Chemical Engineering Journal 405 (2021) 126927

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Chemical Engineering Journal

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

Construction of shape-memory carbon foam composites for adjustable EMI T

shielding under self-fixable mechanical deformation
Xichen Jiaa,b, Bin Shena,b, , Lihua Zhanga, Wenge Zhenga,b
⁎

a
Ningbo Key Lab of Polymer Materials, Ningbo Institute of Material Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang Province 315201, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

HIGHLIGHTS GRAPHICAL ABSTRACT

• Carbon foam composites with shape-

memory polymer coating are fabri-
cated.
• The composites possess excellent
thermally/electrically stimulated
shape-memory behaviors.
• The composites can realize convenient
SE regulation under self-fixable me-
chanical deformation.
• The composites can exhibit smart
function-tunable or function-switch-
able feature.

ARTICLE INFO ABSTRACT

Keywords: The design and fabrication of novel electromagnetic interference (EMI) shielding materials with the capability of
Biomass-derived carbon foam realizing convenient performance regulation under self-fixable mechanical deformation is becoming an urgent
Shaper-memory trans-l,4-polyisoprene challenge due to the increasingly complex application conditions. To alleviate this problem, the composite
MXene construction that consisted of compressible carbon foam (CF) and shape-memory polymer coating was proposed,
Adjustable EMI shielding
and the demo samples were fabricated by coating trans-l,4-polyisoprene (TPI)-MXene layer onto compressible
Self-fixable mechanical deformation
wood-derived CF with multilayer microstructure. The resultant composites (thickness: ~2–10 mm, density:
~150 mg/cm3) with enhanced shielding effectiveness (SE) of ~25.3–44.7 dB could not only adjust their SE value
by changing their compressive strains, but also possess excellent thermally/electrically stimulated shape-
memory behaviors that can be easily deformed and recovered as being heated and fix a temporary shape at low
temperature, thereby realizing convenient SE regulation under self-fixable mechanical deformation. Moreover,
based on different initial SE performance and compression conditions, the EMI SE of the composites can also be
tuned within effective SE range of > 20 dB, or switched between > 20 and < 20 dB, exhibiting smart function-
tunable or function-switchable feature, which provides a promising platform for developing novel EMI shields
for smart electromagnetic response applications.

1. Introduction widely used in various fields such as wireless communication devices

and aerospace equipment, owing to the capability to effectively block
Electromagnetic interference (EMI) shielding materials have been electromagnetic waves. In comparison with the traditional metal-based

⁎
Corresponding author.
E-mail address: shenbin@nimte.ac.cn (B. Shen).

