Carbon 132 (2018) 32e41

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Highly flexible and ultra-thin Ni-plated carbon-fabric/polycarbonate

film for enhanced electromagnetic interference shielding
Di Xing a, Longsheng Lu a, *, Kwok Siong Teh b, **, Zhenping Wan a, Yingxi Xie a,
Yong Tang a
a
School of Mechanical & Automotive Engineering, South China University of Technology, 381#Wushan Road, Guangzhou, 510641, China
b
School of Engineering, San Francisco State University, San Francisco, CA, 94132, United States

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

Article history: We report in this work a highly flexible, mechanically robust, and ultra-thin Ni-plated nonwoven carbon
Available online 15 February 2018 fabric/polycarbonate (CF/PC/Ni) film that exhibits outstanding electromagnetic interface (EMI) shielding
performance. This composite film is fabricated through a four-step process d fabrication of nonwoven
Keywords: carbon fiber/polypropylene/polyethylene (CEF-NF) fabric, catalytic seeding and sensitization, electroless
Electromagnetic interference shielding Ni plating, and lamination with polycarbonate. The as-fabricated ultra-thin (0.31 mm) CF/PC/Ni film
Electroless Ni plating
exhibits superior EMI shielding effectiveness (EMI-SE) of 72.7 dB, which is close to 3
that of an identical
Composite film
film with no Ni plating (25 dB)ddemonstrating Ni plating can substantially improve the EMI shielding
Sandwiched structure
Carbon fiber
performance. Compared with similar lightweight EMI-shielding materials, this CF/PC/Ni film shows a
Nonwoven fabric superior EMI-SE at lower density and smaller thickness (1376.1 dB cm2 g1). 40 min of Ni plating
(yielding a Ni thickness of 1.075 mm), followed by 2 MPa of laminating pressure at 190  C of laminating
temperature were found to provide optimal EMI shielding performance. Based on reliability study, the
CF/PC/Ni film retains 96.36% of its EMI-SE after 5000 cycles of mechanical bending and 50 h of heating.
Therefore, the CF/PC/Ni film exhibits outstanding flexibility, good mechanical strength, and remarkable
electrical properties, making it an excellent EMI shielding material.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction shielding solutions have to be ultra-thin, lightweight, and impor-

tantly, flexible without being fragile and brittle [8,9].
The proliferation of electronic systems and devices, such as To achieve effective EMI shielding in day-to-day applications, a
cellular towers, wireless networks, and personal electronic devices, minimum EMI shielding effectiveness (EMI-SE) of 20 dB is neces-
has been accompanied by the unintended exponential increase in sary [10]. Metals and metal alloys are the common EMI shielding
electromagnetic interferences (EMI) [1,2]. Electronic devices with materials due to their excellent electric conductivity. However,
higher power, smaller size, and faster operating speed will emit metals generally do not have the ductility and flexibility required
undesirable electromagnetic waves, which not only interfere with for extensive deformations encountered in consumer devices.
the operations of adjacent equipment or systems, such as aircrafts Metals are heavy, are subjected to corrosion, and generally require
[3], but also cause potential health risks to human beings [4e6]. elaborate manufacturing procedures [11], which further restrict
Furthermore, the increased prevalence of data theft and hardware their uses in modern-day EMI applications. Therefore, functional
security breaches, such as remote wiping or alteration of data on materials with high EMI shielding property that are ultra-thin,
personal devices, necessitate better, consumer-friendly means of lightweight, highly flexible, and corrosion-resistant are urgently
electromagnetic shielding to enhance digital privacy [7]. Finally, needed [12]. To address these issues, low-density, non-metallic,
with the advent of flexible electronics, wearable devices, and porous composite foams have gained tremendous interest as a
implantable biomedical systems, effective and practical EMI means to reduce the weights of EMI shielding materials. Zhang
et al. [13] fabricated a novel carbon foam by direct carbonization of
phthalonitrile (PN)-based polymer foams, achieving an EMI-SE of
* Corresponding author. 51.2 dB at a thickness of 2 mm. Shen et al. [14] proposed a poly-
** Corresponding author. etherimide/graphene@Fe3O4 composite foam using a water vapor-
E-mail addresses: [email protected] (L. Lu), [email protected] (K.S. Teh).

