materials

Article
Electromagnetic Shielding by
MXene-Graphene-PVDF Composite with
Hydrophobic, Lightweight and Flexible Graphene
Coated Fabric
Kanthasamy Raagulan 1 , Ramanaskanda Braveenth 1 , Hee Jung Jang 1 , Yun Seon Lee 2 ,
Cheol-Min Yang 2, *, Bo Mi Kim 3 , Jai Jung Moon 4 and Kyu Yun Chai 1, *
1 Division of Bio-Nanochemistry, College of Natural Sciences, Wonkwang University, Iksan 570-749, Korea;
raagulan@live.com (K.R.); braveenth.czbt@gmail.com (R.B.); softaqua88@daum.net (H.J.J.)
2 Multifunctional Structural Composite Research Center, Institute of Advanced Composite Materials,
Korea Institute of Science and Technology, Chudong-ro 92, Bongdong-eup,Wanju-gun, Jeollabukdo 55324,
Korea; t14225@kist.re.kr
3 Department of Chemical Engineering, Wonkwang University, Iksan 570-749, Korea; 123456@wku.ac.kr
4 Clean & Science Co., Ltd., Jeongeup 3 Industrial Complex 15BL, 67, 3sandan 3-gil, Buk-myeon 56136,
Jeongeup-si, Korea; jjmoon@cands.kr
* Correspondence: cmyang1119@kist.re.kr (C.-M.Y.); geuyoon@wonkwang.ac.kr (K.Y.C.);
Tel.: +82-63-219-8143 (C.-M.Y.); +82-63-850-6230 (K.Y.C.); Fax: +82-63-841-4893 (K.Y.C.)




Received: 29 August 2018; Accepted: 20 September 2018; Published: 22 September 2018


Abstract: MXene and graphene based thin, flexible and low-density composite were prepared
by cost effective spray coating and solvent casting method. The fabricated composite was
characterized using Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscope
(SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray (EDX). The prepared
composites showed hydrophobic nature with higher contact angle of 126◦ , −43 mN·m−1
wetting energy, −116 mN·m−1 spreading Coefficient and 30 mN·m−1 lowest work of adhesion.
The composites displayed excellent conductivity of 13.68 S·cm−1 with 3.1 Ω·sq−1 lowest sheet
resistance. All the composites showed an outstanding thermal stability and constrain highest weight
lost until 400 ◦ C. The MXene-graphene foam exhibited excellent EMI shielding of 53.8 dB (99.999%)
with reflection of 13.10 dB and absorption of 43.38 dB in 8–12.4 GHz. The single coated carbon fabric
displayed outstanding absolute shielding effectiveness of 35,369.82 dB·cm2 ·g−1 . The above results
lead perspective applications such as aeronautics, radars, air travels, mobile phones, handy electronics
and military applications.

Keywords: graphene; MXene; EMI shielding; composite; fabric

1. Introduction
The rapid advancement in intricate packing of modern electronic systems causes undesirable
radiation; this inevitable radiation is known as electromagnetic interference (EMI), which has negative
effects on humans and neighboring electronic systems. EMI pollution causes health hazards such
as languidness, insomnia, nervousness, and headaches [1–4]. Electromagnetic compatibility can be
achieved by using various materials such as textiles, polymer-based composites, MXene, and fabrics.
EMI shielding is expressed in decibels (dB) [5–15]. Conductive and nonconductive polymers such as
poly-p-phenylene-benzobisthiazole (PBT) [1,4,5], polythiophene (PTh) [1], Polyvinylidene fluoride
(PVDF) [7,8,13], polyacrylic acid (PAA) [1], styrene polymethyl methacrylate (SPMMA) [4,5], and fillers
such as metal nanoparticles [14–18], magnetic materials [13,14], carbon black, graphite [11], carbon

Materials 2018, 11, 1803; doi:10.3390/ma11101803 www.mdpi.com/journal/materials

Materials 2018, 11, 1803 2 of 19

nanotubes [9–12], graphene (GN) [19], and carbon fibers (CF) [17] are used to tune the properties of EMI
shielding materials [20]. The polymer Nano composites (PNC) are widely used as advance engineering
material in different environment. The functional materials, molecular dynamics, molecular details and
micro structure of PNC are important for the application [21]. PNC consist Nano fillers play important
role in generating conductive networks and combination of components alter the physicochemical
properties of the composites [22–25]. Further, surface properties of the materials can be transformed in
to hydrophobic/lyophilic by coating nanoparticle such as TiO2 , ZnO and silica aerogel or polymers like
polydimethylsiloxane (PDMS), polytetraflouroethylene (PTFE). The cross link/hydrogen bond between
constituents cause by surface functional groups. The cross links improve the thermo mechanical
properties [26–28]. Furthermore, in the polymer foams the voids form due to the different nucleation
time of constitutional solid and other external factor like temperature pressure [29]. Advanced EMI
shielding materials should be lightweight, flexible, cost effective, dielectric, and multifunctional,
and should possess a tunable absorption, high thermal resistance, intrinsic conductivity, large aspect
ratio, high corrosion resistance, and good magnetic and electronic properties [19,20,30–34].
Recently, flexible, corrosion resistant, high-density, thin carbon-based materials with satisfactory
electrical conductance have become attractive candidates for EMI shielding applications such as
in the aerospace, aircraft, automobile, and modern electronics fields. Hence, wet-laid synthetic
nonwoven fabrics fulfil these criteria with good EMI shielding [34]. In addition, carbon-carbon-based
composites possess greater EMI shielding effectiveness than carbon-based polymer matrices. Further,
continuous carbon fibers are preferred to discontinuous fibers in carbon-based EMI shielding
materials [35]. This is because the properties of carbon fiber that affect EMI shielding those are
the length and array [36]. Further, MXene resembles graphene, is an attractive engineering material
and used as filler exploited to create flexible electronic devices and other engineering materials [37].
The EMI shielding range of most graphene/PVDF composites of various thicknesses has been reported
to be in the range of 20–30 dB. In addition, the graphene can be functionalized by using reduction,
oxidation, metal nanoparticles, organic molecules and polymers for various applications like solar cell,
antibacterial materials and the EMI shielding of graphene/PVDF has been enhanced by the decoration
of nanoparticles [38–42].
Two-dimensional MXenes are explored intensively for various applications including EMI
shielding. MXenes are sprouting transition metal (Ti, V, Cr, Nb, and Ta) carbides/nitrides with
universal formula Mn+1 Xn Tx (n = 1, 2, and 3), where M is an early transition metal, X is carbon
or nitride, and Tx is a surface functional group (−O, =O and F). MXenes are generated from the
corresponding layered MAX phase with the general formula Mn+1 AXn by selective engraving of the
A-layer (group 13/14 elements) created by a weak M-A bond sandwiched between a strong M-X bond.
Minimally intensive layer-delamination (MILD) etching is carried out using the LiF/HCl method,
which is advantageous over clay etching in which Hydrogen fluoride (HF) is utilized under various
etching conditions [43–47]. Intercalation and exfoliation are conducted using urea, dimethyl sulfoxide
(DMSO), tetramethylammonium hydroxide (TMAOH), NH4 OH, tetrabutylammonium hydroxide
(TBAOH), and sonication. These exfoliation techniques are inevitable in the clay method. However,
LiF/HCl-based in-situ mild etching is highly preferable owing to the number of steps, level of defects
and risk, and the fact that exfoliation can be achieved through manual shaking. However, sonication
at low temperature and in inert environments (Ar) is preferable [34]. MXene thin-films and foams
exhibit the highest EMI shielding in the X-band region. EMI shielding can be achieved by absorption,
reflection, and multiple reflection. The MXene film enables internal multiple reflection which facilitates
absorption. The reflection on the surface due to the electron and layered structure encourages multiple
reflection. When electromagnetic radiation hits the surface, it induces electron mobility (ohmic loss).
The lightweight foaming materials are attractive candidate over metal-shielding materials as the latter
have higher densities which limit the application range in terms of aerospace [34,35].
In this study, we develop a graphene-flake (GN) coated carbon-fiber reinforced-matrix composite
(MC) and solution-casting MXene graphene foam, which exhibit a high EMI shielding effect in the
Materials 2018, 11, 1803 3 of 19

S-band region. The required thickness is achievable by adjusting the spraying and drying cycles.
Further, we developed MXene graphene foam with internal hollow sphere with surface imbedded
balls. Consequently, we analyze the following parameters in detail; EMI shielding, morphology of
GN-coated matrix and MXene-graphene foam, electrical conductivity, constitutional chemical species,
elemental percentage, and hydrophobic nature. In addition, the pristine carbon-fiber-reinforced
matrix composite, graphene, graphene oxide, and reduced graphene oxide are denoted as MC, GN,
GNO, and rGNO, respectively. The GN, GNO and rGNO coated fabrics are denoted as GNMC,
GNOMC, and rGNOMC, whereas the MXene-graphene coated fabric, MXene-graphene composite,
and MXene-graphene oxide composite are symbolized as MGNMC, MGNC, and MGNOC, respectively.

2. Materials and Methods

2.1. Materials
Graphene (GN) (M-25, 99.5%, average size and thickness of 25 µm and 7 nm, respectively) was
obtained from Ditto Technology Co. Ltd., (Gyeonggi-do, Seoul, Korea). Dimethylformamide (DMF)
99.8 w/w%, lithium fluoride (LiF) (98%, 300 mesh), Polyacrylic acid (PAA), and Polyacrylamide (PAM)
were purchased from Sigma Aldrich (Seoul, Korea). Polyvinylidene fluoride (PVDF) (melting point of
155–166 ◦ C) was purchased from Alfa Aesar (Seoul, Korea). Hydrochloric acid (HCl-35%) and nitric
acid (HNO3 -70%) were supplied by Samsung Chemical Co., Ltd. (Seoul, Korea), anhydrous lithium
chloride (LiCl) was purchased from Tokyo Chemical Industry Co., Ltd (Tokyo, Japan), and Ti3 AlC2
was acquired from Forsman Scientific Co., Ltd. (Beijing, China). Carbon fiber (fiber diameter 7 µm,
6 mm) and polyethylene terephthalate (PET) binder (fiber diameter 2.2 dtex, 5 mm) were purchased
from TORAY Product (Osaka, Japan). No purification methods other than those stated were utilized
for the chemicals.

2.2. Preparation of Graphene Oxide (GNO) and Reduced Graphene Oxide (rGNO)
A total of 1 g of graphene was mixed with 50 mL of HNO3 and stirred at room temperature
for 12 h. The reacted graphene was washed with deionized water until it reached a neutral pH.
The resulting black flakes were GNO, and these were dried at 80 ◦ C for 24 h. Equal amounts of
GNO and NaBH4 were mixed together in deionized water and stirred at room temperature for 12 h.
The resultant product was washed several times with deionized (DI) water and dried at 80 ◦ C for 24 h.
The obtained product was rGNO.