https://doi.org/10.1016/j.cej.2020.126927
Received 4 June 2020; Received in revised form 18 August 2020; Accepted 2 September 2020
Available online 08 September 2020
1385-8947/ © 2020 Elsevier B.V. All rights reserved.
X. Jia, et al.
EMI shields, conductive polymer composites (CPCs) are increasingly
needed by taking their advantages of lightweight, tunable conductivity,
and good processability [1–7]. MXene, the new 2D transition-metal
carbides/nitrides, possess both metal-like electrical property and plenty
of polar functional groups on the surface [8–11], and layered MXene
films with thickness of ~45–60 μm could exhibit shielding effectiveness
(SE) as high as ~92 dB [10], showing obvious superiority over gra-
phene and carbon nanotubes (CNTs) as nanofiller for high-performance
CPCs. In addition, compounding polymers with preconstructed 3D
carbon frameworks could generate more effective conductive networks
and enhanced internal multiple reflections, thereby endowing the CPCs
with higher EMI SE than the uniform-dispersion systems [2,12–14].
Although the 3D carbon frameworks fabricated via the pyrolysis of
natural biomass or freeze-dried biomass-based derivative (such as
cotton [15], wood [16,17], straw [18], and sugarcane [19]) are usually
composed of amorphous carbon and exhibit relatively lower EMI-
shielding efficiency in comparison with those constructed by the self-
assembly of carbon constituents (such as CNTs, graphene, and MXene)
or complicated chemical-vapor-deposition (CVD) approach [2,13,20],
the fabrication of preconstructed carbon frameworks by using renew-
able biomass materials with unique configuration is still the future
tendency from the perspective of sustainable development and abun-
dant resources.
On the other hand, increasingly complex application conditions,
such as the condition requiring the function tunable within effective SE
range of > 20 dB or the function switchable between inefficient weak
shielding (SE < 20 dB) and efficient strong shielding (SE > 20 dB),
present the growing demand for the design of smart EMI shields with
convenient performance regulation under external stimuli [21–24]. For
examples, Song and coworkers have recently constructed porous poly-
propylene (PP) non-woven spacer into highly conductive graphite films
for fabricating the composites with novel sandwich structures [21], and
the moisture stimulus (water loading) was utilized to tune the EMI SE of
the resultant composites via changing the polarization and loss of the
porous spacers. Nevertheless, such moisture stimulus is difficult to
precisely control in atmospheric environment. Shen and other re-
searchers further demonstrated the adjustment of EMI SE through re-
versibly stretching or shrinking the conductive elastic films or the
folded films with the 3D saw-tooth structure [22,24], while this process
is accompanied by a large change in sample length. The construction of
polyurethane/graphene composite foams with compressible porous
microstructure are also reported to conveniently realize the SE reg-
ulation through a simple stimulus of compression with only small
thickness variation [23], since the multiple reflections and scattering of
microwave among the cell walls would be changed based on different
applied compressive strain. However, the above composites are limited
by not being able to fix a certain SE value without the external force
during the process of performance regulation, since the formed me-
chanical deformation would recover when the external force is removed
from the materials. Therefore, it is still necessary to develop new stages
for designing advanced smart EMI shields with the capability of rea-
lizing convenient SE regulation under self-fixable mechanical de-
formation.
In this work, compressible carbon foams (CF) with multilayer mi-
crostructure were fabricated as carbon frameworks through pyrolysis of
chemically treated Balsa wood, and trans-l,4-polyisoprene (TPI) was
selected as polymer matrix owing to its shape-memory function. The
resultant composites prepared by constructing conductive TPI-MXene
coating layer on the CF skeletons showed enhanced EMI SE of
~25.3–44.7 dB with increased MXene loading, and tunable SE value by
changing compressive strains. In addition, they also possessed excellent
thermally and electrically stimulated shape-memory behaviors that can
be easily deformed and recovered as being heated and fix a temporary
shape at low temperature, thereby endowing the composites with
convenient SE regulation under self-fixable mechanical deformation.
Moreover, their SE values can also be tuned within effective SE range
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Chemical Engineering Journal 405 (2021) 126927