https://doi.org/10.1016/j.carbon.2018.02.001
0008-6223/© 2018 Elsevier Ltd. All rights reserved.
 D. Xing et al. / Carbon 132 (2018) 32e41 33

induced phase separation method. Their 2.5 mm-thick composite solution was stirred at 700 rpm for 4 min followed by 5 min
exhibited an EMI-SE of 18.2 dB at 10 wt% graphene@Fe3O4 loading. of holding. Then a circular wet preformed CEF-NF was
Chen et al. [15] prepared a lightweight and flexible graphene foam formed through a stainless-steel filter net (#80) mesh and
composite by a one-step process without using foaming agents, dried at 80  C for 30 min. Lastly, the dried specimen was
achieving an EMI-SE of 30 dB at 0.8 wt% graphene loading and a heat-pressed using a thermal bonding procedure with a plate
thickness of 2.5 mm. The critical shortcoming of the aforemen- curing machine. The heat pressing parameters were opti-
tioned porous composite foams is that, to achieve adequate EMI-SE, mally set at 6 MPa pressure, 180  C temperature, and 10 min
relatively thick films are needed which may not be suitable for real holding time [19,20]. All CEF-NF specimens used in this work
applications. In addition, high porosity increases the brittleness and were fabricated with the same parameters: 6 mm-long CFs
hence fragility of these composite foams [15,16]. These disadvan- and ESFs, 40 wt% CF concentration, 40 gsm areal density.
tages constrain the EMI shielding applications of such composite (ii) Process of pretreatment: Before Ni plating process, the as-
foams. prepared CEF-NFs were sensitized in 89 mM stannous chlo-
Aside from porous composite foams, nonwoven fabrics or ride (SnCl2$2H2O)/485 mM hydrochloric acid (HCl) solution
knitted fabrics are ideal EMI shielding materials that can be applied for 10 min and then activated in 1.4 mM palladium chloride
to avionics and flexible electronics owing to their high porosity, (PdCl2)/82 mM HCl solution for 10 min in sequence. Ultra-
being ultra-thin, and excellent flexibility. Bonaldi et al. [17] fabri- sonic pulse was utilized during the activation and sensiti-
cated a polyester nonwoven fabric coated with carbon nanotubes zation processes to ensure uniform treatments.
(CNTs) and found that the inclusion of CNTs effectively enhances (iii) Electroless Ni plating of CEF-NF thin films: Electroless Ni
the EMI-SE of the polyester fabric. Chaudhary et al. [18] prepared a plating process was conducted at 80  C for 10, 20, 30, and
multi-walled CNT-based mesocarbon-microbead composite, which 40 min, respectively, using nickel sulfate (NiSO4$6H2O) and
showed an EMI-SE of 56 dB at a thicknesses of 0.6 mm. However, sodium hypophosphite (NaH2PO2$H2O) as the salt and the
the EMI shielding performance and the mechanical strength of reducing agent in this system. The solution was adjusted to a
most available nonwoven fabrics are notably too low for practical pH value of 8.0 by adding NH3$H2O. Table 1 lists the bath
application. Thus, there remains a critical need for a high- compositions for the electroless Ni plating process. Next the
performance EMI shielding material that is light-weight, flexible, obtained samples were washed several times with distilled
ultra-thin, and mechanically robust. water and dried at room temperature. In addition, it should
In our previous work [19], a flexible nonwoven fabric consisted be mentioned that the thermal bonding strength formed in
of carbon fibers (CFs) and polypropylene/polyethylene (PP/PE) the first stage can effectively prevent the fibrous porous
core/sheath bicomponent fibersdknown as CEF-NF composite structure of the preformed CEF-NF from being damaged by
filmdwas examined as a potential EMI shielding thin film. It is the production of hydrogen gas during the electroless Ni
found that this material possesses good electrical conductivity, plating process.
electromagnetic shielding performance as well as flexibility. (iv) Lamination of Ni-plated CEF-NF thin film: A Ni-plated CEF-
Building on this work, we have successfully fabricated a structurally NF thin film was sandwiched between two 0.125 mm-thick
compact, mechanically robust, ultra-thin, and flexible composite PC films and subsequently laminated together using a ther-
film with excellent EMI-SE (up to 72.7 dB). This film, known as a CF/ mal bonding procedure, forming an ultra-thin CF/PC/Ni film.
PC/Ni film, is a sandwiched composite structure consisted of a Ni-
plated CEF-NF core laminated between polycarbonate (PC) sheets.
This work details the fabrication process of the thin film and 2.2. Characterization
characterization of its electrical, electromagnetic shielding, and
mechanical properties. In addition, to optimize the EMI-SE perfor- The surface morphologies of CEF-NFs before and after electro-
mance of the sandwich composite, the influences of laminating less Ni plating were observed by a scanning electron microscopy
parameters and Ni plating time on the EMI shielding properties of (SEM, ZEISS Merlin, Jena, Germany). Elemental analysis was per-
the CF/PC/Ni film were investigated in detail through experiments. formed by an energy dispersive spectroscope (EDS, X-MaxN 50). All
specimens used for SEM and EDS were prepared as 10
10 mm2
2. Materials and methods square pieces. The cross-sections of CF/PC/Ni films were observed
via a digital optical microscope (VHX-1000, Keyence Company,
2.1. Materials and preparation Japan). A crystalline structure analysis of the CEF-NFs coated with
Ni layer using various plating times was performed using an X-ray
Polyacrylonitrile (PAN)-based carbon fibers (CFs) (Torayca® diffraction device (XRD, D8 Advance, Bruker AXS, Germany).
T700SC-12k, Toray Industries, Inc., Japan), polypropylene/poly- Diffraction peaks were obtained through 2q continuous scanning at
ethylene (PP/PE) core/sheath bicomponent fibers (ESFs) (Qianhai a speed of 5 /min in the range of 20 e80 .
Fiber Technology Company, Hangzhou, China), and 0.125 mm-thick
PC films (LEXAN™, SABIC's Specialty Film & Sheet, Saudi Arabia) 2.3. Electrical conductivity measurement
were used as-purchased without further processing. The complete
manufacturing process of a CF/PC/Ni film mainly consists of four The electrical conductivity of as-prepared CF/PC/Ni films were
major steps, as outlined below illustrated in Fig. 1. measured by four-point probe method. All electrical measurements
were performed at ambient conditions at room temperature (25  C)
(i) Preparation of CEF-NF thin films: pristine CEF-NFs were to eliminate temperature-induced measurement errors. The re-
prepared by a wet papermaking process followed by a ther- ported results are the average value of at least four different
mal bonding process described in detail in previous work specimens. Detailed information was described in previous work
[19,20]. First, chopped CFs and ESFs were weighed and pre- [20].
pared separately according to their specific ratio (CF~40 wt
%). Second, the as-prepared chopped CFs and ESFs were 2.4. EMIeSE measurement
dispersed in a 1.2 wt% hydroxyethyl cellulose solution
(Hengyu Chemical Company, Guangzhou, China). The mixed The EMI shielding measurement was conducted using a vector
34 D. Xing et al. / Carbon 132 (2018) 32e41