2.3. Preparation of MXene and MXene Colloidal Solution

Equal amounts of Ti3 AlC2 and LiF were immersed in 20 mL of 6M HCl solution and stirred at
35 ◦C for 24 h. The resultant mixture was washed with DI water (pH 6) several times by centrifuging
at 3500 rpm for 5 min, and the black flakes were dried at 100 ◦ C for 12 h in a vacuum oven. A total of
0.1 g of MXene was dispersed in 10 mL of DI water by sonication for 1 h in an ice bath. The resultant
exfoliated solution was centrifuged at 3500 rpm for 30 min. The supernatant was collected and stored
at 5 ◦ C for the coating process.

2.4. Preparation of Carbon Fabric

Carbon fiber, PET-binder fiber with a 4:1 weight ratio, and 0.3 wt.% of PAM were dispersed in
DI water. Then, the mixture was rotated at 500 rpm for 10 min. A web was produced using a general
wet-laid method. During this process, a drum dryer was used with a surface temperature of 140 ◦ C
and a speed of 7 m·min−1 . The obtained fabric density was 20 g·m−2 .

2.5. Fabrication of Composite (MC)

A series of GN-coated MCs were prepared by a cost-effective spray-coating process. MC was
spray-coated using 3 g·L−1 of GN, GNO, and rGNO with a 5 g·L−1 PVDF dispersed solution of DMF.
Materials 2018, 11, 1803 4 of 19

After the coating process, the fabrics were subjected to drying at 100 ◦ C for 5 min in a drying oven.
This process was repeated up to ten cycles to alter the quantity of GN coated on the MC in each
case. MNNC and MGNOC were fabricated using a solvent-casting method; 5 g of PVDF, 3 g of GN,
and equal amounts of PAA and LiCl (0.3 g) were stirred in a 50 mL DMF solution at room temperature
for 12 h. The resultant mixture was poured into a casting plate and evaporate DMF in vacuum oven at
80 ◦ C (pressure below 0.8 atm). Then, 100 mL of colloidal MXene solution was added and evaporation
occurred under the same condition. Finally, the resultant film was separated from the casting plate.

2.6. Characterization
The density was measured using a laser flash apparatus, LFA457 (NETZCH, Seoul, Korea).
A high-resolution Raman spectrophotometer Jobin Yvon, LabRam HR Evolution (Horiba, Tokyo, Japan)
was used to identify the structural features of MC, GN, GNO, rGNO, MXene, and GN-based and
MXene composite. The morphologies of the fabrics were investigated using a field-emission scanning
electron microscope (SEM, S-4800; Hitachi, Tokyo, Japan). The X-ray diffraction patterns of the
materials were recorded using a high-power X-ray diffractometer, D/max-2500V/PC (Ragaku, Tokyo,
Japan) with Cu (Kα). The elemental percentages and chemical environments were analyzed using XPS
with a spot-size of 30–400 µm at 100 W of Emax (Al anode) K-Alpha, Thermo Fisher (East Grinstead,
UK). A contact angle meter, Phonix-300A (S.E.O. Co., Ltd., Suwon, Korea), was used to analyze the
wetting ability of the surfaces of the composites. A thermal analyzer, DSC TMA Q400 (TA Instruments
Ltd., New Castle, DE, USA), was used to measure the thermogravimetric data. The EMI shielding
effectiveness (SE) of the composites were recorded using an EMI shielding tent, ASTM-D4935-10,
ASTM International (West Kentucky, PA, USA) at room temperature (For s band). The Savitzky–Golay
function (Origin 2017 graphing and analysis, OriginLab; Boston, MA, USA) was used to plot the
data. The electrical conductivities were measured using a four-probe method FPP-RS8, DASOL ENG
(Seoul, Korea). The thicknesses were measured using a Mitutoyo thickness 2046S dial gage (Mitutoyo,
Kanagawa, Japan). The electromagnetic characteristics of the specimens were measured using a
vector network analyzer (VNA, Agilent N5230A, Agilent Technologies, Santa Clara, CA, USA) and
a rectangular wave guide with the frequency ranging from 8.2 GHz to 12.4 GHz. The samples were
prepared by cutting the free-standing film into rectangular shapes (width is 22.16 mm and height is
10.16 mm) (For X band).

3. Results

3.1. Structural Characterization

3.1.1. Scanning Electron Microscopic (SEM) Analysis of Morphology

SEM images were used to analyze the surface topological morphology of the Ti3 AlC2 , Ti3 C2 Tx ,
graphene, MXene composites, and uncoated fabric (MC). Virtually the cracks and annular gaps are
entailing with fiber surfaces of MC (Figure 1a,d). The SEM image of MC (Figure 1a) expresses the
porous, smooth, and clean nature of the surfaces, which consist of haphazardly packed carbon fibers
and GN, GNO, and rGNO. They are oriented randomly and grooves remain owing to the wrinkly
nature of graphene (Figure 1b,e) [48]. GNO is disseminated planar in nature (rigid stack) over the MC
composite, which exhibits a different pattern to GN and rGNO [49]. This phenomenon is attributed to
the presence of carboxylic groups and the flat nature (Figure 1c) of the GNO regulated arrangement of
the graphene flakes on MC. In addition, the relevantly sized GN flakes could fill the fissures during
fabrication (Figure 1b–e). This could be described in terms of the magnitude of the GN flakes used,
and the size of the carbon fibers and gaps present in the fabric. The diameter of the carbon fibers is
approximately 7–9 µm, whereas the average size of the GN flakes is 25 µm. Thus, the large size of the
GN flakes prevents homogeneous coating of the smaller carbon fiber in the carbon fabric, as shown in
Figure 1b–e. As a result, the majority of the pores are covered by carbon flakes owing to infiltration
Materials 2018, 11, 1803 5 of 19

in the carbon fabric while smaller GN flakes (2–5 µm) are deposited on the surface of the carbon
fiber (Figure
Materials 2018, 11,1d).
x FORAggregation
PEER REVIEWof GN at the carbon-fiber (CF) joints was observed and is shown 5 of in
19
Figure 1b,d,e; this may enhance the hydrophobicity, EMI shielding, and electrical conductivity. Hence,
the porosity
electrical of MC wasHence,
conductivity. attenuated by the of
the porosity coating
MC was process (Figure
attenuated by1b–e) and alignment
the coating of the GN
process (Figure 1b–
flakes can be tuned by oxidation (Figure 1c). This appears to be true
e) and alignment of the GN flakes can be tuned by oxidation (Figure 1c). This appears to be true based on our study. Ti 3 AlC and
based
2
Ti3 C
on 2 Txstudy.
our are layered
Ti3AlCmaterials
2 and Ti3C that
2Tx are
are like graphite
layered (Figure
materials 1f,g)
that are[50].
like The gaps (Figure
graphite in Ti3 C21f,g)
Tx (Figure 1g)
[50]. The
indicate
gaps in that
Ti3Ceffective
2Tx (Figure eradication
1g) indicateof Al,thatand effective
EDX strengthens
eradication this statement
of Al, and (Figure
EDX S3b). The surface
strengthens this
of MXene-graphene
statement (Figure S3b). foamTheillustrates
surface ofthe arrangement of foam
MXene-graphene the GN flakes and
illustrates theMXene
arrangementwith small
of thepores
GN
(Figureand
flakes 1h–k),
MXene wherewithonesmallgraphene flake accommodates
pores (Figure 1h–k), where one several MXene
graphene flakes.
flake This couldseveral
accommodates be an
effectiveflakes.
MXene way toThis enhancecould multiple
be an reflection
effective and way absorption.
to enhanceMoreover,multiple interconnected
reflection and MXene and
absorption.
graphene are
Moreover, responsible for
interconnected electron
MXene andmobility.
graphene Thearecross-sections
responsible for of MGNC
electronand MGNOC
mobility. Theconfirm
cross-
that the of
sections formation
MGNC and of the foam, which
MGNOC confirm is that
a highly attractiveof
the formation structural
the foam,requirement
which is a highly for lightweight
attractive
EMI shielding
structural (Figure 1j,k)
requirement [34,35]. TheEMI
for lightweight cross-sections of MGNC
shielding (Figure 1j,k)and MGNOC
[34,35]. visually confirm
The cross-sections of
the foam
MGNC structure
and MGNOC (Figure
visually 1j–l). It is obvious
confirm the foamthat the pore
structure size of
(Figure MGNOC
1j–l). is smaller
It is obvious than
that the that
pore of
size
MGNC.
of MGNOC Thisiscan be explained
smaller than thatby of the
MGNC. thickness
This canof the
be material.
explainedThe by thethicknesses
thicknessofofGNMC, GNOMC,
the material. The
rGNOMC, MGNC,
thicknesses of GNMC, andGNOMC,
MGNOC rGNOMC, are 0.0191, MGNC, 0.0174, 0.0163,
and MGNOC 0.0192, 0.035, and 0.0243
are 0.0191, 0.0174,cm, respectively.
0.0163, 0.0192,
The thickness
0.035, and 0.0243 of MGNOC is smaller
cm, respectively. The than that ofof
thickness MGNC,
MGNOC which meansthan
is smaller that that
the pores
of MGNC,in MGNOCwhich
are small
means and
that theGNO
pores is in
arranged
MGNOC in aareflat stack.
small andFurther,
GNO the cross section
is arranged of coated
in a flat stack.fabric revealed
Further, the
the cross
infiltration
section of GN,fabric
of coated GNO,revealed
rGNO and the MXene
infiltration(Figure
of GN,S2a–f).
GNO, MostrGNOof theand GNO
MXene flake laid onS2a–f).
(Figure the surface
Most
fabric
of the GNO while
flakefew penetrate
laid (FigureofS2c).
on the surface fabricThe MGNC,
while MGNOC(Figure
few penetrate possessed S2c).internal
The MGNC, hollow sphere
MGNOC
with numerous
possessed internal ballhollow
like structure
sphere (Figure
with numerousS2g,h). The ballsize
likeofstructure
the hollow sphere
(Figure was large
S2g,h). in MGNC
The size of the
whereas GNO densely
hollow sphere was large packed
in MGNC with whereas
small spheres GNO(Figure
denselyS2g,h).
packed ThewithEDX confirms
small spheres the(Figure
constitutional
S2g,h).
elements
The EDXofconfirms
Ti3 AlC2 theandconstitutional
Ti3 C2 Tx (Figure S3a,b) and
elements of that the2 etching
Ti 3AlC and Ti3removed
C2Tx (Figure Al and introduced
S3a,b) and that F and
the
Cl, derived
etching from Al
removed etching solution. The
and introduced F and ratio
Cl,F/O is 6.27
derived from and F/Cl solution.
etching is 100.15, The confirming
ratio F/Othat F isand
is 6.27 the
majorissurface
F/Cl 100.15,functional
confirming group.
that FThe mapping
is the of the MGNC
major surface functionalinveterate
group.distribution
The mapping of the
of elements
the MGNC in
inveterate
the compositesdistribution
are shown of the elements
in Figure in the composites are shown in Figure S3c–f.
S3c–f.