of > 20 dB, or switched between > 20 and < 20 dB according to dif-
ferent initial SE performance and compression conditions, exhibiting
smart function-tunable or function-switchable feature. The composite
construction that consisted of compressible CF and shape-memory
polymer coating would provide a promising platform for developing
novel smart EMI shields with convenient SE regulation under self-fix-
able mechanical deformation.
2. Experimental section
2.1. Synthesis of MXene
Ti3C2Tx MXene is obtained by etching Ti3AlC2 with LiF and HCl
mixed solution. In detail: 1 g LiF was added to 20 ml 9 M HCl and
stirred to dissolve. Then, 1 g Ti3AlC2 was slowly added and stirred for
24 h at 35 °C. The resulted solution was centrifuged repeatedly to wash
by deionized water at 3500 r/min until the PH of the solution reached
neutrality. After that, the supernatant was extracted and sonicated 1 h
under Ar flow followed by centrifuging at 3500 r/min for 1 h to obtain
Ti3C2Tx aqueous solution. Finally, the aqueous solution was filtered,
vacuum dried and grinded for reserve.
2.2. Preparation of TPI-MXene solution
To facilitate the dispersion of Ti3C2Tx in chloroform, Ti3C2Tx was
modified by Hexadecyl trimethyl ammonium Bromide (CTAB) via
electrostatic interaction. In detail: CTAB was added into the Ti3C2Tx
aqueous solution. After magnetic stirring at room temperature for 2 h,
the modified Ti3C2Tx was prepared by filtration and vacuum drying,
and the mass ratio between CTAB and Ti3C2Tx was ~1:4. To prepare the
TPI-MXene package solution, the hydrophobically modified Ti3C2Tx
sheets was added into a 30 ml chloroform followed by sonication for
30 min. Then, 1.2 g TPI particles and 24 mg DCP were added into the
solution, followed by stirring for 4 h at room temperature. The content
of CTAB-MXene in the TPI/MXene mixture was controlled to be ~5,
~10, and ~20 wt%, respectively.
2.3. Fabrication of carbon foam
Balsa wood was modified by a two-stage chemical treatments to
remove most of lignin and hemicellulose. In detail: Balsa wood was
firstly dried at 80 °C for 12 h, and then it was treated in 2.5 M NaOH
and 0.4 M Na2SO3 mixed solution by stirring for 7 h under boiling. After
that, the wood was washed by boiling deionized water for 3–5 times,
and then it was further treated in 2.5 M H2O2 aqueous solution at 95 °C
for 24 h. Finally, the wood foam was obtained by freeze drying for 48 h,
and compressible carbon foam was prepared by carbonization of wood
foam at 1000 °C with heating rate of ~10 °C/min under high-purity Ar
flow for 1 h.
2.4. Preparation of TPI-M/CF composites
The as-fabricated compressible carbon foam was infiltrated in the
TPI-MXene package solution for 30 min and then taken out for drying in
a vacuum oven at room temperature for 12 h. After that, the TPI-M/CF
composites with shape-memory ability were obtained by crosslinking at
160 °C for 15 min under N2 protection, followed by cooling at room
temperature.
2.5. Characterizations
The morphology and structure were studied by Hitachi S-4800 field-
mission scanning electron microscopy (SEM) at an accelerating voltage
of 8 kV. X-ray diffraction (XRD) patterns were collected using a Bruker
AXIS X-ray diffractometer with CuKa radiation at a generator voltage
and current of 40 kV and 40 mA. Thermal gravimetric analysis (TGA)
X. Jia, et al.
Fig. 1. (a) Schematic illustration of the fabrication process of shape-memory TPI-M/CF composites. (b–d) SEM images of (b) Ti3AlC2, (c) clay-like Ti3C2Tx and (d)
few-layer curled Ti3C2Tx sheet. (e) TEM image of flat Ti3C2Tx sheet. (f) Zeta potentials of positively charged CTAB and negatively charged Ti3C2Tx. (g) XRD patterns
of Ti3AlC2, Ti3C2Tx and CTAB-Ti3C2Tx hybrid.
was conducted on Mettler-Toledo TG/DSC analyzer at 10 °C/min from
30 to 800 °C under N2 atmosphere. Differential scanning calorimetry
(DSC) were conducted on PerkinElmer Diamond DSC analyzer at a
heating and cooling rate of 10 °C/min and in the temperature range of
−20 to 100 °C. The chemical composition was analyzed by using
Nicolet 6700 Fourier Transform Infrared (FT-IR) Spectrometry. The
zeta potential was tested using Zetasizer Nano ZS equipment. The
electrical conductivity was tested using a four-probe method on a
Napson Cresbox Measurement System. The mechanical properties were
tested using an Instron 5567 testing system at a rate of 10 mm/min. The
infrared photographs were measured by a FLIR E8 thermal imager. The
EMI SE together with S parameters were measured by the R&S ZVA67
vector network analyzer using the wave-guide method in X-band.
3. Results and discussion
The overall fabrication process of TPI-M/CF composites was de-
