection
(SER) and absorption (SEA) loss. For nonmagnetic Ag NW, the value
of SER and SEA are proportional to electrical conductivity [19]. As
shown in Fig. 5c and d, SER and SEA show little dependance of fre-
quency. Besides, both of them present incremental tendency
at X band with the decrease of sheet resistance. The value of SEA
is larger than that of SER in the whole frequency range. It seems
that absorption loss is the prominent shielding mechanism. How-
ever, as the Ag NWs area density increase from 111.1 to
250.0 mg.m2, the SER value shows an increase of 703.6 %, while
that of SEA increases 335.7 %. To investigate the EMI shielding
mechanism in depth, the power coefficients calculated based on
formulas (2–4) are shown in Fig. 5e. The portion of reflection
G. Wang, L. Hao, X. Zhang et al. Journal of Colloid and Interface Science 607 (2022) 89–99

Fig. 2. (a, b) SEM images of Ag NWs. (c) EDS of the as-synthesized Ag NWs. (d) SEM image of gelatin-based substrate without Ag NWs, which shows a relative smooth surface.
(e) SEM image of Ag NWs deposited on gelatin-based surface. The red circles are the junctions of crossed Ag NWs, and the arrow points to the embedded Ag NW. (f) The XRD
spectra of as-synthesized Ag NWs. (g, h) The cross-sectional SEM images of the G/Ag NW/G film. (i) The FT-IR spectra of the pure gelatin film, glycerol plasticized gelatin
composite film, G/Ag NW/G film, and Ag NWs.

Fig. 3. Schematic illustration of the strong adhesion between Ag NWs and gelatin-based layers. Schematic of (a) as-prepared Ag NW/G film, (b) capillary force induced
welding of Ag NWs, (c) swelling effect of the gelatin-based substrate, (d) the hydrogen bonding interaction between Ag NWs and gelatin-based layers.

93
G. Wang, L. Hao, X. Zhang et al.
Fig. 4. Digital images of the G/Ag NW/G films with different Ag NWs area density. The letters underneath the G/Ag NW/G film are visible. (b) Optical transmittance spectra of
the G/Ag NW/G films. (c) Sheet resistance of the G/Ag NW/G films.
shows a growth trend with the increase of Ag NWs amount, and
the value of R is larger than A when the area density of Ag NWs
over 120 mg.m2 approximately. Given these results, the G/Ag
NW/G film is a reflection-dominated EMI shielding materials.
The underlying shielding mechanisms can be explained as the
follows. First, most part of the incident electromagnetic wave is
reflected when it reaches materials surface, which arises from
impedance mismatching [41]. The reflection loss will occur when
the residual electromagnetic wave penetrates through the surface
into the material. More Ag NWs construct a continuous conductive
path, thus reduce the sheet resistance. As a result, more mobile
charge carriers interact with the incident wave, enhancing the
reflection loss [42]. Then, the current induced by electron migrat-
ing, hopping, and tunneling enhances conductive loss, transform-
ing the remaining EM wave into thermal energy [43–45].
Comparison of the recently reported transparent EMI shielding
materials and their corresponding transmittance and shielding
performance is presented in Fig. 5f and Table 1. The G/Ag NW/G
films proposed in this work integrate high transparency and
remarkable EMI shielding performance, which are superior to most
similar transparent EMI shielding films [8,10,12,13,20,40,46–51].
A wireless power-transfer system is employed to demonstrate
the application of the G/Ag NW/G shielding film. The circuit dia-
gram of Tesla wireless transmission system is shown in Fig. 6a.
Tesla coil, essentially, is a step-up transformer. The magnetic reso-
nance system is made up of receiver and transmitter coil. When
the frequency of oscillating magnetic field generated by the trans-
mitting end is consistent with that of the receiving end, wireless-
power transferring will be realized. The neon light was bright
when the electric power was switched on, and it still bright when
the gelatin-based film was inserted between light and Tesla coil.
While the light was extinguished since inserting the G/Ag NW/G
film because the resonance condition has been damaged by the
shielding film (Fig. 6b-d, Movie S1). These phenomena prove that
the G/Ag NW/G film can be employed in practical application.
Pure gelatin film suffers from poor mechanical properties,
which limits the application in flexible electronics. Glycerol was
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Journal of Colloid and Interface Science 607 (2022) 89–99
used as plasticizer to blended with gelatin, forming a physically
crosslinked network. The intermolecular force was weakened by
increasing the mobility of gelatin chains, which endows the com-
posite film with flexibility [52]. Tensile strength (TS) and elonga-
tion of break (EAB) can be calculated by equations (9) and (10)
[53]:
F max
Ts ¼ ð9Þ
LW
L1  L0
EAB ¼  100% ð10Þ
L0
Where Fmax stands for the maximum tension, L, L0, L1, and W
represent thickness, the initial length, breaking length, and width
of the testing sample, respectively. As presented in Fig. 7a, the Ts
value of series G/Ag NW/G films are around 52 MPa, indicating that
the amount of Ag NWs has little influence on tensile strength. The
EAB value of G/Ag NW/G film increases with the variation of Ag
NWs area density, which may be attributed to the malleability of
Ag NWs [54]. High-performance EMI shielding film with excellent
flexibility and reliable durability are urgently demand in wearable
and portable electronics [55]. The cyclic bending test of the G/Ag
NW250.0/G film was carried out and the results are shown in
Fig. 7b. The EMI shielding performance almost have no difference
after bending 1000 times with a radius of 2 mm. The superior dura-
bility can be ascribed to strong adhesion between Ag NW and sub-
strate, and Ag NWs were embedded tightly in sandwich structure,
thus it is hardly to slide during bending process.
Antioxidation is another attractive function for the practical
application of Ag NW-based EMI shielding films. The G/Ag
NW250.0/G and Ag NW250.0/G films were exposed to air at 25 °C
and relative humidity of 60 ± 5% for several days, and the corre-
sponding EMI shielding performance is shown in Fig. 7c. One can
found that the Ag NWs film without cover layer is prone to be oxi-
dized, which is reflected in the rapid decline of SE/SE0 value in first
20 days. The decline trend of SE/SE0 toward slow down after
20 days aging. These phenomena may be due to the rapid oxidation
G. Wang, L. Hao, X. Zhang et al. Journal of Colloid and Interface Science 607 (2022) 89–99