Figure 1.
Figure Microstructuralimages
1. Microstructural imagesfromfromscanning
scanningelectron
electron microscopy
microscopy of of
(a)(a) surface
surface of MC
of MC (×500),
(×500), (b)
(b) surface of GNMC ( × 300), (c) surface of GNOMC ( × 300), (d) fiber surface
surface of GNMC (×300), (c) surface of GNOMC (×300), (d) fiber surface of GNO-coated GNOMC of GNO-coated GNOMC
(×2000),(e)
(×2000), (e) surface
surface of
of rGNOMC (×300),(f)
rGNOMC (×300), (f)Ti
Ti33AlC (×100,000),(g)(g)TiTi
AlC2 2(×100,000), 3C32C x (×50,000),
T2xT(×50,000), (h) (h) surface
surface of
of MGNC
MGNC (×300),
(×300), (i) MXene
(i) MXene on surface
on surface of MGNC (×3000),(×(j)
of MGNC 3000), (j) cross-section
cross-section of MGNC of(×1000),
MGNC(k) (×cross-
1000),
(k) cross-section
section MGNC(l)(×
of MGNCof(×3500) 3500) (l) cross-section
cross-section of MGNOC MGNOC (×500).
of (×500).

3.1.2. Raman Spectroscopic Analysis of the Structure of Carbon-Based Materials

Raman spectroscopy is a prominent tool with which to investigate the structural and crystalline
nature of Ti3C2Tx, and carbon-based materials including graphite materials [32,33]. In addition, the
level of defect and disorder can be predicted by using (ID/IG) [6]. The ID/IG value of GN, GNO, rGNO
Materials 2018, 11, 1803 6 of 19

3.1.2. Raman Spectroscopic Analysis of the Structure of Carbon-Based Materials

Raman spectroscopy is a prominent tool with which to investigate the structural and crystalline
nature of Ti3 C2 Tx , and carbon-based materials including graphite materials [32,33]. In addition,
the level of defect and disorder can be predicted by using (ID /IG ) [6]. The ID /IG value of GN, GNO,
rGNO were
Materials 2018,0.14, 0.23PEER
11, x FOR andREVIEW
0.17, respectively (Figure S4). Hence, oxidation made more 6 ofdefect
19 in
GNO while reduction minimize the defect rGNO. Furthermore, GNMC, GNOMC, rGNOMC, MGNC,
were 0.14, 0.23 and 0.17, respectively (Figure S4). Hence, oxidation made more defect in GNO while
MGNOC and MC had (ID /IG ) value of 0.4, 0.84, 0.38, 0.17, 0.15 and 0.91 respectively. It was obvious
reduction minimize the defect rGNO. Furthermore, GNMC, GNOMC, rGNOMC, MGNC, MGNOC
thatand
graphene coating diminished defects and films possessed less defects compare with fabric. MGNC
MC had (ID/IG) value of 0.4, 0.84, 0.38, 0.17, 0.15 and 0.91 respectively. It was obvious that
foam consisted
graphene coating littlediminished
high defect thanand
defects MGNOC as MGNC
films possessed lessown large
defects hollow
compare withcavity
fabric.than
MGNC MGNOC
(Figure
foamS2). Introduction
consisted little highof hydroxyl
defect than functional
MGNOC groups as MGNC lessen
owndefect in carbon
large hollow fabric
cavity thanwhile
MGNOC carboxylic
acid(Figure
groupS2). increase
Introductionthe defects
of hydroxyl[37].functional
Even though, carboxylic
groups lessen functional
defect in carbon fabricgroups
while induced
carboxylicplaner
acid groupofincrease
arrangement graphene theflake
defects [37]. 1c).
(Figure Even though,the
Further, carboxylic
in-plane functional
vibrationalgroups
mode induced
of surface planer
functional
arrangement of graphene flake (Figure 1c). Further, − 1
the in-plane
groups Ti and C generate peaks at 624, 263, and 394 cm [51,52]. The weak broad band with similar vibrational mode of surface
functional
intensities groups
at 1350 andTi and
1570Ccm generate peaks at 624,
−1 is attributed to 263,
the D-andand394 G-bands.
cm −1 [51,52].InThe weak broad
addition, band
the presence of
with similar intensities at 1350 and 1570 cm is attributed −1
− 1 to the D- and G-bands. In addition, the
anatase TiO2 caused peaks at 628, 510, and 396 cm (Figure 2b) [43,53]. The Raman spectra G-bands
presence of anatase TiO2 caused peaks at 628, 510, and 396 cm−1 (Figure 2b) [43,53]. The Raman spectra
of GN, GNO, and rGNO show bands at 1578, 1580, and 1579 cm−1 , respectively; these have higher
G-bands of GN, GNO, and rGNO show bands at 1578, 1580, and 1579 cm−−11, respectively; these have
intensities than the corresponding D-bands at 1351, 1352, and 1346
higher intensities than the corresponding D-bands at 1351, 1352, and 1346 cm−1, respectively [51].
cm , respectively [51]. However,
rGNO showsrGNO a weaker − 1
However, showspeak at 1346
a weaker peakcm at 1346(Figure 2a). These
cm−1 (Figure results
2a). These agree
results that
agree thatGN-
GN-and and GN-based
GN-
materials have higher crystallinity. Highly oriented pyrolytic graphite
based materials have higher crystallinity. Highly oriented pyrolytic graphite (HOPG) is a form (HOPG) is a form of of
ordered
graphene
ordered(GN) sheets(GN)
graphene arranged
sheets one over another;
arranged one over the Raman
another; thespectrum
Raman spectrumof HOPG of also
HOPG manifests
also as
manifests
a single bandasata single
1582 cm band−1 at(G1582
mode cm−1E2g)(G mode
which E2g) which corresponds
corresponds to the to the band
band at 1578 cm−cm
at 1578 1 in−1 in
the GN
the GN[32,54,55].
spectrum spectrum The [32,54,55] . The raw material and production methods influence the disparity
raw material and production methods influence the disparity properties of
properties of carbon fiber, in which
carbon fiber, in which the constituents resemble the constituents resemble
graphite graphite
[56]. [56]. Thespectrum
The Raman Raman spectrumof MC of exhibits
MC exhibits numerous peaks, in which the D- and 2D-bands are placed at 1348–1374 − cm-1 and 2680–
numerous peaks, in which the D- and 2D-bands are placed at 1348–1374 cm 1 and 2680–2740 cm−1 ,
2740 cm−1, respectively; these values are from the corresponding boundaries of CF crystalline
respectively; these values are from the corresponding boundaries of CF crystalline graphite. In addition,
graphite. In addition, the presence of HOPG is confirmed by the G-band at 1503–1634 cm−1 (Figure
−1 (Figure 2a) [32,33,56]. The use
the presence of HOPG is confirmed by the G-band at 1503–1634 cm
2a) [32,33,56]. The use of PVDF as a binder in the GN coating influences the shape of the spectrum
of PVDF
owingas to athe
binder
PVDF/GN in theinteractions
GN coating thatinfluences the shape
cause fluctuation of the
at 2750 cm−1spectrum
(2D-band), owing
whichto is the PVDF/GN
absent in
interactions that cause − 1
MC. The bands in thefluctuation
spectrum split at 2750
into acm few new (2D-band),
bands owing which is absent
to the in MC. The
PVDF molecules bands
[57,58]. In in the
spectrum
addition, split into aproduces
GNOMC few newweak bands 2Dowing to the PVDF
band, whereas molecules
less oxidized [57,58].
composites In addition,
exhibit a prominent GNOMC
2D band.
produces weak At 2D
the band,
same time,
whereasthe sharp band at 1503–1634
less oxidized composites cmexhibit
−1 and new peak at 2750 cm−1 provide
a prominent 2D band. At the same
evidence
time, the sharp thatband
the GN coating occurs
at 1503–1634 cm−on MC.new
1 and In addition,
peak at 2750 cm−1 provide
the MGNC and MGNOC composites
evidence that the GN
generate new peaks at 2452, 2976, and 3243 cm −1 while the G- and 2D-band intensities increase
coating occurs on MC. In addition, the MGNC and MGNOC composites generate new peaks at 2452,
significantly. This advocates that effective interaction occurred between MXene, GN, and the
2976, and 3243 cm−1 while the G- and 2D-band intensities increase significantly. This advocates that
polymers (Figure 2b).
effective interaction occurred between MXene, GN, and the polymers (Figure 2b).

MC GNMC
1.0 GNO 1.0 GNOMC
rGNO rGNOMC
GN MGNC
Normalized intensity (a.u.)

0.8 Ti3AlC2 0.8 MGNOC

Normalized intensity (a.u.)

(a)
(b)
0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
500 1000 1500 2000 2500 3000 3500 4000 500 1000 1500 2000 2500 3000 3500 4000

Raman shift (cm-1) Raman shift (cm-1)

Figure 2. Normalized Raman spectra of (a) MXene, MC, GN, GNO, rGNO, and (b) composites.