Fig. 1. (a)e(d) Manufacturing process of CF/PC/Ni film. (e) An as-fabricated CF/PC/Ni film and CF/PC/Ni films subjected to bending and curling, respectively.

Table 1
Bath composition used for electroless Nickel (Ni) plating.
1R 1  S11 j2
Chemical Formula Amount (g/L) SEA ¼ 10 log ¼ 10 log (4)
T S21 j2
Nickel sulfate NiSO4$6H2O 40
Sodium hypophosphite NaH2PO2$H2O 20
Sodium citrate Na3C6H5O7$2H2O 100 where A, R and T represent power coefficients can be obtained from
Ammonium chloride NH4Cl 50 the vector network analyzer in the form of scattering parameters.
Ammonium hydroxide NH4OH Sufficient to adjust pH to 8
“Smn” are the characteristic parameters of the device connected
between the two ports, its first subscript “m” represents the
network analyzer port receiving EMI radiation, and its second
network analyzer (NA7500, Tianjin Deli Electricity Company, subscript “n” represents the port that is transmitting incident en-
China) with a standard enlarged coaxial transmission line sample ergy [24]. Here R, T and A are primarily given as R ¼ |S11|2, T ¼ |S21|2
holder conforming to ASTM D4935-10 in the frequency of and A ¼ 1-R-T.
30e1500 MHz at room temperature. During an EMI-SE test, two
similar specimens were custom-made into the shape of a reference 2.5. Tensile strength measurement
and a load specimen, respectively. The reference specimen is used
to negate the ripple effect [19,21]. It comprises two parts, which are Tensile tests were carried out according to ASTM D3039M  14
(i) a 133 mm-diameter circular disc and (ii) a circular ring with standard on a universal material testing machine (Type 2369, Ins-
76.2 mm inner-diameter and 133 mm outer-diameter. The load tron LTD., USA) whose load error was <1% at room temperature. The
specimen has an outer diameter of 133 mm. rectangular tensile test specimens, which are 100 mm in length and
The EMI-SE of CF/PC/Ni films was evaluated by measuring the 25 mm in width, are carefully cut and prepared from the circular
attenuation of electromagnetic waves (in dB) using the following specimens of CF/PC/Ni films. The tensile test specimens are cut at
equation [22,23,30]: 55 mm away from the center, with its long axis being perpendicular
to the diameter of the CF/PC/Ni film. To minimize experimental
P1 errors, each test was carried out four times from four different
EMI  SE ¼ SET ¼ 10 log10 ¼ SER þ SEA þ SEM (1)
P2 specimens.

