Composites Part B 171 (2019) 204–213

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Achieving high electrical conductivity and excellent electromagnetic

interference shielding in poly(lactic acid)/silver nanocomposites by
constructing large-area silver nanoplates in polymer matrix
Jie Li a, Wen-Jie Peng a, Zeng-Ji Fu a, Xiao-Hong Tang a, Hong Wu b, Shaoyun Guo b,
Ming Wang a, *
a
Chongqing Key Laboratory of Soft-Matter Material Chemistry and Function Manufacturing, Key Laboratory of Applied Chemistry of Chongqing Municipality, School of
Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, PR China
b
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu, 610065, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: Large-area silver nanoplates were constructed in poly(lactic acid) to achieve high electrical conductivity and
Poly(lactic acid) excellent electromagnetic interference shielding at low content of silver. Poly(lactic acid) micro-particles were
Silver nanoplates firstly coated with thin silver layer by electroless plating. The coated micro-particles were then fused together to
Electromagnetic interference shielding
form the poly(lactic acid)/silver nanocomposites with large-area silver nanoplates via a hot pressing. The
Electrical conductivity
thickness and compact degree of silver nanoplates was relative to the etching time of micro-particles and con­
Conductive polymer composites
centration of silver ions in solution, while the lateral size of silver nanoplates was dependent on the diameter of
poly(lactic acid) micro-particles. Because of the large-area silver nanoplates, the microwaves were efficiently
absorbed by repeated reflection-absorption at the interfaces between silver and poly(lactic acid).

1. Introduction Normally, the electrical conductivity of CPCs is very important to the

Development of electronic equipment gives our life convenience but
simultaneously brings electromagnetic pollution, which disturbs the
proper operation of electrical devices and threats biological species
[1–3]. Therefore, electromagnetic interference (EMI) shielding mate­
rials have become great attention to protect living organisms and
operation surroundings from radiation pollution [4–6]. Typically, EMI
shielding materials with shielding effectiveness (SE) more than 20 dB,
which attenuated 99% electromagnetic radiation, were required in in­
dustrial applications [7–9]. Metal materials which could easily reflect
microwaves were the traditional EMI shielding materials. However, the
metal materials have many disadvantages, such as high density, low
corrosion resistance and poor flexibility [10]. Polymer composites have
been well demonstrated to enhance or functionalize polymers [11–17].
For example, conductive polymer composites (CPCs) have attracted
great interest for their potential applications in EMI shielding materials
due to their lightweight, low cost, and facile processability [18–20].
However, to develop CPCs with high performance EMI shielding at low
conductive fillers is still a great challenge up to now.
EMI shielding performance. The EMI SE value increased with increasing
electrical conductivity of CPCs [21–23]. The high performance EMI
shielding was achieved in CPCs with high electrical conductivity, nor­
mally higher than 1 S/m [24–26]. However, the high electrical con­
ductivity usually required high content of conductive fillers, which led
to arise economic cost and deteriorate mechanical properties for CPCs
[27–29]. Therefore, it is necessary to establish a new conductive
network to reduce the content of conductive fillers and enhance elec­
trical conductivity and EMI shielding performance of CPCs.
Double percolation network in co-continuous matrix [30] and
segregated conductive network [31 32] have been constructed to
improve the electrical conductivity and EMI shielding by controlling
dispersion of conductive fillers. For example, polyphenylene sulfide/­
carbon nanotubes composites with a segregated structure exhibited an
electrical conductivity of 72.0 S/m and excellent EMI shielding effec­
tiveness of 49.6 dB with 5.0 wt% carbon nanotubes [33]. The electrical
conductivity and the EMI SE of the poly(lactic acid) (PLA)/poly(ε-cap­
rolactone)/carbon nanotubes (MWCNT) composites with 0.8 wt% car­
bon nanotubes increased from 2.1 � 10 12 S/m and 5.3–8.6 dB to