3.1.3. X-rayFigure 2. Normalized

Diffraction (XRD) Raman spectra of (a) MXene, MC, GN, GNO, rGNO, and (b) composites.
Analysis
3.1.3.
The X-ray Diffraction
crystalline (XRD) Analysis
or amorphous nature of the materials can be confirmed using XRD profiles [59,60].
XRD results of the pristine
The crystalline materials
or amorphous and composites
nature are can
of the materials shown in Figureusing
be confirmed 3a,b. XRD
According
profiles to the
[59,60]. XRD results of the pristine materials and composites are shown in Figure 3a,b. According to
the XRD profiles, all of the materials display a crystalline nature. GN, GNO, and rGNO show two
type of peaks: one intense peak 2θ located at 24.5°–27.5°, and another small peak 2θ positioned at
Materials 2018, 11, 1803 7 of 19

XRDMaterials
profiles, allxof
2018, 11, FORthe
PEERmaterials
REVIEW display a crystalline nature. GN, GNO, and rGNO show 7 of 19 two
type of peaks: one intense peak 2θ located at 24.5◦ –27.5◦ , and another small peak 2θ positioned at
◦ . However,
54.854.8°. However,the thelocation
location ofof 2θ
2θofofthetheintense
intensepeak varies
peak slightly
varies such that
slightly such2θthat
is 26.56°,
2θ is 26.5°, ◦ , 26.5◦ ,
26.56and
and26.52°, ◦
26.52 which
, which represent
represent GN,
GN, GNO,GNO,andandrGNO, respectively.
rGNO, The XRD
respectively. pattern
The XRD of Ti 3Cof
pattern 2TTi
x confirms the
3 C2 Tx confirms
the formation
formationofofMXene. MXene. CaoCao
et al.etreported that the
al. reported delamination
that of MXeneofcan
the delamination be confirmed
MXene by the
can be confirmed
shifting
by the of the
shifting ofpeak from 9.3°
the peak fromto9.37.2° [61,62].
◦ to Hence, synthesized
7.2◦ [61,62]. MXene consisting
Hence, synthesized MXeneofconsisting
two peaks of at two
7.15° and ◦9.5° (002)◦ confirm the formation of partially delaminated Ti 3C2Tx. The composites show
peaks at 7.15 and 9.5 (002) confirm the formation of partially delaminated Ti3 C2 Tx . The composites
three different peaks of 2θ = 19.5°–21.5°, 25.5°–27.2°, and～54.8°. The high intense peaks are located at
show three different peaks of 2θ = 19.5◦ –21.5◦ , 25.5◦ –27.2◦ , and ∼54.8◦ . The high intense peaks are
2θ = 25.5°–27.2°, where MGNOC, GNOMC, rGNOMC, MGNMC, GNMC, and MGNC are positioned
located at 2θ = 25.5◦ –27.2◦ , where MGNOC, GNOMC, rGNOMC, MGNMC, GNMC, and MGNC
at 26.62°, 26.56°, 26.64°, 26.6°, 26.75°, and 26.7°, respectively. The intense peaks are attributed to the
are presence
positioned at 26.62◦ ,and
of graphene 26.56 ◦ , 26.64◦ , 26.6◦ , 26.75◦ , and 26.7◦ , respectively. The intense peaks are
PVDF [59,60]. In addition, the intense peak is absent in MC where the
attributed
broadertopeakthe presence
indicates ofthegraphene
amorphous andnature
PVDFand [59,60]. In addition,
presence the intense structure
of the graphite-like peak is absent
(Section in MC
where the broader peak indicates the amorphous nature and presence of the graphite-like
4.1.2) [63]. The peak at 2θ = 54.8 and 25.5°–27.2° confirms the presence of the graphene structure. In structure
(Section
MGNMC, 4.1.2,extra
[63]).peaks
The are
peak at 2θ by
formed = 54.8
MXene 2θ ◦=–27.2
andat25.5 23.8°◦ and
confirms
27.9°. the
PVDF presence
generates of two
the graphene
weak
structure.
shoulder In 2θ
MGNMC, extraand
peaks at 17.7° peaks arecorresponding
20.6° formed by MXene atand
to alpha 2θ =beta
23.8 ◦ ◦
andrespectively
PVDF, 27.9 . PVDF generates
[60]. MGNC two
weakand MGNOC2θ
shoulder display
peaksweakat 17.7 ◦ and
single peaks
20.6at◦ corresponding
20.4°, which supports
to alphathe peak due to
and beta PVDF.respectively
PVDF, This peak is [60].
absent in the fabric-based composites owing to the low ◦
concentration
MGNC and MGNOC display weak single peaks at 20.4 , which supports the peak due to PVDF. of PVDF.
This peak is absent in the fabric-based composites owing to the low concentration of PVDF.

rGNO

GNO

(a) GN
Intensity (CPS)

Ti3C2Tx

25.5 26.0 26.5 27.0 27.5

2-theta

Ti3C2Tx

GN

GNO

rGNO

10 20 30 40 50 60 70 80
2-theta

MGNOC

GNOMC
rGNOMC

GNMC
(b) MGNMC

MGNC
Intensity(CPS)

MC

MC 26.2 26.3 26.4 26.5 26.6 26.7 26.8 26.9 27.0

GNOMC

MGNMC

GNMC
rGNOMC
MGNOC
MGNC

10 20 30 40 50 60
2-theta

Figure 3. XRD of (a) rGNO, GNO, GN, MXene and (b) composites.

Figure 3. XRD of (a) rGNO, GNO, GN, MXene and (b) composites.
Materials 2018, 11, 1803 8 of 19

3.1.4. X-ray Photoelectron Spectroscopy (XPS) Analysis

Materials 2018, 11, x FOR PEER REVIEW 8 of 19
XPS is useful technique that can deliver the structural nature and functional groups of the
compound analyzed; a Gaussian–Lorentzian
3.1.4. X-ray Photoelectron Spectroscopy (XPS) Analysis function is used to fit the XPS data. Thus, different binding
energy levels were identified by using fitted Ti2p, C1s, F1s, and O1s electron binding energy curves.
XPS is useful technique that can deliver the structural nature and functional groups of the
In addition, the bonding nature of diverse components is reported based on the chemical shift of
compound analyzed; a Gaussian–Lorentzian function is used to fit the XPS data. Thus, different
elements (Figure 4a–f) [64,65]. Table 1 expresses the constitutional elements in different proportions.
binding energy levels were identified by using fitted Ti2p, C1s, F1s, and O1s electron binding energy
In MXene, F isInaaddition,
curves. more dominant the bonding functional
nature ofgroup
diversethan OH. Theisatomic
components percentage
reported based on the of the oxygen
chemical reveals
shift
slight oxidation
of elementsof(FigureGN in GNO (Table 1).
4a–f) [64,65]. The1XPS
Table Ti2p fitting
expresses curve confirms
the constitutional the presence
elements of bonds
in different
such asproportions.
TiO2 (464.5(2p1/2)
In MXene,and F is458.5
a more (2p3/2)
dominant Ti2+ (461.3
eV),functional and than
group 456.4OH.
eV),The andatomic
Ti-C (454.5 eV). of
percentage Further,
the oxygen reveals slight oxidation of GN in GNO (Table 1). The
C1s displays bonds such as C–Ti–Tx (281.1 and 283.2 eV), C–C (284.5 eV), and CHx/C=O (286.1 eV)XPS Ti2p fitting curve confirms the
where presence
the C–Cofbond bondsgivessuch as TiOto
rise 2 (464.5(2p1/2) and 458.5 (2p3/2) eV), Ti 2+ (461.3 and 456.4 eV), and Ti-
a high intense peak. The functional constitutions, namely TiO2
C (454.5 eV). Further, C1s displays bonds such as C–Ti–Tx (281.1 and 283.2 eV), C–C (284.5 eV), and
(529.6 eV), C–Ti–(OH)x (531.1 eV), Al2 O3 (532.3 eV), and H2 Oads (533.8 eV) are inveterate by the O1s
CHx/C=O (286.1 eV) where the C–C bond gives rise to a high intense peak. The functional
fitting curve. The F1s fitting curve is purely responsible for the C–Ti–Fx bond. Hence, MXene is formed
constitutions, namely TiO2 (529.6 eV), C–Ti–(OH)x (531.1 eV), Al2O3 (532.3 eV), and H2Oads (533.8 eV)
with theareformula
inveterate Ti3by
C2the
T(OH,O1s [52,66–68].
F) fitting curve. GNs comprise
The F1s mainly
fitting curve graphene
is purely C-C bonds
responsible with
for the numbers of
C–Ti–Fx
C–O/C=O bond.bonds.
Hence, MC MXene comprises
is formed 8.8% oxygen
with (TableTi1);
the formula 3Cnevertheless, C=OGNs
2T(OH, F) [52,66–68]. or C–O belonging
comprise mainlyto the
C1s peak are notC-C
graphene observed
bonds with prominently,
numbers which is confirmed
of C–O/C=O bonds. MC by the C1s fitting
comprises 8.8%curve
oxygen of (Table
GN. However,
1);
nevertheless,
the addition of PVDF C=O or C–O belonging
introduces two maintonew thepeaks
C1s peakat 286 areand
not290.5
observed prominently,
eV. These peaks mightwhichoriginate
is
confirmed by the C1s fitting curve of GN. However, the addition
from the C–C–F and C–F bonds, respectively, and the 286 eV peak arises owing to the MXene C=O of PVDF introduces two main new
peaks at 286 and 290.5 eV. These peaks might originate from the C–C–F and C–F bonds, respectively,
bond (Figure 4f). In addition, the newly generated MGNC and MGNOC peak at 288.1 eV may arise
and the 286 eV peak arises owing to the MXene C=O bond (Figure 4f). In addition, the newly
owing to the addition of PAA and LiCl [68]. However, the intense peak intensity and corresponding
generated MGNC and MGNOC peak at 288.1 eV may arise owing to the addition of PAA and LiCl
binding energy
[68]. causedthe
However, byintense
the composites vary asand
peak intensity follows: GNMC (284.17
corresponding bindingeV), GNOMC
energy causedandbyrGNOMC
the
(284.25composites
eV), MGNMC (284.21 eV), and MGNC and MGNOC (284.5
vary as follows: GNMC (284.17 eV), GNOMC and rGNOMC (284.25 eV), MGNMC eV) (Figure 4f). The XPS graphs of
GN and othereV),
(284.21 coated carbonand
and MGNC composites
MGNOC (284.5showeV) a combination
(Figure 4f). The ofXPS
GN, PVDF,
graphs of and
GN andcarbon
otherfabric
coatedpeaks.
carbon of
The amount composites
O variesshow witha thecombination
combinationof GN,ofPVDF, and carbonwhich
the composite, fabric peaks. The amount
is strongly of O from
evidenced
varies with the combination of the composite, which is strongly evidenced
the XPS data (Table 1). After the GN coating, we observed that there is defect at 285.0 eV, which may from the XPS data (Table
reduce1).theAfter the GNofcoating,
strength the GNMC we observed
fabric.that there is defect at 285.0 eV, which may reduce the strength
of the GNMC fabric.
4500 TiO2 (2p3/2) Ti2p
C1s
4000 4000 C-C
3500
Ti-C (2p3/2)
3000
Intensity (a.u.)
Intensity (a.u.)

2500
Ti2+
2000 Ti2+ (2p1/2) 2000

TiO2(2p1/2) C-Ti-Tx C-Ti-Tx

1500

1000
CHx/CO
500

0 0
465 460 455 450 292 290 288 286 284 282 280
Binding energy (eV) Binding energy (eV)

(a) (b)

5500
O1s C-Ti-Fx F1s
5000 50,000
4500 TiO2
4000 40,000
3500
Intensity (a.u.)

Intensity (a.u.)