picted in Fig. 1a. Firstly, Ti3C2Tx MXene was fabricated by MILD
method: Al atom layers of Ti3AlC2 were selectively etched out with a
mixed LiF-HCl solution, followed by centrifugation and sonication to
prepare the uniform Ti3C2Tx suspension. After hydrophobic modifica-
tion of Ti3C2Tx with CTAB via electrostatic interaction (to facilitate the
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Chemical Engineering Journal 405 (2021) 126927
dispersion of Ti3C2Tx in chloroform), the packaging TPI-MXene solution
was prepared by blending the modified Ti3C2Tx with TPI-chloroform
solution. Then, nature Balsa wood (NW), the lightest wood with unique
microstructure (the channel-like and grid-like microstructure of nature
wood) and thin cell wall, was selected as the raw material to fabricate
compressible and conductive CF through two-stage chemical treatment
as well as high-temperature carbonization under insert atmosphere,
since the excellent mechanical compressibility could ensure the struc-
tural integrity of conductive CF skeletons during mechanical deforma-
tions, thereby keeping the shielding performance relatively stable. Fi-
nally, the TPI-M/CF composites were prepared by infiltrating the CF
into the TPI-MXene solution with different CTAB-MXene loading and
followed by vacuum-drying and cross-linking. As we know, semi-
crystalline TPI is a shape-memory polymer, which can fix the temporary
deformation at low temperatures thanks to the presence of crystalline
TPI domains and then recover its original, undeformed shape upon
heating owing to the entropic elasticity of crosslinking networks
[25–27]. The introduction of TPI-MXene coating could not only endow
the compressible CF with excellent thermally/electrically stimulated
shape-memory ability, thereby realizing convenient SE regulation of the
composites under self-fixable mechanical deformation, but also en-
hance the EMI-shielding performance owing to the superior electrical
X. Jia, et al.
performance of Ti3C2Tx MXene sheets.
As shown in Fig. 1b, Ti3AlC2 powders exhibited a multilayered block
structure, while the interlayer space of clay-like Ti3C2Tx increased ob-
viously after etching (Fig. 1c), which is attributed to the reaction of HF
with Al layers of Ti3AlC2 to produce a large amount of H2. Moreover,
the intercalation of lithium ions also leaded to increase the interlayer
space of clay-like Ti3C2Tx. After ultrasonic exfoliation, the few-layer
curl and flat lamellar structure of Ti3C2Tx MXene was observed
(Fig. 1d–e). The similar results can be also revealed by XRD analysis
(Fig. 1g), in which the (0 0 2) peak of Ti3C2Tx shifted to a smaller angle
compared to that of Ti3AlC2 in account of their larger interlayer space,
further proving the success of the etching process. On the other hand,
the zeta potential of CTAB and Ti3C2Tx aqueous solutions at different
pH values (Fig. 1f) indicated that CTAB is positively charged and
Ti3C2Tx is negatively charged in aqueous solution. Under neutral con-
dition of pH = 7, their zeta potential were around 40 mV and −35 mV,
confirming that they could be combined by electrostatic interaction.
The long-chain alkyl groups of CTAB greatly improves the hydro-
phobicity of Ti3C2Tx, so that the modified Ti3C2Tx can be uniformly
dispersed in chloroform to prepare the TPI-MXene solution. XRD ana-
lysis was carried out to obtain further insight into the structural evo-
lutions of the modified Ti3C2Tx (Fig. 1g), showing that its (0 0 2) peak
shifted to a much smaller angle after modification, mainly because of
the reason that the CTAB can play the role of intercalation agent and
embed into the Ti3C2Tx lamella by combining the surface functional
groups of Ti3C2Tx via electrostatic interaction, resulting in the increased
interlayer spacing of Ti3C2Tx.
The novel shape-memory TPI-M/CF composites were obtained by
the TPI-MXene encapsulation of compressible CF derived from wood
foam (WF). Fig. 2 shows the morphological variation of different ma-
terials in the process of TPI-M/CF preparation. Nature wood was yel-
lowish in color (Fig. 2a) and exhibited a channel-like and grid-like
microstructure in the X-plane and Y-plane (Fig. 2e and 2i), respectively.
After being treated by NaOH/Na2SO3 and H2O2, the WF weight de-
creased by ~58% and its density decreased from ~120 to ~45 mg/cm3
owing to the remove of most of the lignin and hemicellulose as well as
partial cellulose, and the residual cellulose resulted in the color of the
Fig. 2. (a–d) Photographs of (a) nature Balsa wood, (b) wood foam (treated by NaOH/Na2SO3 and H2O2), (c) carbon foam (carbonized at 1000 °C), and (d) TPI-M/CF
composite. (e–h) SEM images showing the X-plane microstructure of different materials. (i–l) SEM images showing the Y-plane microstructure of different materials.