where P1 and P2 are the incoming power and transmitted power,

3. Results and discussion
respectively. SER, SEA, and SEM are the shielding effectiveness
attributed to reflection, absorption, and multiple reflections,
3.1. Laminating parameters selection
respectively. The value of SEM is negligible if SET > 15 dB [23]. Thus
these terms can be also calculated according to following formulas:
The performance of a composite film is greatly affected by
laminating parameters such as laminating temperature and lami-
1
SET ¼ 10 logj j ¼ SEA þ SER (2) nating pressure [25,38], as the laminating process may cause
T
damage to the Ni layer and affect its EMI shielding performance.
Therefore, several tests were conducted to obtain a set of optimal
1 1 processing parameters. All the as-prepared specimens for the tests
SER ¼ 10 log ¼ 10 log (3)
1R 1  S11 j2 were Ni-plated for 20 min in an electroless plating bath, achieving
an average thickness of 0.345 mm. Their laminating temperatures
varied from 160 to 210  C in increments of 10  C to elucidate the
 D. Xing et al. / Carbon 132 (2018) 32e41 35

effect of temperature, while keeping the laminating pressure at nanoscale protrusions and indentations on the bare fiber surfa-
2 MPa. For the laminating pressure study, the laminating pressure cedwhich act as nucleating sites for the Ni film. The nuclei grow
was altered from 0 to 5 MPa in increments of 2 MPa, at a constant isotropically, forming hemispherical nodules [28] as the plating
temperature of 190  C. The process times for all specimens were set time increases from 10 to 40 min. Moreover, it is observed that the
at 10 min. Ni thickness increase visibly, from 0.160 mm to 1.075 mm, as the
Figs. 2 and 3 show the EMI-SE variation versus different lami- plating duration increases from 10 to 40 min. Fig. 4f illustrates the
nating parameters and images of some typical as-prepared com- cross-sectional SEMs of several CF/PC/Ni films with different Ni
posite films, respectively. For CF/PC/Ni films produced at a constant plating times, ranging from 0 to 40 min. All these CF/PC/Ni films
laminating pressure (2 MPa), varying the laminating temperature were fabricated at a laminating parameters of 190  C and 2 MPa.
between 160  C and 210  C appeared to have negligible effect on Table 2 shows the composition of the as-plated Ni measured via an
their EMI-SE. As the laminating temperature increases, the EMI-SE electron dispersive x-ray spectroscopy (EDS) (Fig. 5). It is known
of CF/PC/Ni films remain at about 56 dB. On the other hand, at the that during electroless plating, the intermetallic compound, nickel
lower end of this laminating temperature range (i.e. 160  C), inad- phosphide (Ni3P), forms within the Ni matrix [27]. As plating time
equate bonding strength caused delamination between PC films increases from 10 to 40 min, sodium hypophosphitedthe source of
and the Ni-plated CEF-NF film (as show in Fig. 3a). To improve phosphorousdgradually depletes, causing the relative composition
interfacial bonding and prevent delamination, 190  C was found to of phosphorous to decrease from 8.02 wt% to 4.37 wt%. In addition,
be an optimal laminating temperature for a CF/PC/Ni film. the relative composition of C and O also decreases substantially as
In contrast, as the laminating pressure increases from 0 to plating progresses. This produces a significant increase in the
5 MPa, the EMI-SE of CF/PC/Ni films changes more significantly. The relative composition of pure Ni, from 51.26 wt% (at 10 min plating
effect of laminating pressure can be divided into two main stages, time) to over 80 wt% (at 40 min plating time). We surmise that the
with a major transition at 2 MPa. Below 2 MPa pressure, the EMI-SE high content of pure Ni on the surface of the plated Ni plays a key
of a CF/PC/Ni film remains at around 56 dB. While above 2 MPa, the role in the high EMI-SE of the composite. It is worth mentioning
EMI-SE of a CF/PC/Ni film begins to deteriorate. This result can be that, during electroless Ni plating, hydrogen gas evolves and as the
attributed to the fact that cracks form in the CF/PC/Ni films when gas pressure builds up, could cause irreversible deformation to the
laminated at a high pressure, as shown in Fig. 3b. The high pressure porous network [33]. No visible deformation nor damage, however,
deforms PC film significantly, causing irreversible damage to the was detected in the random fiber network after 40 min of Ni
internal structure of CF/PC/Ni films [38]. Therefore, to satisfy the plating, indicating excellent structural strength resulting from an
EMI shielding requirement and avoid cracks, the laminating pres- optimal thermal bonding process. Overall, CEF-NFs bond very well
sure of an optimum CF/PC/Ni film was set to 2 MPa in this work. with PC films after lamination, with no visible delamination, as
shown in Fig. 4f.
3.2. Microscopic observations and EDS analysis
3.3. XRD analysis
Fig. 4a to e shows the surface morphologies of several electro-
Fig. 6 shows the XRD patterns of CEF-NFs plated Ni layer with
less Ni-plated CEF-NFs fabricated with different plating times. For a
different plating times and thicknesses. For a pure CEF-NF film, a 2-
pristine CEF-NF, the CFs and ESFs are uniformly distributed and are
theta peak around 26 results due to the presence of CFs. After
intimately connected at their contact points, forming a mechani-
10 min of Ni plating, a distinct 2-theta peak at 44.8 appears,
cally robust, three-dimensional reticulated structure. This porous
indicating the nucleation of Ni(111). During crystallization, Ni
network has high structural integrity and is not subjected to clog-
atoms naturally self-organize into face-centered cubic unit cells
ging easily [20]. At high magnification, the surface morphology of
(lattice parameter ¼ 0.352 nm), whose highest planar density occur
plated Ni layer shows spherical nodular structure more clearly
on the (111) facets. Increasing plating time from 10 min to 40 min,
which is consistent with the studies of both Balaraju et al. [26] and
accompanied by a growth in the Ni film thickness, produces a
Kim et al. [27]. This phenomenon is primarily attributed to the
growing and sharper intensity peak at 44.8 . This higher intensity
peak corresponds to an increase in the number of Ni(111) facets as
Laminating temperature ( C) the relative wt% of Ni on the outer surface of the Ni film increases
160 170 180 190 200 210 with thickness, while the wt% of Ni3P drops [26,29]. Additional
70 65 peaks at 51.8 and 76.4 , corresponding to Ni(200) and Ni(220)
facets, begin to appear after 30 min of plating. As observed, the
Pressure (at 190 C)
increasingly prominent presence of Ni(111), Ni(200), and Ni(220)
65 Temperature (at 2 MPa) 60 facets indicates that the crystallinity of the as-plated Ni film in-
creases as plating progresses and more Ni are present in the outer
EMI-SE (dB)