3000 C-Ti-(OH)x 30,000

2500 Al2O3
(*)H2O 20,000
2000

1500

1000 10,000

500

0 0
536 534 532 530 528 526
Binding energy (eV) 690 688 686 684 682 680
Binding energy (eV)

(c) (d)
Figure 4. Cont.
Materials 2018, 11, 1803 9 of 19
Materials 2018, 11, x FOR PEER REVIEW 9 of 19

GNMC
C1s-GN C1s GNOMC
Sp3 C rGNOMC
50,000 80,000 MGNMC
MGNC
70,000 MGNOC
40,000 Mxene
60,000 GNO
GN
Intensity (a.u.)

Intensity (a.u.)
30,000 50,000

40,000
20,000
30,000

10,000 C-O 20,000

O-C=O 10,000
287.0 287.5 288.0 288.5 289.0 289.5 290.0 290.5 291.0 291.5
Binding energy (eV)

0
0
292 290 288 286 284 282
-10,000
Binding energy (eV) 280 281 282 283 284 285 286 287 288 289 290 291
Binding energy (eV)

(e) (f)
Figure 4. XPS
Figure fitting
4. XPS curves
fitting of of
curves TiTi
3 C3C
2T
2Txx (a) Ti2p(b)
(a) Ti2p (b)C1s,
C1s,(c)(c) O1s,
O1s, (d)(d)
F1s,F1s,
andand (e) fitting
(e) fitting curvecurve of the GN
of the GN
C1s; (f) overlapping
C1s; (f) overlappingcurves of of
curves GNO,
GNO,rGNO,
rGNO, GN, MXene,
MXene,and and graphene/
graphene/ MXene-graphene
MXene-graphene composites.
composites.

1. Atomic
TableTable percentages
1. Atomic ofof
percentages TiTi
3C 2 2TTXX,, GN,
3C
GN,GNO,
GNO,rGNO,
rGNO,andand composites
composites fromfrom XPS analysis.
XPS analysis.

ElementsC1s (%)
Elements C1s (%) O1sO1s
(%)(%) F1s
F1s (%)
(%) Ti (%)
Ti (%) SS(%)
(%) N (%)
N (%)Si (%) Cl (%)Cl (%)
Si (%)
MXeneMXene 20.54
20.54 14.86
14.86 58.27
58.27 6.32
6.32 -- - - - - - -
MC MC 89.5489.54 8.8 8.8 - - -- -- 1.161.16 0.51 0.51 - -
GNMC GNMC 81.38
81.38 2.462.46 15.31
15.31 -- -- 0.850.85 - - - -
GNOMCGNOMC 73.3473.34 8.168.16 15.02
15.02 -- -- 0.630.63 2.85 2.85 - -
rGNOMC 75.4975.49
rGNOMC 7.667.66 1.71
1.71 -- -- - - - - - -
MGNC MGNC 56.5556.55 33.69 33.69 2.41
2.41 3.48
3.48 -- 1.551.55 - - 2.34 2.34
GN GN 95.4295.42 4.074.07 - - -- 0.52
0.52 - - - - - -
GNOGNO 92.4992.49 7.517.51 - - -- -- - - - - - -
rGNO rGNO 93.1293.12 6.886.88 - - -- -- - - - - - -

3.2. Surface
3.2. Surface Property
Property of Composites
of Composites
The hydrophilicity associated with wettability plays a vital role in moistening the surfaces. A
The hydrophilicity associated with wettability plays a vital role in moistening the surfaces.
contact angle above 90° is considered hydrophobic, and below 90° is hydrophilic. Water-loving
A contact angle above 90◦ is considered hydrophobic, and below 90◦ is hydrophilic. Water-loving
constitutions reduce the contact angle, whereas water-abhorring compounds increase the contact
constitutions
angle. The reduce
contactthe contact
angle can beangle,
tunedwhereas
by usingwater-abhorring
organic or inorganic compounds increase
materials [69]. the contact
The spreading of angle.
The contact
the liquid angle can
on the be tuned
surface dependsby onusing organic
the surface or inorganic
energy between thematerials
solid and[69].
liquid. The
Thespreading
increasing of the
liquidsurface
on theroughness
surface depends
and surface on energy
the surface
causesenergy between nature
the hydrophobic the solid[70].and
When liquid. The increasing
the roughness
increases,
surface roughness the airand
is trapped
surface in energy
nano or micro
causesgrooves. This air minimizes
the hydrophobic nature the[70].
wetting area and
When theleads
roughness
increases, the air is trapped in nano or micro grooves. This air minimizes the wetting area andasleads to
to hydrophobicity. Hence, the topography of the materials and their other properties, such
morphology, roughness, and chemical homogeneity, influences the surface wettability [71]. The
hydrophobicity. Hence, the topography of the materials and their other properties, such as morphology,
wetting ability of the composites are shown in Figure 4. GNMC, GNOMC, and rGNOMC exhibit a
roughness, and chemical homogeneity, influences the surface wettability [71]. The wetting ability of
hydrophobic nature at 125°, 124°, and 126°, respectively, whereas MGNC and MGNOC show
the composites
hydrophilicare shown at
behavior in 78°
Figure
and4.81°,
GNMC, GNOMC,
respectively. Theand rGNOMC
wetting energies exhibit
of GNMC,a hydrophobic
GNOMC, nature
◦ , 124◦ , and 126◦ , respectively, whereas MGNC and MGNOC show hydrophilic
at 125rGNOMC, behavior ◦
MGNC, and MGNOC are −41.85, −41, −42.82, 14.89, and 11.48 mN·m , respectively. −1 It is at 78
and 81 ◦ , respectively. The wetting energies of GNMC, GNOMC, rGNOMC, MGNC, and MGNOC
obvious that the positive wetting energy increases the hydrophilic nature. The most negative wetting
are −energy −41, −mN·
41.85, (−42.82 m−1) 14.89,
42.82, causes and
the highest mN·m−
11.48 contact 1 , respectively.
angle and the contactIt angle is incommensurate
is obvious that the positive
with
wetting the wetting
energy energy.
increases the The spreadingnature.
hydrophilic coefficients of −114.65,
The most −113.8,
negative −115.62,
wetting −57.91,(−
energy and mN·m−1 )
−61.31
42.82
mN·m−1 were generated from GNMC, GNOMC, rGNOMC, MGNC, and MGNOC, respectively. The
causes the highest contact angle and the contact angle is incommensurate with the wetting energy.
spreading coefficient also expresses a similar behavior to the wetting energy in terms of hydrophobic
The spreading coefficients of −114.65, −113.8, −115.62, −57.91, and −61.31 mN·m−1 were generated
behavior. The rising work of adhesion increases the water-loving behavior, for instance, GNMC,
from GNOMC,
GNMC, GNOMC, rGNOMC, MGNC, rGNOMC, MGNC, engender
and MGNOC and MGNOC, values respectively. The spreading
of 30.95, 31.8, 29.98, coefficient
87.69, and 84.28
also expresses a similar behavior to the wetting energy in terms of hydrophobic
mN·m , respectively; the increasing work of adhesion increases the hydrophilicity of the surface
−1 behavior. The rising
work [69,70].
of adhesion increases the water-loving behavior, for instance, GNMC,
Hence, coating the graphene-based materials increases the hydrophobicity of the surfaces.GNOMC, rGNOMC,
MGNC, and MGNOC engender values of 30.95, 31.8, 29.98, 87.69, and 84.28 mN·m−1 , respectively;
the increasing work of adhesion increases the hydrophilicity of the surface [69,70]. Hence, coating the
graphene-based materials increases the hydrophobicity of the surfaces. Tissera et al. reported that
GO-coated cotton showed an improvement in hydrophobicity with a maximum contact angle of
Materials 2018, 11, 1803 10 of 19

