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Ionic Conductive Polyurethane-Graphene Nanocomposite for Performance

Enhancement of Optical Fiber Bragg Grating Temperature Sensor

Article  in  IEEE Access · August 2018

DOI: 10.1109/ACCESS.2018.2867220

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Received June 16, 2018, accepted August 6, 2018, date of publication August 27, 2018, date of current version September 21, 2018.
Digital Object Identifier 10.1109/ACCESS.2018.2867220

Ionic Conductive Polyurethane-Graphene

Nanocomposite for Performance Enhancement of
Optical Fiber Bragg Grating Temperature Sensor
FAREEZA JASMI1 , NUR HIDAYAH AZEMAN 1 ,
AHMAD ASHRIF A. BAKAR1 , (Senior Member, IEEE),
MOHD SAIFUL DZULKEFLY ZAN1 , (Member, IEEE),
KHAIRIAH HAJI BADRI2 , AND MOHD SUKOR SU’AIT3
1 Center of Advanced Electronic and Communication Engineering, Faculty of Engineering and Built Environment, Universiti Kebangsaan Malaysia,
43600 Bangi, Malaysia
2 Faculty of Science and Technology, School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 Bangi, Malaysia
3 Solar Energy Research Institute, Universiti Kebangsaan Malaysia, 43600 Bangi, Malaysia

Corresponding authors: Nur Hidayah Azeman (nhidayah.az@ukm.edu.my), Mohd Saiful Dzulkefly Zan (saifuldzul@ukm.edu.my),
and Mohd Sukor Su’ait (mohdsukor@ukm.edu.my)
This work was supported in part by the Undergraduates Research Fund through the Electrical and Electronic Engineering Program, in part
by the Faculty of Engineering and Built Environment, UKM, under Grant DIP-2017-003, and in part by the UKM Top-Down Research
under Grant TD-2015-008.

ABSTRACT Polyurethane-graphene (PU-graphene) nanocomposite was utilized as the sensing mate-

rial for a fiber Bragg grating (FBG) temperature sensor. The nanocomposite was characterized using
a Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron
microscopy (SEM), and electrochemical impedance spectroscopy (EIS) to study the morphology and
physical properties of the materials for FBG temperature sensing application. The physical, chemical, and
conductivity of PU-graphene improve after graphene was introduced in pristine PU. The FTIR shows that the
strong intermolecular interaction between –O–C = O (ester) and hydrogen in graphene in the PU-graphene
was indicated by the shift to lower wavenumber of ether (C–O–C) peak at ∼1220 cm−1 to ∼1218 cm−1 .
TGA shows the thermal stability of PU increases to 217 ◦ C due to the strong intermolecular interaction with
the presence of graphene flakes. EIS shows a good electrical conductivity of 1.39 × 10−9 Scm−1 in the
PU-graphene due to the electron transfer provided by the graphene. The SEM shows a rough and uneven
texture on the surface of FBG coated by PU-graphene nanocomposite which shows that the graphene flakes
are completely coated by polyurethane polymer. The PU-graphene was then dip-coated on the optical fiber-
based Bragg grating, and the sensor performance for a temperature sensor was evaluated, where a good
linearity with the sensitivity of 6 pm/◦ C was achieved.

INDEX TERMS Fiber Bragg grating, graphene, polyurethane, temperature sensor.

I. INTRODUCTION coefficient of silica with the variation of temperature is a

Fiber Bragg Grating (FBG) as an optical sensor has been major drawback of bare FBG application in temperature sens-
widely applied in various fields for measurement of numerous ing which makes the sensor less sensitive [5]. A normalized
parameters, such as temperature, pressure, strain and motion. responsivity of 6.67 x 10−6 ◦ C−1 was reported for a bare
It has been used extensively for temperature measurement FBG with 1.3 µm wavelength over the range of 5◦ C to
in various industrial control system processes [1], [2]. FBG 85 ◦ C. Previous studies reported that there are two factors
is known as an optical filtering device, reflecting optical affecting the dependence of the Bragg wavelength towards
signals at a certain wavelength within the core of an optical temperature: (i) the dependence of the glass refraction index
fiber [3], [4]. Simple fabrication, light weight, immunity towards temperature and (ii) the glass thermal expansion [6].
to electromagnetic interference and long-range monitoring Basically, an FBG is not very sensitive towards the external
system are the highlights of the FBGs to be utilized as a changes of the refractive index, hence the thermal sensitivity
promising sensor [5]. However, the low thermal expansion of the FBG sensor can be improved by the application of