EMI-SE (dB)

Ni layer [26]. A corresponding decrease in the bulk resistivity of the

60 55 Ni film should also be expected. Moreover, as thickness increases,
the C(002) peak gradually disappears due to the complete coverage
of the CEF-NFs by the Ni layer.
55 50
3.4. Electrical property
50 45
High electrical conductivity is a prerequisite for acceptable EMI
shielding [27]. The electrical conductivities of CF/PC/Ni films
45 40 fabricated with different Ni plating times are shown in Fig. 7.
0 1 2 3 4 5 Compared to a CF/PC-film (i.e. CF/PC/Ni film fabricated with 0 min
Laminating pressure (MPa) Ni plating), significant improvement in the electrical conductivities
was observed in CF/PC/Ni films with increasing Ni plating times.
Fig. 2. Effect of laminating pressure and temperature on the EMI-SE of CF/PC/Ni films. Fig. 7 shows that the conductivity increases from 165.3 S/cm to
36 D. Xing et al. / Carbon 132 (2018) 32e41

Fig. 3. Surface and cross-sectional morphologies of CF/PC/Ni films fabricated with different laminating parameters. (a), (b) and (c) show the effect of increasing laminating
temperatures while keeping a constant laminating pressure at 2 MPa (d), (e) and (f) show the effect of increasing laminating pressure while keeping a constant laminating
temperature at 190  C.