* Corresponding author.
E-mail address: mwang@swu.edu.cn (M. Wang).

https://doi.org/10.1016/j.compositesb.2019.05.003
Received 6 January 2019; Received in revised form 7 April 2019; Accepted 1 May 2019
Available online 4 May 2019
1359-8368/© 2019 Elsevier Ltd. All rights reserved.
J. Li et al.
0.012 S/m and ~17 dB, respectively, by constructing double percolation
network in the polymer matrix [34].
In addition, multilayered structure [35–38] and cellular structure
[39–42], were also found to improve EMI SE values via enhancing
multiple reflection of electromagnetic radiation. For example, the mi­
crowave absorbing efficiency of carbon black filled polypropylene
increased from 12 to 33 dB by increasing the number of layer from 2 to
128 layers for the composites [43]. The outstanding EMI shielding
performance was found in the PLA/MWCNT foam with an EMI SE value
of close to 30 dB by adding an extremely low MWCNT content of just
0.0024 vol %, because of the multiple reflection of microwaves in the
cellular structure [44].
Carbonaceous conductive fillers, such as carbon black and carbon
nanotubes, were usually added to polymer matrix to form CPCs for EMI
shielding [45–47]. Recently, two-dimensional (2D) conductive fillers,
such as graphene [48–50] and MXenes [51–54], have well demonstrated
to be more efficient to improve EMI SE for CPCs. For example, the
graphene filled ethylene-vinyl acetate copolymers film exhibited the
EMI SE values of 23 dB at thickness of ~350 μm [55]. The segregated
polystyrene/MXene nanocomposites exhibited not only a low percola­
tion threshold of 0.26 vol% but also an outstanding EMI SE of >54 dB
with the low MXene content of 1.90 vol% [56]. The high performance of
EMI shielding for the CPCs with 2D conductive fillers was ascribed to the
large lateral area of fillers, which could reflect and absorb electromag­
netic waves efficiently [56]. However, the back draws for the develop­
ment of CPCs with 2D fillers were the complex preparation process of 2D
fillers and the low cost performance ratio. Noticeable, the 2D metal
materials with cost efficient have been rapidly developed in the field of
energy and environment [57–59]. Unfortunately, constructing 2D metal
materials in polymer matrix was very difficult to improve EMI SE of
CPCs because of the lost controlling dispersion of 2D metal materials in
polymer matrix, although controlling dispersion of 0D and 1D metal
materials in polymer matrix has been well demonstrated to improve EMI
SE of CPCs [60–64].
In this work, the 2D large-area Ag nanoplates were also constructed
in PLA matrix to achieve high performance EMI shielding at low content
of Ag nanoplates. First, the PLA micro particles were coated with com­
pacted Ag layer by electroless plating. The PLA micro particles etched in
NaOH methanol/water to rough the surface and enhance the interfacial
interaction between Ag and PLA mirco-particles. Second, the PLA/Ag
composites with uniform dispersion of 2D large-area Ag nanoplates were
achieved by fusing the Ag coated PLA micro-particles together via a hot
pressing at 180 � C and 10 MPa. During the hot pressing, the Ag layer on
the surface of the PLA micro-particles was broken into 2D large-area Ag
nanoplates. Because of the in-situ breaking up, the 2D large-area Ag
nanoplates were uniform dispersion in PLA matrix. Furthermore, the
thickness of Ag nanoplates was tuned by the etching time of PLA micro-
particles and the concentration of Agþ solution, while the lateral area of
Ag nanoplates was regulated by the diameter of PLA micro-particles.
Finally, the PLA/Ag nanocomposites exhibited high electrical conduc­
tivity and excellent EMI shielding at low content of Ag owing to the Ag