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Chemical Engineering Journal 405 (2021) 126927
WF altered to white (Fig. 3b). Moreover, most of thin grid cell walls in
nature wood were destroyed during chemical treatments, and they
tended to attach onto the nearest unbroken ray under the driven of ice
template during the freeze-drying, thereby leading to the WF mor-
phology changing to a cellulose-oriented and multilayer microstructure
(composed of numerous layers stacked together) in the X-plane and Y-
plane direction (Fig. 2f and 2j). The FT-IR spectra corresponding to
nature wood in different stages are also shown in Fig. 3a, in which the
characteristic peaks of OeC]O at ~1731 and ~1238 cm−1, as well as
aromatic skeletal vibrations at ~1598, ~1504 and ~1458 cm−1 dis-
appeared basically, confirming that the components of hemicellulose
and lignin has almost been removed from nature wood by NaOH/
Na2SO3 and H2O2 [28,29]. Nevertheless, the XRD patterns in Fig. 3b
revealed that the process of chemical treatments has little effect on the
crystal form and arrangement of residual cellulose, since their typical
(1 0 1), (0 0 2) and (0 4 0) diffractions at 2θ values of ~15.1°, ~22.5° and
~34.3° were almost unchanged [28,30].
The conductive and compressible CF composed of amorphous
carbon was further prepared via pyrolysis of the WF sample at 1000 °C,
and the color turned black as well as the size reduced by about half due
to the decomposition of most oxygen substances in cellulose (Fig. 2c),
thereby resulting in the shrinkage of the cellulose-oriented micro-
structure in the X-plane (Fig. 2g). In addition, though the weight and
density of CF further decreased by ~90% (similar with the TGA result
in Fig. 3c) and ~73% (~12 mg/cm3), the similar multilayer micro-
structure in the Y-plane was well preserved as shown in Fig. 2k, which
can not only endow the CF with excellent mechanical compressibility,
but also facilitate the microwave attenuation via the enhancement of
multi-reflections. Fig. 2d, h and l represented the morphology of the
TPI-M/CF composites (the density increased to ~150 mg/cm3),
showing that the internal CF skeletons were relatively evenly covered
by the TPI-MXene layer, and extra SEM images without obvious MXene
aggregates (Fig. S1) have confirmed the homogeneous distribution of
MXene inside the TPI matrix. The appearance of the typical diffraction
peaks belong to the β-form crystallites of TPI in the XRD curve (Fig. S2)
confirmed the successful TPI-MXene encapsulation [31,32]. Moreover,
the TGA analysis (Fig. 3c) showed the high initial thermal
X. Jia, et al.
Fig. 3. (a) FT-IR and (b) XRD spectra of nature wood at different stages of chemical treatments. (c) TGA curves of wood foam and TPI-M/CF with 10 wt% CTAB-
MXene. (d) DSC spectra of carbon foam and TPI-M/CF with 10 wt% CTAB-MXene.
decomposition temperature of ~326 °C for TPI-M/CF composite, re-
vealing its ideal thermal stability.
The outstanding compression performance of the WF and CF was
investigated subsequently, and as seen in Fig. 4a–b, they could easily
bear a 50% compressive deformation on account of high porosity be-
tween layers, and immediately recover to the original thickness without
obvious skeleton destruction. The compressive stress (σ) as a function of
strain (ɛ) for the WF and CF samples (as well as those of nature wood
and carbonized wood) are also given in Fig. 4c–d, and they were pre-
stabilized by applying several compression cycles before testing. Ob-
viously, nature wood deformed permanently after being compressed
over 60% due to the elimination of air voids in the grid-like holes and
the destruction of fragile vertical cell walls, which is also the reason
why the carbonized wood crashed into small pieces after compression
(Fig. S3). In contrast, the σ-ɛ plots of the WF and CF were close to other
reported foam-like porous materials [33–35], exhibiting a linear stage
and non-linear increasing stage at around 0 ~20% and 20 ~60%
compressive strain, which reflected the elastic bending and buckling of
cell walls as well as the elimination of inside air holes in the multilayer
structure. The applied strain can decrease to nearly zero after releasing
the stress under compression of ~20%, ~40% and ~60%, suggesting
the almost complete shape recovery without obvious plastic deforma-
tion. This superior compressibility is the key to ensure the structural
integrity of conductive CF skeletons during the performance regulation
of TPI-M/CF composites.
The thermally and electrically stimulated shape-memory behaviors
of TPI-M/CF composite have also been demonstrated using CTAB-