Materials 2018, 11, x FOR PEER REVIEW 10 of 19

143◦ [72]. Zhang et al. reported that poly (vinylidene fluoride—hexafluoropropylene)/graphene
Tissera et
composite al. reported
is super that GO-coated
hydrophobic in naturecotton showedthis,
[73]. Despite an the
improvement in hydrophobicity
MXene-graphene-based foamwith a
exhibits
maximum contact
a hydrophilic angle is
nature which ofdue
143°to [72]. ZhangMXene
the surface et al. flakes.
reported that
The poly (vinylidene
produced composite fluoride—
can be used
hexafluoropropylene)/graphene composite is super hydrophobic in nature [73]. Despite this, the
to protected instruments from harmful water environments.
MXene-graphene-based foam exhibits a hydrophilic nature which is due to the surface MXene flakes.
3.3.The produced
Electrical composite can be used to protected instruments from harmful water environments.
Conductivity
The
3.3. electrical
Electrical conductivity of MC is significantly affected by the spray-coating process.
Conductivity
The incorporation of 2D materials in the polymer alters the electric conductivity owing to the
The electrical conductivity of MC is significantly affected by the spray-coating process. The
arrangement of the 2D material in the polymer matrix [74]. In graphene, the carbon atoms are
incorporation of 2D materials in the polymer alters the electric conductivity owing to the arrangement
arranged hexagonally with sp2 hybridization and the free π valance electron aligns at right angles to
of the 2D material in the polymer matrix [74]. In graphene, the carbon atoms are arranged
thehexagonally
hexagonal plane. This electron is responsible for the out-of-plane π bond and electron mobility.
with sp2 hybridization and the free π valance electron aligns at right angles to the
Thehexagonal
conductivityplane.ofThis
the electron
graphene influences by
is responsible forthethe number of graphene
out-of-plane π bond and layers. When
electron the number
mobility. The
of layers
conductivity of the graphene influences by the number of graphene layers. When the number of of
increases, the electrical conductivity reduces, which is due to the interfacial alignment
GNlayers
which increasethe
increases, the resistance
electrical [75]. GNOMC
conductivity reduces,displays
which isthe duehighest electric conductivity
to the interfacial alignment of of GNthe
composites,
which increase whichthe is supported
resistance [75]. by the SEM image
GNOMC displays of GNOMC
the highest (Figure 1c).conductivity
electric GNO arranges of thein a
flat-stack manner with possible touching of the GNO flakes, which leads
composites, which is supported by the SEM image of GNOMC (Figure 1c). GNO arranges in a flat- to interfacial electron transfer.
Hence,
stacketching
mannerwith withHNO 3 is the
possible best option
touching of theto tuneflakes,
GNO the self-assembly
which leadsof toGNO flakeselectron
interfacial on the MC matrix.
transfer.
TheHence,
conductivity
etchingiswith
inversely
HNO3proportional to the thickness
is the best option to tune the [76], and the conductivity
self-assembly of GNO flakes and Rons ofthe
GNOMC
MC
arematrix.
13.68 SThe −1 and 4.2 Ωis·sq
·cmconductivity −1 , respectively,
inversely proportional at ato the thickness
thickness [76], and
of 0.0174 the conductivity
cm (Figure and Rs
5). Nevertheless,
of GNOMC
GNOMC are from
deviates 13.68 theS·cm behavior, exhibits a low electric conductivity (9.3 S·cm−1 ) while
−1 and 4.2 Ω·sq−1, respectively, at a thickness of 0.0174 cm (Figure
MGNC 5).
Nevertheless,
showing the lowestGNOMC deviates from
sheet resistance (3.1 Ω the − 1
·sqMGNC ) at a behavior,
0.0350 cmexhibits
thickness; a low electricexhibits
MGNOC conductivity cm−1
8.97 S·(9.3
S·cm
with
−1) while
a 4.6 Ω·sq−showing the lowestand
1 sheet resistance sheet resistance
thickness (3.1 Ω·sq
of 0.0243 cm.) Of
−1 at the
a 0.0350 cm thickness;
fabricated composite, MGNOCMGNC
exhibits 8.97 S·cm −1 with a 4.6 Ω·sq−1 sheet resistance and thickness of 0.0243 cm. Of the fabricated
shows a maximum thickness of 0.0350 cm, while the others, such as GNMC (0.0191 cm), GNOMC
composite,
(0.0174 MGNC shows
cm), rGNOMC (0.0163a maximum
cm), MGNMC thickness of 0.0350
(0.0192 cm),cm,andwhile
MCthe others,
(0.0127 cm)such as GNMC
exhibit values(0.0191
below
cm), GNOMC (0.0174 cm), rGNOMC (0.0163 cm), MGNMC (0.0192 cm), and MC (0.0127 cm) exhibit
0.0200 cm. Hence, the highest thickness of MGNC minimizes the electric conductivity. In addition,
values below 0.0200 cm. Hence, the highest thickness of MGNC minimizes the electric conductivity.
MGNMC shows the highest Rs value owing to the aggregation of the hydrophobic PVDF and
In addition, MGNMC shows the highest Rs value owing to the aggregation of the hydrophobic PVDF
hydrophilic MXene. The highest electrical mobility increases the EMI SE. Hence, the lowest sheet
and hydrophilic MXene. The highest electrical mobility increases the EMI SE. Hence, the lowest sheet
resistance of MGNC causes it to possess the highest surface electron mobility, which leads to the surface
resistance of MGNC causes it to possess the highest surface electron mobility, which leads to the
reflection of EMI SE [47]. Further, the resistivity of GNOMC, rGNOMC, GNMC, MGNMC, MGNC and
surface reflection of EMI SE [47]. Further, the resistivity of GNOMC, rGNOMC, GNMC, MGNMC,
MGNOC
MGNCwere 0.073, 0.083,
and MGNOC were0.087,
0.073,0.101,
0.083,0.108
0.087,and 0.111
0.101, Ω·and
0.108 cm, respectively. Despite theDespite
0.111 Ω·cm, respectively. conductivity
the
depend on thickness
conductivity depend of on
thethickness
materials.ofThe the functionalized
materials. The graphenefunctionalized increased
graphenethe resistivity
increased while
the
presence of MXene
resistivity significantly
while presence of MXeneincreased the resistivity
significantly increased of the
fabric and foam
resistivity (Figure
of fabric and6b).
foamDespite
(Figurethis,
other
6b).parameters
Despite this,suchotherasparameters
thickness such and as some other and
thickness structural features
some other (foams)
structural also influence
features (foams) also EMI
SE influence
[46]. Further, the[46].
EMI SE lowest Rs and
Further, thehigh
lowestresistivity
Rs and highof MGNC is due
resistivity to the presence
of MGNC is due to theof MXene
presence onofthe
surface
MXene of on
thethe
composite
surface of(Figure 1i). Further
the composite explanation
(Figure 1i). Further is explanation
given in theisEMI-shielding section.
given in the EMI-shielding
section.

Figure
Figure 5. 5. Contact
Contact anglesofof(a)
angles (a)GNMC,
GNMC,(b)
(b)GNOMC,
GNOMC, (c)
(c) rGNOMC,
rGNOMC,(d)
(d)MGNC,
MGNC,and
and(e)(e)MGNOC.
MGNOC.
Materials 2018, 11, x FOR PEER REVIEW 11 of 19
Materials 2018, 11, 1803 11 of 19
Materials 2018, 11, x FOR PEER REVIEW 11 of 19

Figure 6. (a) Electric conductivity and sheet resistance of the composites and (b) resistivity of the
composites (Rs: sheet resistance; σ: electric conductivity).
Electric conductivity
Figure 6. (a) Electric conductivity and
and sheet
sheet resistance
resistance of
of the composites
composites and (b) resistivity of the
composites (Rs: sheet
sheet resistance;
resistance; σ:
σ: electric
electric conductivity).
conductivity).
3.4. Electromagnetic Shielding Effectiveness of Composites
3.4. Electromagnetic
3.4.In this study, solution
Electromagnetic Shielding Effectiveness
Shieldingcasting and spray
Effectiveness of
of Composites
coating were performed to produce EMI shielding
Composites
composites.
In MC was spray-coated by a dispersed mixture of GN, GNO, and rGNO (3 g·L−1) and PVDF
In this
this study,
study, solution
solution casting
casting and and spray
spray coating
coating were
were performed
performed to to produce
produce EMI EMI shielding
shielding
(5composites.
g·L ) in in aMC
−1 DMF wassolution.
spray-coatedThe thickness of MC was adjusted by changing therGNOnumber of·Lcoating
− 1 ) and
composites. MC was spray-coated byby a dispersed
a dispersed mixture
mixture of GN,
of GN, GNO, GNO,
and and
rGNO (3 g·L(3−1)gand PVDF
cycles.
PVDF All
(5 of
g · the
L −1 )EMI
in inSEa calculations
DMF solution. were carried
The out according
thickness of MC wasto the Gamage
adjusted by et al. study.the
changing The EMI
number
(5 g·L ) in in a DMF solution. The thickness of MC was adjusted by changing the number of coating
−1
shielding
of coating of all of
cycles. the composites
AllSE ofcalculations is
the EMI SEwere illustrated
calculations in Figure
were 7. It is
carried to obvious
outthe that
according all of
to al.the composites
thestudy.
Gamage
cycles. All of the EMI carried out according Gamage et The et EMI al.
show
study.a maximum
The EMI EMI SE inofthe
shielding all frequency
of the range ofis1.9–2.6
composites GHz in
illustrated in Figure
S band 7.region
It is whereasthat
obvious GNMC all of
shielding of all of the composites is illustrated in Figure 7. It is obvious that all of the composites
showed
the increasing
composites trend
show in X band region EMI SEand other composites exhibited slight downward
S bandtrend.
show a maximum EMIa SEmaximum
in the frequency in the
range frequency
of 1.9–2.6 GHz range inofS1.9–2.6 GHz
band region in
whereas region
GNMC
Ofwhereas
the composites,
GNMC MGNC
showed yields
increasing the maximum
trend in X and
band minimum
region and EMI
other shielding
composites of 41 and 31 slight
exhibited dB,
showed increasing trend in X band region and other composites exhibited slight downward trend.
respectively,
downward whereas
trend. MGNOC
OfMGNC
the composites,exhibitsMGNC a 36 dByields
maximum and 23.14 dBminimum
the maximum minimum EMIshielding shielding in41
Of the composites, yields the maximum and minimum and EMI shieldingEMI of 41 and 31ofdB,
S and
band31region. The
dB, respectively, maximum whereas EMI shielding
MGNOC of GNMC, GNOMC, rGNOMC, MGNMC, MC, and
respectively, whereas MGNOC exhibits a 36exhibits a 36 dBand
dB maximum maximum
23.14 dBand 23.14 dBEMI
minimum minimum
shielding EMI in
GNMC-single
shielding in S are
band 35.3, 36.2,The
region. 34.6, 35.2, 28.5,
maximum EMI and 33.4 dB,
shielding of respectively,
GNMC, GNOMC, and rGNOMC,
the correspondingMGNMC,
S band region. The maximum EMI shielding of GNMC, GNOMC, rGNOMC, MGNMC, MC, and
minimum
MC, EMI shieldingare
and GNMC-single is 35.3,
28.4, 36.2,
29.7,34.6,
28.4,35.2,
28.8, andand 23.2, 28dB, dB,respectively,
respectively. andThe the average EMI
GNMC-single are 35.3, 36.2, 34.6, 35.2, 28.5, 28.5,
and 33.433.4 dB, respectively, and the corresponding
corresponding
shielding
minimum of GNMC, GNMC-single, GNOMC, rGNOMC, MGNMC, MGNC, and MGNOC is 32, 30,
minimum EMI EMIshielding
shieldingis 28.4,is 28.4,29.7, 28.4,28.4,
29.7, 28.8,28.8,
and 23.2,
and 28 dB, 28
23.2, respectively. The average
dB, respectively. The EMI
averageshielding
EMI
32.66,
of 31.43, GNMC-single,
GNMC, 31.87, 35.7, andGNOMC, 32.86 dB,rGNOMC,respectively in S band
MGNMC, region.
MGNC, and This trend changed
MGNOC is 32, 30, in X band
32.66, 31.43,
shielding of GNMC, GNMC-single, GNOMC, rGNOMC, MGNMC, MGNC, and MGNOC is 32, 30,
region
31.87, that can be represented as follow,S band the maximum EMI shielding of in
GNMC 53.89 dB with
32.66, 35.7,
31.43,and 32.86
31.87, dB,and
35.7, respectively
32.86 dB,inrespectively region.
in SThis
bandtrend changed
region. This trendX band region
changed in that
X bandcan
reflection
be of
represented 13.10 dB
as and
follow, absorption
the maximum of 43.38
EMI dB (Figure
shielding 7 and
of GNMC Table S2).
53.89 The
dB maximum
with EMI
reflection SE
of range
13.10 dB
region that can be represented as follow, the maximum EMI shielding of GNMC 53.89 dB with
ofand
composites
absorption was 53.89–31.73
ofdB43.38 dB while minimum range was 52.4–30.15 dB (Table S2). The maximum
reflection of 13.10 anddB (Figure 7 of
absorption and Table
43.38 dBS2). The7maximum
(Figure and Table EMI SE range
S2). The maximum of composites
EMI SE range was
reflection
53.89–31.73 lossdB(SE R) and absorption loss (SE A) range were 14.75–11.73 dB and 43.38–20.01 dB,
while minimum range was 52.4–30.15 dB (Table S2). The maximum reflection loss
of composites was 53.89–31.73 dB while minimum range was 52.4–30.15 dB (Table S2). The maximum
respectively
(SE ) and (Table S2).loss
absorption Further,
(SE )SE R was high in GNMC with 14.75 dB of maximum while exhibited
range were 14.75–11.73 dB and 43.38–20.01 dB, respectively (Table S2).
R
reflection loss (SER) and absorption A loss (SEA) range were 14.75–11.73 dB and 43.38–20.01 dB,
maximum
Further, absorption
SER (Table
was high of 26.97 dB. Among fabricated fabric, absorption played a major role in EMI
respectively S2).inFurther,
GNMC SE with 14.75 dB of maximum while exhibited maximum absorption of
R was high in GNMC with 14.75 dB of maximum while exhibited
shielding.
26.97 dB. Among fabricated fabric, absorption played afabric,
majorabsorption
role in EMIplayed
shielding.
maximum absorption of 26.97 dB. Among fabricated a major role in EMI
shielding. MC
MC GNMC
GNMC-single
GNMC
55 GNOMC
40 GNOMC rGNOMC
rGNOMC MGNMC
MC
MGNMC MGNC
MGNCMC GNMC
38 GNMC-single
MGNOC 50 55 MGNOC
GNOMC
GNMC
40 GNOMC rGNOMC
36 rGNOMC MGNMC
MGNMC MGNC
MGNC
38 MGNOC 45 50 MGNOC
EMI SE (dB)