nanoplates with large area. For example, outstanding EMI SE of
60.4 dB at the thickness of 2.7 mm was achieved in the PLA/Ag nano­
composites with only 0.99 vol% Ag.
2. Experimental
2.1. Materials
Poly(lactic acid) (PLA) micro-particles with four different average
diameters of 700, 500, 350, and 150 μm, AgNO3 (99.8%), SnCl2⋅2H2O
(98%) were kindly provided by Shenzhen Esun Industrial Co. Ltd.,
China, Tianjin Ruijinte Chemicals Co., Ltd., China and Sigma-Aldrich
Co., LLC., St. Louis, USA, respectively. The PLA micro-particles have a
melt index of ~7 g/10min (210 � C/2.16 kg) and a density of
1.25 � 0.05 g/cm3. Glucose, sodium tartrate, sodium hydroxide,
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Composites Part B 171 (2019) 204–213
methanol were bought from Chongqing Chuandong Chemicals Co., Ltd.,
China.
2.2. Preparation of Ag coated PLA micro-particles
Fig. 1 shows the processing procedures of the Ag coated PLA micro-
particles and the PLA/Ag nanocomposites with large-area Ag nano­
plates. First, PLA micro-particles with different average diameters of
700, 500, 350, and 150 μm were etched in 0.025 mol/L NaOH meth­
anol/water (2/1) solution for 0, 6, 12, and 48 h, respectively, to get the
surface with high roughness and hydrophilicity. For convenience, the
samples named as diameter-etching time. For instance, the 700-E48
sample means that the average diameter is 700 μm and the etching
time is 48 h for the PLA micro-particles. Second, the Ag layer was
deposited on the surface of the etched PLA micro-particles by electroless
plating, according to our previous work [65]. Before Ag deposition, the
PLA micro-particles were sensitized in the SnCl2 acid aqueous solution,
which was composed of 1.0 g SnCl2⋅2H2O and 200 mL dilute HCl solu­
tion (1.0 vol.%), for 20 min. The Sn2þ was absorbed onto the surface of
the PLA micro-particles (Fig. S1). After absorption of Sn2þ, the Ag par­
ticles were deposited onto the PLA surface. Double reductants of glucose
and sodium tartrate were applied to ensure the Ag particles grew stably
and uniformly. The sensitized PLA micro-particles were added into
0.08 mol/L silver ammonia solution and reduction solution composed
with glucose (1.4 g), sodium tartrate (3 g), NaOH (0.5 g), and distilled
water (50 mL) for 4 h after washing three times by distilled water.
Finally, the Ag coated PLA micro-particles (Ag@PLA) were dried in a
vacuum oven at the 80 � C over night for the hot pressing. The PLA
micro-particles with Ag layer were confirmed by an EDS and XRD
evaluation (Figs. S2 and S3).
2.3. Preparation of the PLA/Ag nanocomposites with large-area Ag
nanoplates
The PLA/Ag nanocomposites with large-area Ag nanoplates were
hot-pressed at 180 � C and 10 MPa. The Ag@PLA micro-particles were
compressed into ϕ12 mm circular sheets with various thickness of 1.0,
1.5, and 2.7 mm, respectively, for electrical conductivity and EMI
evaluation.
2.4. Characterizations
2.4.1. Scanning electron microscope
The morphology of etched PLA micro-particles, Ag coated PLA
micro-particles, and the PLA/Ag nanocomposites were evaluated by a
field-emission scanning electron microscope (FE-SEM) (JEOL-7800F) at
an accelerating voltage of 10.0 kV. For the PLA/Ag nanocomposites, the
samples were cryo-fractured and coated with thin layer platinum before
the SEM observation. In order to further proof the formation of the large-
area Ag nanoplates, the PLA/Ag nanocomposites was dissolved in
dichloromethane and collected the sediments which were the Ag
nanoplates. The SEM test was used to observe the sediments.
2.4.2. Electrical conductivity
The electrical conductivity of the PLA/Ag nanocomposites was tested
on a four-point probe instrument (RTS-8, Guangzhou Four-Point Probe