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 F. Jasmi et al.: Ionic Conductive PU-Graphene Nanocomposite

different types of coating materials such as polymer and Appendix A. The small segment of FBG (2.5 cm – 3.0 cm)
metal whose thermal expansion coefficient is greater than was dip-coated with bio-based polyurethane (PU) synthe-
silica [2], [5], [7]. The sensitivity of the FBG wavelength to sized from palm kernel oil-based monoester-OH (PKO-p)
temperature can be controlled by the thermal characteristics doped with graphene for the development of temperature
of the coating materials [1]. sensor. The coating material was synthesized and character-
Li et al. [8] have reported that the temperature sensitivity ized by using attenuated total reflection Fourier transform
of FBG sensor could be enhanced by using nickel metal as infrared (ATR-FTIR) spectroscopy, temperature dependence
coating material. Wu et al. in [9] claimed that by introducing electrochemical impedance spectroscopy (EIS), thermogravi-
capillary steel tubes, metalized and organic polymer packages metric analysis (TGA) and scanning electron microscopy
can enhance the sensitivity of the FBG sensor for the low tem- (SEM) to study the morphology and physical properties of
perature measurements down to 0.0213 nm/◦ C, 0.0283 nm/◦ C the materials for FBG sensor application. The performance
and 0.1376 nm/◦ C, respectively. Recently, Park et al. [5] used of the PU-graphene nanocomposite as a coating material for
FBG with coated poly-dimethylsiloxane (PDMS) for sensi- temperature sensor was evaluated at different temperature
tivity enhancement due to the higher thermal expansion coef- using FBG sensor based on the observation of changes in
ficient possessed by PDMS in comparison to metal. Better refractive index (RI) of the transducer. The sensitivity and
sensitivity was reported for a higher cross-section areas (Ap ) stability of the non-coated FBG, FBG coated with PU and
of the PDMS jackets with 0.026 nm/◦ C (for Ap = 25 mm2 ), FBG coated with PU-graphene were studied.
0.033 nm/◦ C (for Ap = 100 mm2 ), 0.042 nm/◦ C (for Ap =
400 mm2 ). II. MATERIALS
Ionic conductive solid polymer electrolytes possess both 2,40 -Methylene diphenyl diisocyanate (MDI) was com-
mechanical properties of polymers and electrical properties mercially obtained from Cosmopolyurethane Sdn. Bhd.
of conductors which are excellent for the development of (Malaysia). Palm kernel oil-based monoester-OH (PKO-p)
electronic and optical devices. Features such as, high elec- were synthesized by polyesterification reaction in UKM lab-
trical conductivity, ease of synthesis, good thermal and envi- oratory using established method by Wong and Badri [17].
ronmental stability make them superior compared to other Graphene flakes was supplied by KGC Sdn, Bhd. (Malaysia).
conductive materials for instance carbon nanotubes and their Acetone and ethanol 99.9 % were supplied by SYSTERM
derivatives [10]. ChemAR (Poland).
Polyurethane (PU) is a type of a conductive polymer
consists of polyols and isocyanates in its polymeric chain III. SYNTHESIS AND PREPARATION OF
structure. The soft and hard segments in the PU polymeric BIO-BASED POLYURETHANE
chain is due to the presence of polyols and isocyanates respec- Polyurethane polymer was synthesized by pre-mixed palm
tively [11]. The PU soft segment act as a polymer solvent kernel oil-based monoester-OH (PKO-p) in 5 mL of acetone
to solvate the cations favoring the transportation of the ions and stirred for 1 h. Afterward, the graphene powder was dis-
hence contribute to the conductivity of the PU. Meanwhile, persed in PKO-p solution using magnetic stirrer for the first
the PU hard segment act as supporting fillers, whereby it is 1 h and the dispersion was prolonged using Vortex mixer for
interconnected throughout the soft phase segment, henceforth another 20 minutes to improve homogeneous distribution of
contribute to the mechanical strength of the PU [12] and to the graphene in PKO-p solution. The PU-graphene nanocom-
preserve the stability of the sensor [13]. posite was prepared via in-situ addition polymerization of
Superior electrical conductivity is the most imperative ele- isocyanate ends segment to hydroxyl groups of PKO-p. The
ment of graphene. Graphene is a sp2 -hybridized single layer, 2,40 -methylene diphenyl diisocyanate (MDI) was dissolved
which also well-known for its high thermal conductivity in 5 mL acetone solution for 1 h prior to PU synthesis. The
as well as excellent mechanical properties [14]. Recently, solution was later added into PKO-p–graphene mixture under
the incorporation of graphene into PU greatly improved the continuous stirring (5000 – 6000 rpm) for 1 h. The reaction
physical, chemical and conductivity of the polymer compos- was conducted at ambient temperature under nitrogen gas
ite [15], because of the covalent bond formation between the atmosphere in a glass vessel. The mixture was stirred for
hydroxyl groups at the surfaces of graphene with the iso- an hour before casted onto Teflon mould in glovebox and
cyanate groups of PU chain [14]. Pokharel et al. [16] reported allowed to evaporate at room temperature. The produced
many hydroxyl groups on the surface of graphite derivatives films were kept in the desiccator for further characterization.
offers abundant active sites for the covalent grafting of PU
onto the surface of graphite derivatives, thus PU interact more IV. CHARACTERISATION OF THE MATERIAL
effectively with the graphite derivatives for effective load A. ATTENUATED TOTAL REFLECTION-FOURIER
transfer. TRANSFORM INFRARED SPECTROSCOPY (ATR-FTIR)
In this work, a Type 1 uniform grating FBG was used. It has ANALYSIS
a wavelength, length, period and reflectivity of 1550.233 nm, ATR-FTIR analysis was recorded by computer interfaced
10 mm, 530.90 nm and 99.38 %, respectively. The detailed with Perkin Elmer 2000. The films were placed onto ATR
specifications of the FBG used in this study were given in crystal and analyzed in the frequency range of 4000 cm−1 to