34
EMI SE (dB)

36
32
40 45
EMI SE (dB)

34
EMI SE (dB)

30
32
28 35 40
30
26
28 30 35
24
26
0 1 2 3 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5
30
24 Frequency (GHz) Requency (GHz)
0 1 2 3 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5
(a) (GHz)
Frequency (b) (GHz)
Requency

(a) Figure 7. Cont. (b)

 Materials 2018, 11, 1803 12 of 19
Materials 2018, 11, x FOR PEER REVIEW 12 of 19

MC
GNMC
45 GNOMC 15 MC
rGNOMC GNMC
GNOMC
MGNMC
rGNOMC
MGNC MGNMC
40 MGNOC
14 MGNC
MGNOC

35
13

SER
SEA

30
12

25
11

20
10
8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 12.5
Frequency (GHz) Frequency (GHz)

(c) (d)

100
MX/PET
Cu bulk stainless steel
90
CNT/Polym
80 MX/Praf

Cu foil
70 MX/foam
EMI SE (dB)

Al foil Ni fiber
60
MGNC- X band
rGO/PbTiO3
50 CNT/PP
MGNC-S band
MWCNT/PC
40 GNP/B4C GN/PVDF

MWCNT/PS
30 MWCNT/NCF
CF-30 g/m2
MX/Cellu PF/GN/CNT
GN/Fe3O4
CB/ABS CB/EPDM
20 NCF-20 g/m2

10
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Thickness (mm)

(e) (f)
Figure
Figure 7. 7.
EMIEMI shielding
shieldingeffectiveness
effectivenessofofcomposites
composites (a)
(a) EMI SESE in
inS-band,
S-band,(b)
(b)EMI
EMISESEinin X-band,
X-band, (c)(c)
SER ,
SE(d)
R, (d) SE , (e) comparison of EMI SE with thickness and (f) Basic mechanism
SEA , (e) comparison of EMI SE with thickness and (f) Basic mechanism in MGNC.
A in MGNC.

The
The mechanism
mechanism of of GNMC
GNMC can
can bebe explained.
explained. according
according to to structure
structure that
that thethe MXene
MXene filmfilm and
and
graphene
graphene nanoplates
nanoplates reflects
reflects incident
incident rays
rays caused
caused byby moving
moving charges
charges while
while internal
internal hollow
hollow structure,
structure,
free
free carriers
carriers andand layered
layered structure
structure of MXene
of MXene caused
caused multiple
multiple reflection
reflection and scattering
and scattering within within
the core, the
core, leads
finally finallytoleads to absorption
absorption [77,78]. [77,78].
Further,Further, the highest
the highest EMI shielding
EMI shielding of MGNC of MGNC arisesto
arises owing owing
its
to its physical
physical nature,
nature, i.e., lowest i.e., lowest
sheet sheet resistance,
resistance, highinternal
high resistivity, resistivity,pores,internal pores, and
and thickness thickness
(Figure 6b).
(Figurethe
Among 6b). AmongMC
fabricated the composites,
fabricated MC GNOMCcomposites,
showsGNOMC the highest shows
EMI the highestinEMI
shielding S bandshielding
regionin
S band
owing region
to the owing
planer natureto the
causedplaner nature
by the causedgroup
functional by thederived
functional groupofderived
by means etchingby means
[79]. Evenof
etchingin[79].
though, X band Even though,
region, GNMC,in XMGNMC
band region, GNMC, MGNMC
and rGNOMC exhibitedand higherrGNOMCEMI SEexhibited
compare with higher
EMI SE compare with GNO as they possessed relatively higher
GNO as they possessed relatively higher reflection and absorption loss (Figure 7b–d and Table S2). reflection and absorption loss
(Figure
This can be7b–d andcorrelated
further Table S2).with Thiscross
can section
be further correlated
of fabric that made withcores
crossandsection of fabric
randomly that GN,
arrange made
coresand
rGNO andMXene
randomlyflakearrange GN, rGNO(Figure
caused absorption and MXene
7b–d and flake caused
Table S2). absorption
In addition,(Figure 7b–d and
GNO exhibited
Table
high EMI S2). In addition,
shielding in S bandGNO exhibited
region whichhigh EMI
is due shielding
to the in S band region
high conductivity and inwhichX bandisregion
due toitsthe
high
EMI SEconductivity and in X band
decrease significantly owing region its EMIresponse
to dielectric SE decrease significantly
rather than electron owing to dielectric
mobility response
[80]. Further,
rather than electron mobility [80]. Further, planar structure
planar structure of GNOMC diminished absorption (Figure 7b–d and Table S2). Formation of of GNOMC diminished absorption
(Figure 7b–d
functional groups andpromotes
Table S2).interfacial
Formation of functional
touching of the groups promotes
flake-created plannerinterfacial
surfacetouching
with higher of the
flake-created
conductivity planner1csurface
(Figures and 7). with
GNMChigherand conductivity
MGNMC (Figures display 1c and 7).
similar EMI GNMC and MGNMC
shielding values.
display similar
However, EMI shielding
MXene-graphene foam values. However,
exhibits good EMI MXene-graphene
shielding which foamcanexhibits good EMI
be explained shielding
by the fact
which
that can be explained
the coating of hydrophilic by the fact that
MXene the coating
colloidal solution of and
hydrophilic MXene colloidal
the hydrophobic GN-PVDF solution
polymer and
the hydrophobic
coating on the carbon GN-PVDF
fiber arepolymer coatingtoon
limited owing thethe carbon between
adhesion fiber are MXene
limited and owing to the adhesion
graphene. Thus,
between electron
interfacial MXene and graphene.
transfer Thus, interfacial
is minimized owing to electron
the impropertransfer is minimized
arrangement of GNowing
andto the improper
MXene flake
arrangement
increasing of GN and
the surface MXene(Figure
resistance flake increasing
7). Hence,thethesurface
reflection resistance
was low(Figure 7). Hence,
for all the compositethe (Figure
reflection
wasand
7b–d lowTable
for allS2).
the The
composite
specific(Figure 7b–d andeffectiveness
EMI shielding Table S2). The (SSE)specific
of MC, EMI shielding effectiveness
GNMC-single, GNMC,
(SSE) of MC,
GNOMC, rGNOMC, GNMC-single,
MGNMC, GNMC,
MGNC, GNOMC,
and MGNOC rGNOMC, MGNMC,
is 381.5, 452.73,MGNC,
394.91, and MGNOC
189.90, is 381.5,
183.8, 185.3,
46.4, and 56.18 dB·cm3·g−1, respectively; the single GN-coated composite shows the highest SSE.
Furthermore, SSE range of all the composite in X band region was 449.95–68.05 dB·cm3·g−1 (Table S2).
Materials 2018, 11, 1803 13 of 19

452.73, 394.91, 189.90, 183.8, 185.3, 46.4, and 56.18 dB·cm3 ·g−1 , respectively; the single GN-coated
composite shows the highest SSE. Furthermore, SSE range of all the composite in X band region was
449.95–68.05 dB·cm3 ·g−1 (Table S2). Of the fabricated single-coated composites, GNMC shows the
highest absolute EMI shielding effectiveness (SSE/t) of 35,369.82 dB·cm3 ·g−1 , whereas MC, GNMC,
GNOMC, rGNOMC, MGNMC, MGNC, and MGNOC exhibit values of 30,039, 10,914, 11,275.78,
9649.42, 1324.29, and 2311.83 dB·cm3 ·g−1 , respectively in S band region while SSE/t of composite in
X band region was 35428.4–1944.3 dB·cm3 ·g−1 in which MGNC displayed lowest SSE/t (Table S2).
Further, the thickness influences the EMI shielding. Reducing the amount of PVDF increases SSE/t
(PVDF (1 g·L−1 ) and GN (3 g·L−1 ) in DMF, yielding 31,095.13 dB·cm2 ·g−1 in S band region). According
to reported data, PVDF exhibits an EMI shielding effectiveness of approximately 1.1 dB, which is not an
effective barrier against electromagnetic radiation compared with carbon-based PVDF composites [48].
Most of the carbon base composite reported showed lower EMI shielding compared to the
composite produced and thickness proportional to EMI SE and increasing graphene loading increase
the EMI SE. However, in each case, equal amount of dispersed solutions was utilized. Thus, in this
case, not only component loading but also structural feature of composite affect EMI SE (Table S1 and
Figure 1, Figure 7e and Figure S2) [77,81,82]. Further, the MXene based composite with less thickness
generate relatively good EMI SE compare with other composite reported (Figure 7e) and the Al and
Cu foil show exceptional EMI shielding of approximately 70 dB (~10 µm). Gonzalez et al. reported
that the reflection from CNT and graphene is approximately 10 dB with an absorption of 20 dB. At the
same time, ultrathin graphene-based composites have also shown a lower reflection of approximately
10 dB [75,83–85]. According to Zhao et al. the EMI shielding of the PVDF/graphene composite was
22.58 dB at a thickness 0.1 mm and electrical conductivity of 6.56 × 10−3 S·cm−1 [40]. Poly (ether
imide) (PEI-rGO nanocomposite films exhibited EMI shielding values of approximately 26 dB at a
thickness of 0.086 mm [41]. PVDF/graphene quantum dots showed a 31 dB EMI shielding at an 8 GHz
frequency. Further, Ag-nanoparticle reinforced PVDF/graphene quantum dots increase EMI shielding
(43 dB at 12 GHz) [42]. Hence, the composition, amount, and status of graphene in the composition
alter the EMI shielding. In addition, the incorporation of nanoparticles improves the EMI shielding of
the graphene composites [40–42]. Yuan et al. reported that reduced graphene oxide nano-composite
films exhibit EMI shielding of 32 dB with 0.27 mm [85]. Based on the literature reviewed, our study
shows excellent EMI shielding effectiveness over a frequency range of 1–3 GHz and 8–12.4 GHz.