Technology Co., Ltd., China) at room temperature. At least five speci­
mens were tested and the average data was given.
2.4.3. Electromagnetic interference shielding
The EMI SE of the samples in the frequency range of 8.2–12.4 GHz
(X-band) was tested by using an Agilent N5247A vector network
analyzer at room temperature via the coaxial method. The samples were
compressed into ϕ12 mm circular sheets with various thickness of 1.0,
1.5, and 2.7 mm for the test.
J. Li et al.
Fig. 1. Schematic illustration of the processing procedure for the Ag coated PLA micro-particles and the PLA/Ag nanocomposites with large-area Ag nanoplates.
3. Results and discussion
3.1. Morphology
In order to enhance the interfacial interaction between Ag particles
and PLA, the surface of PLA micro-particles was etching in a NaOH
methanol/water solution. After etching, the hydrophilicity of PLA
micro-particles was improved (Fig. S4), which was benefit to deposit Ag
particles on their surface. Furthermore, some PLA chains in the amor­
phous phase were removed by the solution, which left micro- or nano-
holes on the surface [66]. The micro- or nano-holes also increased the
interfacial interaction between PLA micro-particles and Ag layers. Fig. 2
shows the surface of PLA micro-particles and etched PLA
micro-particles. Without etching, the surface of PLA micro-particles was
too compact to deposit Ag particles on the surface stably. After etching,
the surface of PLA micro-particles became rough and had many micro-
or nano-holes. The holes and roughness of surface increased with
increasing the etching time.
Fig. 3 shows Ag coated PLA micro-particles with different etching
time. After Ag electroless plating, a thin of Ag layer, which was
composed of Ag nanoparticles, was coated on the surface of the PLA
micro-particles. For convenience, the coated PLA micro-particles were
defined as Ag@PLA particles. As expected, the more compact Ag layer
Fig. 2. SEM images of the PLA micro-particles (700 μm) without etching (a, d), etching 12 h (b, e), and etching 48 h (c, f).
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was found in the samples with longer etching time. The Ag layer of the
non-etched PLA micro-particles was sparse with exposed holes, as shown
in Fig. 3g. After 12-h etching, the Ag layer gradually became dense and
the holes disappeared (Fig. 3h). The Ag layer was more compact after
the 48-h etching (Fig. 3i), indicating that more Ag particles were
deposited on the surface of PLA micro-particles with longer etching
time. Certainly, the thickness of the Ag layers could be regulated by
controlling the etching time.
Finally, the PLA/Ag nanocomposites with large-area Ag nanoplates
were fabricated by the hot compression molding under high compres­
sion pressure. Fig. 4 shows the morphology and the dispersion of Ag
particles in the PLA/Ag nanocomposites prepared by compression
molding different diameter of PLA micro-particles. As expected, Ag
nanoplates with large area were found in all the samples by compression
molding form the PLA micro-particles. It was because that the coated Ag
layers were crushed into Ag nanoplates during fusing the Ag@PLA
micro-particles. Obviously, the Ag nanoplates were distributed uni­
formly in PLA by this kind of fabrication, as shown in Fig. 4. Further­
more, the lateral size of Ag nanoplates was much relative to the average
diameter of Ag@PLA micro-particles. The average length of Ag nano­
plates was shorter than the average diameter of Ag@PLA micro-
particles. The average lengths of Ag nanoplates were ~150, ~200,
~350, and ~500 μm for the 150-E12, 350-E12, 500-E12, and 700-E12,
J. Li et al. Composites Part B 171 (2019) 204–213