Fig. 5. (a) Total EMI SE of gelatin-based film and G/Ag NW/G films. (b) The theoretical calculated and experimental SE value versus sheet resistance. (c) Reflection loss, (d)
absorption loss, and (e) power coefficients of G/Ag NW/G films with different Ag NWs area density. (f) The comparison of transparent EMI shielding materials.

Table 1
Comparison of the recently reported transparent EMI shielding materials and corresponding transmittance and shielding performance.

Materials Transmittance/% SE/dB Rs/X.sq-1 Ref.

Metallic oxide ITO 81.5 18 16.5 8
Al-doped ZnO 85.93 6.5 / 46
1D&2D materials CNT/PLA 78 13 / 47
Ni-Pd-SWCNT 71.4 21.37 87.26 48
Monolayer graphene 97.7 2.27 635 10
graphene/PET 80.5 19.14 / 49
MXene 45 10 / 12
MXene/MWCNT 33 2.8 463 13
MXene/SWCNT 41 3.3 503 13
Ag NW-based materials Ag NW666/PDMS 76.8 42.5 2 40
PES/Ag NW/PET 70 38 1.8 50
Graphene/Ag NW 47 40.1 5 51
MXene/Ag NW632-PVA 52.3 32 17.2 20
G/Ag NW194.4/G 79.70 20.94 19.3 This work
G/Ag NW222.2/G 75.94 30.07 6.9 This work
G/Ag NW250.0/G 71.98 37.74 2.9 This work

MWCNT: multi-wall carbon nanotube; SWCNT: single-wall carbon nanotube; PLA: polylactic acid; PES: poly (ethersulfones).