3.5. Thermal Stability and Thermo Gravimetric Analysis of Composites

Thermal stability studies were carried out using well-known thermogravimetric analysis
(TGA) and differential thermal analysis (DTG). The temperature range was maintained from room
temperature to 1000 ◦ C with a heating rate of 10 ◦ C·min−1 , and during the TGA and DTG analysis,
the Al2 O3 crucible and nitrogen environment were maintained. The mass loss and enthalpy changes
were investigated using TGA and DTG, respectively. All of the samples exhibit outstanding stability
over a higher temperature range (Figure 8a). Swift degradation of all of the composites occurred about
375 ◦ C to 500 ◦ C, which is higher than that of MC, which exhibits a 5% weight loss between 280 ◦ C and
400 ◦ C [7]. Further, MGNOC and MGNC exhibit a 65% and 52% weight loss, respectively, whereas the
MC-based composites exhibit a loss of 20% in the aforementioned temperature range. These composites
(MGNOC and MGNC) show a higher weight loss than MC (6.5%) [7]. This is due to the introduction
of a polymer binder (PVDF and PAA) and GN/GNO to the composite [60,86]. The weight-loss
temperature of pristine PVDF and graphene are approximately 400 and 200 ◦ C, respectively [87–91].
We noticed that all of the fabrics exhibit similar behavior below 400 and above 500 ◦ C. All of the fabric
shows a minimal weight loss (~20%) which is due to the introduction of graphene species and MXene
(Table 2). In addition, the thermal stability of the composites can be altered by amount filler loading,
types of polymers used, environment of experience, exposure temperature and duration of exposure
of the composites. Presence of oxygen environment burn both polymer, MXene and graphene [92].
The MC had the minimum temperature of the degradation was 40 ◦ C and 174 ◦ C. This trend changed
Materials 2018, 11, 1803 14 of 19

after introduction of graphene (Table 2). Though, minimum degradation temperature of the all
composite bellow 300 °C that is intermediate temperature of graphene and PVDF. The introduction
Materials 2018, 11, x FOR PEER REVIEW 14 of 19
of the oxygen on graphene increase the weight loss considerably (Table 2). On the whole, PVDF,
graphene,
compare with MXene carbonfilmfabric-based
possessed low thermal stability
composites. compare
Hence, the carbonwith carbon
fabric fabric-based
induces the thermal composites.
stability
Hence, the carbon fabric induces the thermal stability of the
of the composite [7]. MGNC and MGNOC lost 5% and 20% weight at approximately 100 °C composite [7]. MGNC and MGNOC
which
lost
was5% dueand 20%water
to the weight atand
loss, approximately 100 ◦ C which
then both constrained was due up
degradations to the water
to 400 °C. loss, and then
In addition, both
above
constrained degradations up to 400 ◦ C. In addition, above 400 ◦ C, MGNC and MGNOC exhibit a 50%
400 °C, MGNC and MGNOC exhibit a 50% and 65% weight loss, respectively. The DTG curve of the
and 65% weight
composites shows loss, respectively.
endothermic peaksThe at DTG curve
different of the composites
positions. GNMC, GNOMC, shows endothermic
rGNOMC, MGNMC, peaks at
different
MGNC, positions.
and MGNOC GNMC, show GNOMC,
prominent rGNOMC,
peaks atMGNMC,
476.9, 468.7,MGNC,
490.5,and MGNOC
422.4, 453.1, show prominent
and 469.33 °C,
peaks at 476.9,(Figure
respectively 468.7, 8b).
490.5, 422.4,
This 453.1, where
indicated rapid◦ C,
and 469.33 respectively
weight (FigureIn8b).
loss occurred. This indicated
addition, MC exhibitswherea
rapid
broadweight loss occurred.
endothermic peak in theInrange
addition, MC exhibits
of 243–390 °C Hence, a the
broad endothermic
stability peak indramatically
of the composite the range of
increases◦ Cwith
243–390 the coating
Hence, process.
the stability Thecomposite
of the introduction of MXene increases
dramatically minimizeswiththe the
degradation of the
coating process.
composite,
The which
introduction of means
MXenethat all of the
minimizes the MXene-based
degradation ofcomposites
the composite,showwhich
a lowmeans
thermalthatstability.
all of the
Further, GNOMC
MXene-based and rGNOMC
composites show a low show another
thermal endo-thermic
stability. Further,peak
GNOMCat 350and
°C,rGNOMC
which is more
showintense
another
in rGNO thanpeak
endo-thermic in GNO. ◦ C,introduction
at 350The which is more of intense
GNO and rGNO than
in rGNO generates
in GNO.newThe
peaks where they
introduction ofwere
GNO
and rGNO generates new peaks where they were absent in GN, and a similar peak is observedtoat
absent in GN, and a similar peak is observed at 313 °C, which shifts to a lower temperature owing
the ◦presence
313 C, whichofshiftsMXene. to a MGNC and MGNOC
lower temperature exhibit
owing to the
the same endo-thermic
presence of MXene.peaksMGNC at 117
and°C owing
MGNOC
to the thermal
exhibit the sameconductivity
endo-thermicoGN/PVDF, ◦ C owing
peaks at 117internal pores,
to theLiCl, and PAA.
thermal The TG oGN/PVDF,
conductivity curve supports this
internal
statement [76]. Finally, the rGO-based composite displays a higher thermal
pores, LiCl, and PAA. The TG curve supports this statement [76]. Finally, the rGO-based composite stability than the other
composites
displays fabricated.
a higher thermal stability than the other composites fabricated.

Figure 8. (a)
Figure 8. (a) TGA and (b)
TGA and (b) DTG
DTG curves
curves of
of composites.
composites.

Table 2. Comparison of mass changes of composites.

Table 2. Comparison of mass changes of composites.
Rapid Change Rapid Mass Whole Mass Degradation Starting
No. Composites Rapid Change Rapid Mass Whole Mass Degradation Starting
No. Composites Range (◦ C) Change (%) Change (%) Temperature (◦ C)
Range (°C) Change (%) Change (%) Temperature (°C)
1 GNMC 425–505 15.5 26.0 245.0
1 GNMC 425–505 15.5 26.0 245.0
2 GNOMC 435–500 11.6 19.5 245.0
23 GNOMC
rGNOMC 435–500
460–510 11.6
16.1 19.5
22.2 245.0
265.0
34 rGNOMC
MGNMC 460–510
420–510 16.1
12.0 22.2
19.1 265.0
275.0
45 MGNC
MGNMC 373–490
420–510 38.6
12.0 52.1
19.1 78.5
275.0
56 MGNC 35–75
373–490 22.1
38.6 52.1 35.0
78.5
MGNOC 65.5
375–510 32.6 75.5
35–75 22.1 35.0
6 MGNOC 65.5 40.0
7 MC 175–570
375–510 6.2
32.6 6.5 75.5
174.0
40.0
7 MC 175–570 6.2 6.5
174.0
4. Conclusions
Spray-coated composites and solvent casting films were successfully fabricated with high
4. Conclusions
flexibility, low apparent density (~0.77 to 0.081 g·cm−3 ) and low thickness (0.0120–0.0350 cm).
Spray-coated composites and solvent casting films were successfully fabricated with high
The fabricated composites exhibited an uppermost contact angle of 126◦ and the range of wetting
flexibility, low apparent density (~0.77 to 0.081 g·cm−3) and−low thickness (0.0120–0.0350 cm). The
energy of all of the composites was −42.82 to 14.89 mN·m 1 . Thus, graphene-based constitutions
fabricated composites exhibited an uppermost contact angle of 126° and the range of wetting energy
of all of the composites was −42.82 to 14.89 mN·m−1. Thus, graphene-based constitutions improve the
hydrophobicity. The surface-coated MXene and graphene oxide minimized the sheet resistance and
showed a high conductivity of 13.68 S·cm−1 with a sheet resistance of 3.1 Ω·sq−1. The MXene-graphene-
Materials 2018, 11, 1803 15 of 19

improve the hydrophobicity. The surface-coated MXene and graphene oxide minimized the sheet
resistance and showed a high conductivity of 13.68 S·cm−1 with a sheet resistance of 3.1 Ω·sq−1 .
The MXene-graphene-PVDF composition improved the thermal stability and constrained the dramatic
weight changes up to 400 ◦ C. The flat stack-like composition displayed an excellent EMI shielding of
41 dB (99.99% efficiency) in S band while exhibited maximum EMI shielding of GNMC 53.8 (99.999%)
with reflection of 13.10 dB and absorption of 43.38 dB (Figure 7 and Table S2). and the size of the pore
comparatively advanced the property of EMI shielding. The single-coated graphene fabric showed an
outstanding absolute shielding effectiveness of 35,369.82 dB·cm2 ·g−1 . Hence, the composites with high
EMI SEs and that are hydrophobic in nature can be applied in various applications such as aeronautics,
locators, air travel, mobile phones, handy electronics, and military application.

Supplementary Materials: The following are available online at http://www.mdpi.com/1996-1944/11/10/1803/

s1, Figure S1: EMI shielding sample loading; Figure S2: Cross section of SEM image; Figure S3: EDX and mapping;
Figure S4: Normalized curve of Raman spectrum; Table S1: Comparison of EMI SE with thickness; Table S2:
Comparison of maximum (MAX), minimum (MINI), average (AVE) shielding, SSE and SSE/t of composite in
each case.
Author Contributions: K.Y.C. and R.B. designed the project; K.R., B.M.K. and J.J.M. were performed experiment;
H.J.J. and Y.S.L. were analyzed the data; C.M.Y. supervised the analysis; K.R. wrote the manuscript.
Funding: This research was supported by the Leading Human Resource Training Program of Regional Neo
industry through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and
future Planning (NRF-2017H1D5A1043865). C.M.Y. acknowledges the financial support from the Korea Institute of
Science and Technology (KIST) Institutional Program and from Nanomaterial Technology Development Program
through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future
Planning (2016M3A7B4027695).
Conflicts of Interest: There are no conflicts to declare.

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