Fig. 3. SEM images of Ag coated the PLA micro-particles (700 μm) without etching (a, d, g), etching 12 h (b, e, h), and etching 48 (c, f, i).

Fig. 4. SEM images of the PLA/Ag nanocomposites with large-area Ag nanoplates by the compression molding from different average diameter of PLA micro-
particles: 150 (a), 350 (b, c), 500 (d) and 700 μm (e, f). The etching time was 12 h for all the PLA micro-particles. The red arrows in the images indicated the
large-area Ag nanoplates. (For interpretation of the references to colour in this figure legend, the reader is referred to the Web version of this article.)

respectively. The results indicated that the larger lateral size could be
formed in the samples with larger PLA micro-particles.
Fig. 5 shows the sediments of the PLA/Ag nanocomposites preparing
from 700-E0 and 700-E12 particles. Indeed, the large-area Ag nano­
plates were found in the sediments, suggesting that it is reliable for our
strategy to fabricate large-area Ag nanoplates. Furthermore, the
compact and thick Ag nanoplates were found in the samples after
etching, indicating the etching procedure was really beneficial to the
deposition of Ag particles. The results were consistent with the obser­
vation of the Ag@PLA micro-particles. We believe that the large-area Ag
nanoplates formed in PLA matrix can abruptly enhance the EMI
shielding of the PLA/Ag nanocomposites.

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J. Li et al. Composites Part B 171 (2019) 204–213

Fig. 5. The sediments of the PLA/Ag nanocomposites after removing PLA phase: (a, c) 700-E0 and (b, d) 700-E12.

3.2. Electromagnetic interference shielding
3.2.1. Effect of Agþ concentration during the deposition
The amount of Ag particles coated on the surface of PLA micro-
particles was an important issue for improving the electrical conduc­
tivity and EMI shielding of the PLA/Ag nanocomposites. Herein, the PLA
micro-particles were coated with different Agþ concentration to
construct a high efficient conductive network in the PLA/Ag nano­
composite and finally improve the electrical conductivity and EMI SE. In
order to investigate the effect of Agþ concentration during the deposi­
tion on EMI shielding and electrical conductivity, the PLA micro-
particles with the same size (700-E0) were coated under the same pro­
cedure and conditions. The electrical conductivity and EMI SE of PLA/
Ag nanocomposite with the thickness of 1.5 mm increased with
increasing the Agþ concentration, as shown in Fig. 6. For example, the
electrical conductivity and EMI SE of PLA/Ag nanocomposite increased
from 0.4 S/m and ~5 dB to 495 S/m and 32 dB by increasing the Agþ
concentration from 0.02 to 0.08 mol/L.
The EMI SE, which is the sum of absorption shielding (SEA), reflec­
tivity shielding (SER), and multiple reflections shielding (SEM), can be
evaluated by the incident (Pin) and transmitted electromagnetic power
(Pout), SETotal ¼ 10 log (Pin/Pout) ¼ SEA þ SER þ SEM [65,67]. The com­
mercial requirement of EMI shielding materials is above 20 dB, indi­
cating the materials attenuated 99% microwave. Herein, the EMI SE of
the PLA/Ag nanocomposites with the Agþ concentration of 0.08 mol/L
was 32 dB, suggesting that the nanocomposite attenuated 99.94% mi­
crowave. In addition, the SEM can usually be negligible when SETotal is
above 15 dB [63]. Therefore, the SEA, and SER can further be calculated
by SEA ¼ 10 log (T/(1-R)) and SER ¼ 10 log (1-R), respectively, where
R is the power coefficient of reflectivity and T is the power coefficient of
transmissivity. Fig. 6b shows the SEA and SER of the nanocomposites
preparing with the Agþ concentration of 0.04, 0.06 and 0.08 mol/L. The

Fig. 6. (a) EMI SE as a function of frequency (X-band) for the PLA/Ag nanocomposites with the thickness of 1.5 mm prepared from the Ag@PLA micro-particles (700-
E0) that were coated with various Agþ concentration (mol/L); (b) Comparison of SEA, SER at 12.4 GHz and electrical conductivity for the PLA/Ag nanocomposites.