MXene loading of 10 wt% as an example, and the DSC analysis showed
that its melting temperature (Tm) was ~51.7 °C (Fig. 3d). As seen in
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Chemical Engineering Journal 405 (2021) 126927
Fig. 4e, unlike the CF whose compressive deformation would recover
when the external force is removed (Fig. 4b), the TPI-M/CF composite
could be compressed easily at ~60 °C (above the Tm), and fix the
compressive deformation of ~50% quickly when decreasing the tem-
perature to ~0 °C. The as-formed deformation could be well kept at
room temperature without the external force on account of the crys-
talline TPI domains. After being placed on a heating table at ~100 °C,
the deformed TPI-M/CF could recover to the original thickness in ~90 s
owing to the entropic elasticity of crosslinking networks as well as the
super elastic resilience of CF skeletons. To show the electrically sti-
mulated recovery, the deformed TPI-M/CF was pasted with two copper
electrodes and connected with the stabilized voltage power supply.
Under 3 V voltage, the sample was totally recovered in only ~15 s,
since the abundant CF skeleton as well as conductive MXene networks
can generate strong Joule-heating effect and enhance the inside heat
transfer, thus heating the structure more uniformly and inducing the
transformation of TPI from semicrystalline to amorphous state more
effectively and quickly in comparison with the traditional heating
process. The infrared thermal images also confirmed that the TPI-M/CF
was heated gradually from bottom to top on a heating table, while the
whole sample was heated more uniformly during the Joule-heating
process. Moreover, after repeating ten compressive testing cycles
mentioned above, the TPI-M/CF could substantially regain the original
thickness based on the Joule-heating under 3 V voltage, indicating the
good cyclic reproducibility. The above results suggested that, the TPI-
M/CF composites possessed excellent shape-memory ability that can be
easily deformed and recovered as being heated above the Tm and fix a
temporary shape at low temperature, which should mainly originated
from the double network consisting of semicrystalline TPI elastomer
X. Jia, et al.
Fig. 4. Photographs of (a) wood foam and (b) carbon foam during the compression and release process. Stress-strain curves of (c) wood foam and (d) carbon foam
with different compressive strains. (e) Photographs and corresponding infrared thermal images showing the thermally and electrically stimulated shape-memory
behaviors of TPI-M/CF composite with 10 wt% CTAB-MXene loading.
and compressible CF skeletons. We believe that this advantage can be
integrated closely with the EMI-shielding performance to realize con-
venient SE regulation under self-fixable mechanical deformation.
The EMI SE of different TPI-M/CF samples with thickness of
~10 mm were firstly measured using the wave-guide method in the X-
band frequency range. As shown in Fig. 5a, the SE total of neat TPI/CF
(without MXene) was as high as ~25.3 dB, which indicated more than
~99% of incident microwave was shielded. With the TPI/MXene
coating, the SE total of TPI-M/CF with ~5, ~10, and ~20 wt% CTAB-
MXene was enhanced to ~26.3, ~36.7 and ~44.7 dB, verifying the
shielding enhancement because of more and more efficient conductive
MXene networks. In addition, the SE values could be tuned by changing
the sample thickness. For instance, the SE total of TPI-M/CF with
~10 wt% CTAB-MXene decreased from ~36.7 to ~21.9 and ~14.9 dB
by reducing the thickness from ~10 to ~5 and ~2 mm (Fig. 5b), re-
spectively. As presented in Fig. 5g, the excellent EMI SE of TPI-M/CF
composites should mainly result from the synergistic effects of
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Chemical Engineering Journal 405 (2021) 126927
microwave reflection at the air-sample interface with impedance mis-
match, and microwave absorption by conduction loss, interface polar-
ization (appear at the interface among MXene, CTAB, TPI and CF ske-
letons) and dipole polarization (come from the doped elements and
other defects), as well as internal multiple reflections and scattering in
the multilayer microstructure [13,36–41].
To identify the EMI-shielding mechanism, the SEA-SER contributions
and R-A coefficients presenting the ability of a shield for reflecting and
absorbing microwave were further calculated from S parameters based
on the followed calculations:
R = |S11 |2 , T = |S21 |2 , A = 1 R T
SER (dB) = 10lg(1 R), SEA (dB) = 10lg(T /(1 R))
SET (dB) = 10lg(PI / PT ) = SER + SEA
As displayed Fig. 5d, by increasing the CTAB-MXene loading, the
X. Jia, et al. Chemical Engineering Journal 405 (2021) 126927