376.6 S/cm as the Ni plating time increases from 10 min to 40 min plated Ni films all qualified as effective EMI shielding films. More-
(corresponding to an increase in Ni thickness from 0.160 mm to over, the EMI-SE of a CF/PC/Ni film shows frequency dependence
1.075 mm). This phenomenon is a direct result of the increased after Ni plating. And this frequency dependence become stronger
amount of electroless Ni layer on the fiber surface with increasing with increasing plating time. This phenomenon is attributed to the
plating time. As metal (Ni) has a higher electrical conductivity than specific electromagnetic properties of Ni [27,32].
carbons, this leads to a faster drift velocity for the electrons in the In general, the ability of a shielding material to dissipate the
Ni film compared to CFs [26,31]. Therefore, a more effective incident EM radiation is linked to three key shielding mechanisms,
conductive pathway is formed through this Ni layer in addition to namely: reflection, absorption, and multiple reflections [40].
the original electrical conductive CF network [20]. Reflection is related to the impedance mismatch between air and
shielding materials. The presence of surface nomadic charges or
3.5. EMI shielding property mobile charge carriers (electrons or holes) is considered as the
most important factor for the reflection mechanism [1]. Absorption
Fig. 9a shows the EMI-SE of CF/PC/Ni films with different Ni arises from ohmic loss and polarization loss. Ohmic loss is attrib-
plating times tested in the frequency range of 30e1500 MHz. The uted to the dissipation of energy by nomadic charges through
CF/PC/Ni film used were prepared at 2 MPa laminating pressure and conduction, hopping, and tunneling mechanisms [1,30,40e42],
190  C laminating temperature. It is evident that Ni coating on the whereas polarization loss originates from functional groups, de-
CF conductive network greatly enhances the EMI-SE of a CF/PC/Ni fects, and interfaces within the material [42,46e48]. Multiple
film. A pure CF/PC-film without Ni coating layer shows a low EMI- reflection is due to reflections at various surfaces or interfaces as a
SE value of about 25 dB. The 40 min Ni-plated CF/PC/Ni film with a result of material volume inhomogeneity and can be negligible if
Ni thickness of 1.075 mm shows the highest EMI-SE of SET > 15 dB [44].
72.7 dBdabout 180% higher than that of a pure CF/PC-film. Since As shown in Fig. 8a, when the EM radiation impinges on the
Nickel plating can effectively enhance the electrical conductivity as surface of CF/PC/Ni film, a portion of the EM wave is reflected off
well as magnetic permeability of the materials, it can contribute to the shielding material owing to interaction with the surface free
both conductance loss and magnetic loss [46,47]. Based on general charge carriers and another portion penetrates through the
requirement of EMI-SE of 20 dB [10], CF/PC/Ni film with or without shielding material with its energy dissipated via absorption
 D. Xing et al. / Carbon 132 (2018) 32e41 37

Fig. 4. SEM of Ni-plated CEF-NF with different plating times: (a) 0 min; (b) 10 min; (c) 20 min; (d) 30 min; (e) 40 min; (f) Cross-sectional images of CF/PC/Ni film at different plating
times.

Table 2 [39,42,43]. Fig. 9b illustrates the EMI shielding coefficients A, R and

Elemental compositions of Ni-plated CEF-NFs at different plating times. T as a function of frequency measured in the range of 30e1500 MHz
Ni/CEF-NF fabricated with Element composition (wt.%) for different CF/PC/Ni films. It can be seen that as the Ni plating time
Different Ni plating times (min)
C O Ni P
and therefore thickness increase, R increases while A decrease. This
result attributes to that as the electrical conductivity increases,
10 min 28.30 12.42 51.26 8.02
more EM waves are reflected first leaving only a small part of EM
20 min 19.15 10.02 63.05 7.78
30 min 10.37 4.04 80.37 5.22 waves incident into the material [44]. For the CF/PC/Ni film with
40 min 9.86 5.07 80.70 4.37 20 min of Ni plating, its R and A are 0.103 and 0.897, respectively.
The value of R is significantly higher than that of A, and hence its

(a)4.0 (b)4.0
3.5 3.5
Ni Ni
3.0 3.0
Ni
Ni
2.5 2.5
KCnt
KCnt

2.0 2.0
C
1.5 1.5

1.0 P 1.0
P
0.5 O Ni 0.5 OC Ni

0.0 0.0
0 2 4 6 8 10 12 14 16 18 20 0 2 4 6 8 10 12 14 16 18 20
Energy-keV Energy-keV
Fig. 5. EDS spectrums of Ni-plated CEF-NFs fabricated with (a) 10 min Ni plating and (b) 40 min Ni plating.
38 D. Xing et al. / Carbon 132 (2018) 32e41

contribution to the overall incident power is considerably greater.