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J. Li et al.
SEA value was higher than the SER value, indicating the
absorption-dominated EMI shielding for all the samples. For example,
SEA and SER of the nanocomposites preparing with the Agþ concentra­
tion of 0.08 mol/L were 26.8 dB and 6.1 dB at the frequency of
12.4 GHz, respectively, which SEA had a contribution of 81.5%, while
SER had 18.5%, to the shielding performance. Obviously, the SEA value
increased greatly while SER increased slightly with the Agþ concentra­
tion, indicating that the increasing EMI SE was mainly due to the
increasing SEA. Therefore, the PLA/Ag nanocomposite with large-area
Ag nanoplates was a typically absorption-dominated shielding mecha­
nism, mainly depending on the high electrical conductivity and the
large-area Ag nanoplates.
3.2.2. Effect of etching time and diameter of PLA micro-particles
Fig. 7 shows the EMI SE of the PLA/Ag nanocomposite prepared from
the PLA micro-particles with the average diameter of 700, 500, 350, and
150 μm with different etching time at the X-band (8.2–12.4 GHz). In
order to obtain excellent EMI SE, the Agþ concentration of 0.08 mol/L
was selected to study the influence of lateral size of the Ag nanoplates
and etching time on electrical conductivity and EMI SE. Because of the
large-area Ag nanoplates and their well dispersion, the PLA/Ag nano­
composites exhibited high electrical conductivity and excellent EMI
shielding. For example, the electrical conductivity and EMI SE of the
PLA/Ag nanocomposites reached 2967 S/m and ~45 dB, when the
particle size was 700 μm and the etching time was 48 h. It should be
noticed that the content of Ag was only 0.82 vol%, indicating that the
large-area Ag nanoplates were more efficient to enhance EMI SE than
that of the segregated Ag chains in PLA matrix [63].
Fig. 7. EMI SE as a function of frequency (X-band) for the PLA/Ag nanocomposites with the thickness of 1.5 mm prepared from the PLA micro-particles with the
average diameter of 700 (a), 500 (b), 350 (c), and 150 μm (d) with different etching time.
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First, the electrical conductivity and EMI SE increased with
increasing the etching time for all the samples preparing from the
different average diameter of PLA micro-particles. For example, the
electrical conductivity and EMI SE of the PLA/Ag nanocomposites,
which were formed from PLA micro-particle with the diameter of
350 μm, increased from 401 S/m and ~25 dB to 2725 S/m and ~44 dB
from without etching to the 48-h etching, respectively. The improve­
ment on the electrical conductivity and EMI SE was ascribed to the more
Ag coating on PLA surface with longer time etching. The fraction of Ag
for the PLA/Ag nanocomposites were tested by a thermogravimetric
analyzer (TGA) (TA Q600, USA) at a heating rate of 10 � C/min from 40
to 600 � C under N2 atmosphere (50 mL/min) (Fig. S5). The content of Ag
in PLA matrix increased from 0.38 to 0.93 vol% from without etching to
the 48-h etching. Due to the improvement on the hydrophilicity and
roughness of the PLA micro-particles after etching, the surface could
provide more active sites for the Ag electroless plating, resulting in
higher content of Ag in the nanocomposites. The higher Ag loadings
turned out the thicker and more compact Ag nanoplates, leading to
higher electrical conductivity and EMI SE. However, the conductivity of
the composites was still lower than that of Ag materials which can reach
6.3 � 107 S/m. The result was ascribed to the junction resistance in the
composites. Because the Ag nanoplates were trapped in the PLA matrix,
the junction resistance existed between Ag nanoplates.
Second, the electrical conductivity and EMI SE decreased with
increasing the average diameter of PLA micro-particles at the same