Fig. 5. SE Total of TPI-M/CF composites (a) with different CTAB-MXene loading (~10 mm in thickness) and (b) with different sample thickness (~10 wt% CTAB-
MXene). (c) SE Total of TPI-M/CF composite (~10 wt% CTAB-MXene) during the compression-recovery process with different compressive strains, exhibiting
function-tunable EMI-shielding behavior. (d–f) The average SEA-SER contributions and R-A coefficients corresponding to different TPI-M/CF composites in Fig. 5a–c.
(g) Schematic illustration showing possible EMI-shielding mechanism for TPI-M/CF composites. (h) SE Total of TPI-M/CF composite (~5 wt% CTAB-MXene) with
different compressive strains, exhibiting function-switchable EMI-shielding behavior.

SEA of TPI-M/CF was greatly improved, while their SER value changed
slightly, suggesting more microwave penetrating the material were at-
tenuated by absorption. Interestingly, an obviously decrease of R
coefficient and increase of A coefficient was appeared in the TPI-M/CF
with ~5 wt% CTAB-MXene in comparison with neat TPI/CF, which
could be understood in terms of the explanation that the dispersive
MXene in the TPI coating didn’t form efficient conductive network (the
composite with 5 wt% CTAB-MXene only showed a very low electrical
conductivity below ~10−7 S/m), thereby weakening the impedance
mismatch at the air-sample interface compared to neat TPI/CF, leading
to less microwave being reflected and pushing more microwave into the
material for absorption. By further increasing the MXene loading, the R
coefficient increased while the A coefficient decreased, since more ef-
ficient conductive networks were constructed inside the TPI-MXene
(the composites with 10 and 20 wt% CTAB-MXene exhibited an elec-
trical conductivity of ~0.008 and ~1.03 S/m) and TPI-M/CF compo-
sites, which enhanced the interface impedance mismatch, thus resulting
in more microwave being reflected and less microwave being atte-
nuated by absorption. In addition, with the decrease of sample thick-
ness, the value of SEA and A changed more than that of SER and R
(Fig. 5e), because the variation of sample thickness had little effect on
microwave reflection owing to the similar impedance mismatch at the
air-sample interface. On the other hand, whatever the CTAB-MXene
loading or sample thickness is, the R coefficients (> 0.5) of TPI-M/CF
was always higher than their A coefficients (< 0.5), exhibiting a re-
flection-dominant shielding mechanism for such composites.
The EMI-shielding variation of the TPI-M/CF composite during the
compression was then investigated. As a demonstration, the SE total of
sample with ~10 wt% CTAB-MXene was compared in terms of com-
pressive strain in Fig. 5c (the specimen with a certain self-fixed strain
was prepared by compressing at ~60 °C and rapid cooling at ~0 °C),
showing that the SE value was changed from ~36.7 to ~28.1 and
~23.0 dB when increasing the self-fixed strain to ~30% and ~60%.
Particularly, the SE total can be almost restored to the initial level
during the recovery process (~27.4 and ~35.6 dB for recovering to
~30% strain and the original thickness), confirming the realization of
convenient SE regulation under self-fixable mechanical deformation by
taking advantages of the superior compressibility of CF and the shape-
memory function of TPI-MXene coating. On the other hand, EMI SE of
20 dB is acknowledged as the critical value for practical application.
Because of all the SE performance > 20 dB, the above TPI-M/CF with
~10 wt% CTAB-MXene could play as the effective, function-tunable
EMI shields upon different compression conditions. In addition, as an-
other example, the SE total of TPI-M/CF sample with ~5 wt% CTAB-
MXene was adjusted from ~26.3 to ~16.1 when being compressed to
~60% strain (Fig. 5h), achieving the function switch between