Ni (111)
This result suggests that the actual shielding mechanism for the CF/
Ni (200)
C (002) Ni (220) PC/Ni film in the frequency range of 30e1500 MHz is dominated by
reflection [43].
Ni/CEF-NF 40 min Fig. 9c illustrates absorption and reflection effectiveness (SEA
and SER) for different CF/PC/Ni films. Unlike the absorption
Intensity (a.u.)

shielding coefficient A, the SEA is based on EM waves penetrating

into the material excluding their reflected waves. In other words,
Ni/CEF-NF 30 min
absorption and reflection effectiveness represent the potential
shielding ability of the materials [44]. As plating time increase, both
Ni/CEF-NF 20 min SEA and SER increase. Moreover, the SEA is a more significant
contributor to the EMI-SE. Essentially, in conductive materials, both
Ni/CEF-NF 10 min reflection effectiveness and absorption effectiveness have a direct
correlation to electrical conductivity and magnetic permeability
Pure CEF-NF [42,43,45]. High electrical conductivity can contribute to both
reflection and absorption effectiveness. High magnetic perme-
25 30 35 40 45 50 55 60 65 70 75 80 ability can contribute to absorption effectiveness, but it diminishes
reflection effectiveness [40,45]. It is noteworthy that film thickness
2 (degree) is also an important factor of absorption effectiveness [40,45].
Fig. 6. XRD patterns of the Ni-plated CEF-NFs showing different peak intensities under
However, for this paper, the average thickness of CF/PC/Ni films
different plating times. with different Ni plating times stays around 310 mm. Cao et al.
[42,43] proposed the physical models of electron hopping and
conductive networks in carbon fiber composites, which could well
500 describe the electron transport in composites. As shown in Fig. 8b
and c, the enhanced absorption characteristics of CF/PC/Ni films
Electrical conductivity (S/cm)

may be due to Ni-coated CF conductive network providing effective

400 conductive paths for dissipation of incident electromagnetic waves,
which enhanced the ohmic loss [26,42]. In addition, Ni coating on
the CF surface will also attenuate the shielding by reflection loss
300 [40,45].
On the other hand, there is a major research demand for effec-
tive electromagnetic shielding materials that are ultra-thin and
200 lightweight, two properties critical to the aerospace industry [3,18].
The shielding effectiveness, density and thickness of the materials
are listed in Table 3. It can be found that the CF/PC/Ni film possesses
100 standard EMI shielding property at extreme thin thickness.
Although the density of the CF/PC/Ni film is a little high, it still
much better than the metal materials. To comprehensively and
0 effectively capture the EMI-SE performance of EMI shielding ma-
0 10 20 30 40 terials, a new parameter defined as EMI-SE/density/thickness
Nickel plating time (time) (simplified as SSEt, dB$cm2$g1) was proposed as a design crite-
Fig. 7. Electrical conductivities of CF/PC/Ni films with different Ni plating times.
rion in recent years [15]. This parameter shows that a material with
excellent EMI-SE, light weight, and ultra-thin could produce rela-
tively high SSEt [3]. According to the data listed in Table 3, it is noted
that the CF/PC/Ni film with 40 min Ni plating possesses an SSEt of
1376.1 dB cm2 g1, which is multiple times higher than those of
several competing materials.
For the CF/PC/Ni film with 40 min Ni plating, electroless Ni
plating confers it high EMI shielding performance. Moreover,
combining with PC films through laminating technique ensures its
excellent stability under mechanical deformation and high tem-
perature condition, which was validated by its EMI-SE measure-
ment before and after 5000 times repeated bending and then be
heated at 120  C for 50 h. During the bending test, the bending
radius was less than 10 mm. As shown in Fig. 9d, it is observed that
the EMI-SE of the CF/PC/Ni film shows a very small decrease of
3.17% after repeatedly bending 5000 times. After bending test, the
specimen was then used for thermal stability test. As shown in
Fig. 9e, it is observed that the EMI-SE of the CF/PC/Ni film is reduced
by only 0.47% after 50 h holding at 120  C temperature, almost no
change. This experimental result indicates that Ni plating combined
with laminating process confers the CF/PC/Ni film with excellent
mechanical robustness, thermal stability and good flexibility. All
Fig. 8. Illustrations of EMI shielding mechanism and electron transport in Ni coated CF these properties are highly desirable in the fields of wearable de-
conductive network. vices and flexible electronics [15].
 D. Xing et al. / Carbon 132 (2018) 32e41 39

(a) 100 (b)

0min
10min 1.0 T R A
20min
80 30min 0.8

Power coefficient
40min
EMI-SE (dB)

0.6
60
0.4

40 0.2

0.0
20
0 300 600 900 1200 1500 0 10 20 30 40
Frequency (MHz) Ni-plated time (min)

(c) 80
SET
SEA
60 SER
EMI-SE (dB)

40

20

0
0 10 20 30 40
Ni-plated time (min)

Fig. 9. (a) EMI-SEs of CF/PC/Ni films with different Ni plating times; (b) Power coefficients A, R and T of CF/PC/Ni films fabricated with different Ni plating times; (c) SET, SER and SEA
of CF/PC/Ni films fabricated with different Ni plating times; (d) EMI-SE of a CF/PC/Ni film before and after bending to a radius of 2.5 mm repeatedly for 5000 times, in which the CF/
PC/Ni film is plated for 40 min; (e) EMI-SE of a CF/PC/Ni film before and after being heat at 120  C, in which the CF/PC/Ni is the one after bending test.