etching time. For example, the 150-E48 samples had the highest elec­
trical conductivity and EMI SE among 150-E48, 350-E48, 500-E48, and
700-E48 samples. According the above discussion, the lateral size of the
J. Li et al.
Ag nanoplates increased with increasing the average diameter of PLA
micro-particles. The results indicated that electrical conductivity and
EMI SE was irrelative to the lateral size of the Ag nanoplates but relative
to the 2D structure of the Ag nanoplates. However, we noticed that the
content of Ag increased with decreasing the average diameter of PLA
micro-particles because of the larger surface area in the smaller micro-
particles. For instance, the Ag loading of the 700-E0 samples was
0.24 vol%, but the 150- E0 samples reached 0.42 vol%. The more Ag
loadings usually leaded to the higher electrical conductivity and EMI SE.
Fig. 8 shows the SETotal, SEA and SER of the PLA/Ag nanocomposites
preparing from the PLA micro-particles with the average diameter of
700, 500, 350, and 150 μm and different etching time. Obviously, SETotal
and SEA increased with etching time, while SER increased slightly,
indicating that the improvement of EMI SE was mainly attributed to the
increase of SEA. For example, the SETotal, SEA and SER of the 500-E0
samples are 24.7, 18.1, and 6.6 dB at the frequency of 9.0 GHz. The
contribution of the absorption and reflection to the total EMI SE were
73.3 and 26.7%, respectively. However, the SETotal, SEA and SER of the
500-E48 samples are 40.2, 29.3, and 10.9 dB at the frequency of
9.0 GHz. The contribution of the absorption and reflection to the total
EMI SE were 72.9 and 27.1%, respectively. The results indicated that the
PLA/Ag nanocomposites exhibited an absorption-dominated shielding
mechanism. The etching process was conducive to increase the Ag
loading, as well as the absorption of electromagnetic waves, and finally
improved EMI SE of the PLA/Ag nanocomposites.
Fig. 8. Comparison of total EMI shielding effectiveness (SETotal), microwave absorption (SEA) and microwave reflection (SER) at the frequency of 9.0 GHz for the
PLA/Ag nanocomposites with the thickness of 1.5 mm prepared from the PLA micro-particles with the average diameter of 700 (a), 500 (b), 350 (c), and 150 μm (d)
with different etching time.
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3.2.3. Effect of thickness of the PLA/Ag nanocomposite
Fig. 9 shows EMI SE of the PLA/Ag nanocomposites with different
thickness. Obviously, the EMI SE of the PLA/Ag nanocomposites
increased with increasing the thickness from 1.0 mm to 2.7 mm, because
of the increasing amount of Ag nanoplates in the nanocomposites to
attenuate the incoming electromagnetic waves. Exhilaratingly, the
nanocomposites with thickness of only 1.0 mm presented a satisfactory
EMI SE of 36.9 dB, which already exceeded the requirement for EMI
shielding industrial applications. The high performance EMI shielding of
the nanocomposites was also ascribed to low skin depths of the com­
posites which were less than 300 μm (Fig. S6). Normally, the composites
had high performance EMI shielding when the skin depths was lower
than the thickness of the samples [63]. When the sample thickness was
2.7 mm, the EMI SE reached 60.4 dB which attenuated 99.9999% the
incoming electromagnetic waves. In addition, the contribution of SEA to
SE Total was larger than that of SER, also demonstrating the
absorption-dominated shielding mechanism.
3.3. Mechanism
Table 1 gives comparison of EMI SE of the PLA/Ag nanocomposites
in this work and the reported values of some CPCs in the X-band. In this
work, the EMI SE reached 36.9 dB with only thickness of 1.0 mm and the
Ag content of 0.99 vol%. Compared with the reported work for the PLA-
based CPCs, the high-performance EMI SE was achieved in the PLA/Ag
J. Li et al. Composites Part B 171 (2019) 204–213