7
X. Jia, et al.
inefficient weak shielding (< 20 dB) and efficient strong shielding
(> 20 dB), which suggested that it could be considered as the function-
switchable EMI shields upon compression.
The underlying mechanisms for the SE regulation of TPI-M/CF
composite during the compression process were also discussed based on
the SEA-SER contributions and R-A coefficients. With the increase of
compressive deformation, the SER and R coefficient of sample with
~10 wt% CTAB-MXene enhanced while its SEA and A coefficient ac-
cordingly decreased (Fig. 5f), which can be explained by associating
with the competition effect between conductivity and thickness varia-
tion of sample during the deformation. The compressed specimen
leaded to more layer-to-layer contacts in the CF skeleton with TPI-
MXene coating, which facilitated the construction of more conductive
paths, thereby enhancing the interface impedance mismatch and more
microwave was consumed by reflection. However, the enormous
weakening of microwave absorption occurred as well owing to the less
microwave that entered into the sample and the decrease of sample
thickness, which outweighed the increased reflection loss derived from
the enhanced conductive paths and resulted in the SE decrease for TPI-
M/CF after compression. The opposite result can also be observed in the
recovery process with the decrease of compression deformation, further
proving the above mechanism analysis.
Overall, the coating of conductive shape-memory polymer onto the
frameworks of compressible CF could bring excellent thermally/elec-
trically stimulated shape-memory capability and enhanced EMI-
shielding performance to them, and further realize the adjustment of
their SE value under simple self-fixable compression deformation
during EMI shielding. In addition to the above wood-based carbon
foams, we believe that other conductive and compressible carbon foams
(such as graphitized graphene foam) or hybrid foams (such as cellulose/
AgNWs foam) could also be served as the frameworks of the composites
[42,43]. However, the TPI is the one-way shape-memory polymer, and
thus there is no “back-compression” upon sample cooling in this work
since the compressive deformation must be realized with the aid of
external stress. If the shape-memory polymer we used for coating has
the external stress-free two-way reversible shape-memory feature
(making reversible shape changes between two shapes without external
stress) [44], it can be combined with compressible carbon foam to
prepare EMI-shielding materials with two-way reversible SE modula-
tion. On the other hand, according to the initial EMI SE value of the
composites, two types of smart electromagnetic response materials can
be obtained, including function-tunable EMI shields within effective SE
range of > 20 dB and function-switchable EMI shields with the SE value
switched between > 20 and < 20 dB. We believe that the change of
sample thickness and the significant tuning of composite conductivity
may be the feasible method to tune the SE modulation range in future.
In general, the composite construction that consisted of compressible
CF and shape-memory polymer coating would provide a promising
platform for developing novel smart EMI shielding materials with
convenient SE regulation under self-fixable mechanical deformation.
4. Conclusions
In summary, the design of shape-memory TPI-M/CF composites that
consisted of compressible wood-derived CF skeletons and conductive
TPI-MXene coating layer were reported and the resultant samples not
only showed enhanced EMI SE of ~25.3–44.7 dB with CTAB-MXene
loading of ~0–20 wt%, but also possessed excellent thermally/elec-
trically stimulated shape-memory behaviors that can be easily de-
formed and recovered as being heated above the Tm and fix a temporary
shape at low temperature. Moreover, the EMI SE of TPI-M/CF compo-
sites could be adjusted in a certain range based on different initial SE
performance and compressive strain, thereby realizing the adjustment
of their SE value under self-fixable mechanical deformation.
8
Chemical Engineering Journal 405 (2021) 126927
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors are grateful to the financial supports from S&T
Innovation 2025 Major Special Programme of Ningbo (2018B10054),
China, Natural Science Foundation of Ningbo (2018A610004), China
and National Natural Science Foundation of China (51603218), China.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2020.126927.
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