95
G. Wang, L. Hao, X. Zhang et al.
Fig. 6. The circuit diagram of wireless power-transfer system. Digital photographs of wireless power-transfer system (b) without EMI shielding film, (c) with gelatin-based
film, and (d) with G/Ag NW/G film. The neon light was extinguished because G/Ag NW/G film blocks the power transmission.
of Ag NWs at the beginning, the oxides on the surface of the Ag
NWs damage the electrical conductivity. After the formation of oxi-
des on the surface, the oxidation rate was slow down. Although the
EMI SE of G/Ag NW/G film exhibits gentle decline, it can still shield
EM wave over 99.95% after 120 days aging. These results indicate
that the Ag NWs encapsulated by gelatin-based layer inhibits oxi-
dation. The XRD spectra of Ag NW250.0/G and overcoated counter-
part is shown in Fig. S4. Both pristine films show the two
characteristic peaks corresponding to the (1 1 1) and (2 0 0) Ag
NWs lattice plane. After aging, the intensity of the G/Ag NW250.0/
G film decreases slightly. As for the Ag NW250.0/G film, the intensity
of it decreases obviously, and the (2 0 0) plane almost disappear.
The Ag 3d XPS data of Ag NW250.0/G and G/Ag NW250.0/G is shown
in Fig. 7d. The existence of cover layer reduces the relative content
of Ag element, thus the XPS curve of G/Ag NW250.0/G exhibits an
obvious fluctuation. According to the previous work, the binding
energy of Ag 3d5/2 and Ag 3d3/2 are 368.2 and 374.2 eV, respec-
tively [56]. After 120 days aging process, the binding energy of
Ag 3d5/2 of the Ag NW/G and G/Ag NW/G are located at 367.88
and 368.08 eV, and the Ag 3d3/2 peak are located at 373.78 and
374.08 eV. The binding energy of Ag 3d shifts to the lower energy
region, indicating that the Ag NWs have been oxidized [57,58].
Compare with the not overcoated counterpart, the G/Ag NW250.0/
G shows low oxidation degree. As shown in Fig. 7e and f , the
SEM images of the G/Ag NW250.0/G and Ag NW250.0/G films after
120 days aging also demonstrate the anti-oxidation properties of
the gelatin-based layer. It can be found that there are many protru-
sions on the surface of Ag NWs (right side), which proves that the
Ag NWs has been severely oxidized without cover layer. On the
contrary, the Ag NWs protected by gelatin-based cover layer (left
side) maintained original microstructure without any protrusions.
These results suggesting that the Ag NWs encapsulated by gelatin-
based layers have antioxidation property to some extent.
To the best of our knowledge, most of the transparent film or
glass will fog at low temperature, which affects the visual affect.
96
Journal of Colloid and Interface Science 607 (2022) 89–99
The ice crystals formed on the surface of PET after frozen at
10 °C, 35% humidity for one day, and the letter underneath the
PET became blurred. The same situation was found in Ag NW/
PET film (Fig. 8a and b, and Fig. 8e and f). Interestingly, the
gelatin-based substrate and G/Ag NW/G film was maintained high
transparency and mechanical flexibility after frozen process
(Fig. 8c and d, and Fig. 8g and h). This phenomenon may be attrib-
uted to the introduction of glycerol decreases the freezing point of
the gelatin, thus achieve the function of antifreeze and fog-
prevention.
4. Conclusions
In this work, transparent and flexible EMI shielding film was
assembled by Ag NWs network and biodegradable layers. The
biodegradable layers, consisting of glycerol and gelatin, were used
to prepare substrate and cover layer. The hydrogen-bonding inter-
action was formed between Ag NWs and substrate, which
enhances the adhesion without any sophisticated pretreatment.
Moreover, the swelling behavior of gelatin-based gel further
improve adhesion. The optical transmittance and EMI shielding
performance can be controlled by Ag NWs loading density. The
superior SE value of the resultant G/Ag NW250.0/G film is
37.74 dB with optical transmittance of 71.98 %. Besides, the G/Ag
NW/G film possess excellent mechanical properties with tensile
strength of approximately 52 MPa. It also shows fantastic durabil-
ity that can bear cyclic bending 1000 times and long-time oxida-
tion. Besides, it possesses good flexibility and antifogging
properties at low temperature, which widens the working temper-
ature range of the real-world applications. Therefore, the multi-
functional G/Ag NW/G film has significant prospect in the
application of wearable devices, flexible optoelectronics, as well
as EMI shielding.
G. Wang, L. Hao, X. Zhang et al. Journal of Colloid and Interface Science 607 (2022) 89–99

Fig. 7. (a) Mechanical properties of the G/Ag NW/G films with different Ag NW loading density. (c) EMI SE variation of the G/Ag NW/G film before and after bending 1000
times. The inset shows the bending state with a bending radius of 2 mm. (c) EMI SE changes of the Ag NW250.0/G and G/Ag NW250.0/G during 120 days ageing process. (d) XPS
spectra of Ag NW250/G and G/Ag NW250.0/G films after aging process. (e, f) SEM images of as prepared transparent Ag NWs-based film with different magnification. The left
side is the overcoated Ag NWs/G film and the right side is the Ag NWs/G film without cover layer.

Fig. 8. Digital images of the (a, e) PET; (b, f) Ag NW/PET; (c, g) gelatin-based substrate; (d, h) G/Ag NW/G film at initial state and stored at 10 °C, 35% humidity for one day.

CRediT authorship contribution statement
Gehuan Wang: Methodology, Investigation, Data curation, For-
mal analysis, Writing – original draft. Lele Hao: Methodology,
Investigation. Xindan Zhang: Investigation. Shujuan Tan: Soft-
ware, Formal analysis, Data curation, Writing – review & editing.
Ming Zhou: Software, Resources. Weihua Gu: Visualization, Data
curation. Guangbin Ji: Conceptualization, Writing – review & edit-
ing, Supervision, Funding acquisition.

97
G. Wang, L. Hao, X. Zhang et al. Journal of Colloid and Interface Science 607 (2022) 89–99

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