3.6. Tensile strength Fig. 10a, all CF/PC/Ni-film specimens exhibit a specific linear elastic
period followed by a dramatic fracture without an apparent yield
Uniaxial tensile tests were performed according to ASTM stage which is much different from the tensile behavior of a pure
D3039M  14 standard. Four specimens were tested for each case PC. Fig. 10b shows the tensile strength comparison among a pure PC
to minimize testing errors. Fig. 10 shows the tensile properties film, a CEF-NF film, and several CF/PC/Ni films with different plating
comparison among a pure PC film, a pristine CEF-NF film, and times. It is observed that the pure CEF-NF and PC film have tensile
several CF/PC/Ni films with different plating times. As shown in strengths of 15.6 MPa and 55.1 MPa, respectively. On the contrary,
40 D. Xing et al. / Carbon 132 (2018) 32e41

Table 3
Specific EMI shielding performance of various materials.

Materials Filler Matrix Thickness Density (g/cm3) EMI-SE SSE SE/thickness SSEt
(mm) (dB) (dB$cm3$g1) (dB/mm) (dB$cm2$g1)

CF/PC/Ni film (40 min, this work) Ni-CF PC 0.31 1.7 72.7 42.6 234.5 1376.1
Carbon foam [37] / / 2.0 0.17 40 241 20 1205
graphene/PMMA composites [16] graphene PMMA 0.24 0.76 19 25 79.1 1041.6
PS/Graphene composites [36] Graphene PS 2.0 0.45 29 64.4 145 322
PEI/graphene foams [9] rGO PEI 2.3 0.29 12.8 44 55.7 191.3
CB/ABS nanocomposites [34] CB ABS 1.1 0.96 20 20.9 181.8 190
G@Fe3O4 foams rGO/Fe3O4 PEI 2.5 0.41 18 44 72 176
[14]
MWCNT/PC composites [35] MWCNT PC 2.1 1.13 39 34.5 185.7 164
Copper / / 3.1 8.9 90 10 290.3 32.3
[18]

(a) 100 40min-1.125mm Ni CEF-NF

(b)100
30min-0.665mm Ni Pure PC film

Tensile strength (MPa)

80 20min-0.345mm Ni 80
Tensile strength (MPa)

10min-0.161mm Ni
0min-0mm Ni
60 60

40 40

20 20

0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 PC
-20 CEF-NF
CEF-NF
-10 0 0min 1010
min 2020min 3030min 40
40min
Strain (%) Uniaxial tension tensile specimens

Fig. 10. (a)Tensile stress-strain curves, (b)Tensile strength comparison among a PC film, a CEF-NF and several CF/PC/Ni films with different plating times.

after laminating a CEF-NF and two PC films together into a sand- thermal stability of the Ni layer, enhancing both its tensile strength
wich composite film, all CF/PC/Ni films show a significant increase and durability. After being mechanically bent for 5000 times and
in their tensile strengths, which range from 63.8 MPa to 85 MPa. 50 h of heating at 120  C, the CF/PC/Ni film retains 96.36% of its
However, it is worth noting that the tensile strength of a CF/PC/Ni EMI-SE performance, demonstrating its good electrical and me-
film decreases with increasing Ni plating time, i.e., a CF/PC/Ni film chanical robustness.
with Ni plating shows lower mechanical strength than pure com-
posites without Ni plating. It is possibly due to that the weaker Acknowledgment
interfacial bonding strength of Ni layer-PC or Ni layer-CF as
compared to CF-PC. For a 40 min Ni plating CF/PC/Ni film with a Ni The present research was supported by the National Natural
thickness of 1.075 mm, the tensile strength is 63.8 MPa, which is Science Foundation of China (Nos. 51375175 and 51775197), the
about an increase of 13.9% compared to a pure PC film. These testing Natural Science Foundation of Guangdong Province, China
results prove that CF/PC/Ni films possess higher mechanical tensile (Nos.2015A030313201 and 2014A030312017) and the Science and
property than both pure PC and CEF-NFs. Technology Planning Project of Guangdong Province, China (No.
2015A010105007). The authors also thank to the Pearl River S&T
4. Conclusions Nova Program of Guangzhou.

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