Fig. 9. EMI SE as a function of frequency (X-band) for the PLA/Ag nanocomposites prepared from the PLA micro-particles with the average diameter of 150 μm with
etching time of 48 h: (a) effect of thickness on EMI SE, (b) comparison of the SETotal, SEA, and SER at the frequency of 9.0 GHz.

Table 1
Comparison of EMI SE of the PLA/Ag composites with large-area Ag nanoplates and the reported values of some CPCs in the X-band. Our results were indicated by the
bold font.
Filler Polymer matrix Filler content Thickness EMI SE (dB) Method Ref.

Ag nanoplates PLA 7.75 wt% (0.99 vol%) 1.0 mm 36.9 Electroless plating This work
1.5 mm 46.1 Electroless plating This work
2.7 mm 60.4 Electroless plating This work
Ag PAN 20 wt% 0.75 mm 40 Electroless plating [68]
Ag PLA 2.3 vol% 1.5 mm 33 Electroless plating [63]
AgNW WPU 28.6 wt% 2.3 mm 20 Dipping [61]
AgNW PDA/PPy 20 wt% 95 μm 25.9 In-situ polymerization [69]
Ag/BaTiO3 PVDF 20 vol%/15 vol% 1.2 mm 21 Solvent processing [70]
Graphite PLLA 5 wt% 2.0 mm 45 Injection molding [71]
MWCNT PLLA 10 wt% 2.5 mm 23 Foaming [72]
MWCNT PLLA/PDLA 1.48 vol% 3.7 mm 21.6 Freeze drying [26]
GNP PLLA 15 wt% 1.5 mm 15.5 Melt processing [48]
MWCNT PDMS 3 wt% 2.0 mm 31.02 Melt processing [45]
Cu PS 7 vol% 3 mm 30 Electroless plating [73]
Au/MWCNT PVDF 3 wt%/3 wt% 0.5 mm 26.7 Solvent processing [74]

nanocomposites with large-area Ag nanoplates at low conductive filler
loadings and thin samples. The excellent EMI SE for the PLA/Ag nano­
composites was ascribed to the large-area Ag nanoplates, which could
attenuate incoming microwaves efficiently. Fig. 10 illustrates the
mechanism of EMI shielding for the PLA/Ag nanocomposite with large-
area Ag nanoplates. When the incident waves transmitted though the
nanocomposites, it would separate into the reflected waves, the trans­
mitted waves and the absorbed waves. Because of the large-area Ag
Fig. 10. Schematic representation of mechanism of EMI shielding for the PLA/
Ag nanocomposite with large-area Ag nanoplates.
nanoplates, the microwaves were efficiently absorbed by repeated
reflection-absorption at the interfaces between Ag nanoplates and PLA
matrix.
4. Conclusion
In this work, the PLA/Ag nanocomposites with large-area Ag nano­
plates were fabricated by Ag electroless plating on the surface of the PLA
micro-particles to achieve high electrical conductivity and excellent EMI
SE. Because of the improvement on the hydrophilicity and roughness of
the PLA micro-particles after etching, the thick and compacte Ag
nanoplates was coated on the surface of the particles, which induced the
higher electrical conductivity and EMI SE. For example, the electrical
conductivity and EMI SE of the PLA/Ag nanocomposites, which weskire
formed from PLA micro-particles with the diameter of 350 μm, increased
from 401 S/m and ~25 dB to 2725 S/m and ~44 dB from without
etching to the 48-h etching, respectively. In addition, the average lateral
lengths of Ag nanoplates were ~150, ~200, ~350, and ~500 μm for the
150-E12, 350-E12, 500-E12, and 700-E12, respectively, indicating the
Ag nanoplates with larger lateral size were achieved by using the bigger
PLA micro-particles. However, the electrical conductivity and EMI SE
were weak correlation with the lateral size of Ag nanoplates, but
dependent on the amount and the 2D structure of Ag nanoplates. For
example, the electrical conductivity and EMI SE of PLA/Ag nano­
composite increased from 0.4 S/m and ~5 dB to 495 S/m and 32 dB by
increasing the Agþ concentration from 0.02 to 0.08 mol/L, because more

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J. Li et al. Composites Part B 171 (2019) 204–213

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The authors are grateful to the Opening Project of State Key Labo­
Fabrication of a flexible electromagnetic interference shielding Fe3O4@reduced
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Appendix A. Supplementary data
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