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F. Jasmi et al.: Ionic Conductive PU-Graphene Nanocomposite

650 cm−1 at a scanning resolution of 2 cm−1 . The purpose

of this analysis was to observe the functional groups and
chemical interaction in the system.

B. THERMAL ANALYSIS
Thermogravimetric analysis was carried out using a
Mettler–Toledo TGA/SDTA 851 instrument under nitrogen
gas atmosphere from room temperature to 600◦ C at a heating
rate of 10 ◦ C/min. A sample of mass ∼5 mg was used to
determine the weight loss of the polymers.
FIGURE 1. Experimental setup for FBG temperature sensor.
C. IMPEDANCES ANALYSIS
The dielectric studies of the PU membranes were carried
out by alternating current (AC) electrochemical impedance
spectroscopy (EIS) Princeton Model VERSASTAT4 using
a frequency resonance analyzer (FRA) with applied fre-
quency from 1 MHz to 0.01 Hz at 100 mV amplitude. The
16 mm in diameter disc-shaped sample was sandwiched
between two stainless steel block electrodes. All the electrical
parameters were extracted from the Nyquist plot given by
EIS measurement.

D. RESISTIVITY AND ELECTRICAL CONDUCTIVITY

The resistivity was obtained by the equation, ρ = [(A.Rb )
/l] and the electrical conductivity σ = 1/ρ. Bulk resistance
(Rb ) was determined from the equivalent circuit analysis by
using the Zview analyzer software, contact area of the thin film
(A = 1.77 cm2 ), and average thickness of 0.01 cm (measured
FIGURE 2. FTIR spectra for pristine PU and PU-graphene nanocomposite.
by Mitoyo digital caliper).

E. ELECTRICAL MODULUS
setup for the FBG fabrication. Based on the figure, the light
Electrical modulus (M∗ ) is an effective tool to predict the
was released from a broadband source into the optical fiber
relaxation behavior of conducting polymeric materials. The
and the spectrum of the reflected light was analyzed. In this
essential quantities in impedances spectroscopy given by the
system, the optical circulator was used to transmit the emitted
modulus function in equation (1) and (2):
light into the transmission fiber and redirect the reflected light
Mi (ω) = εr /(εr 2 + εi2 ) (1) back to the optical spectrum analyzer. The wavelength shift
was observed as the temperature was varied.
Mr (ω) = εr /(εr 2 + εi2 ) (2)
Where εi is the dielectric loss, εr is dielectric constants and ω VI. RESULTS AND DISCUSSION
is 2π f , f is the frequency in Hz. A. ATR-FTIR
ATR-FTIR analysis in Figure 2 indicates the disappearance
V. FBG FABRICATION of isocyanate (NCO) peak of MDI around ∼2230 cm−1
FBG sensor was cleaved with a cleaver to ensure the end shows that diisocyanate is reacted completely with PKO-
tip of the FBG is perpendicular (90◦ ) with the length of the p polyols. This signifies that free diisocyanate is removed
FBG. The FBG was cleaned with ethanol to remove the dust completely during nucleophilic substitution reactions by
on the surface of the FBG before coated with PU-graphene amine functional groups in PKO-p as nucleophile [17]. The
nanocomposite. The FBG was dip-coated with PU-graphene disappearance of –OH stretching mode which belongs to
nanocomposite by using a dip coating technique from the hydroxyl groups of PKO-p at 3387 cm−1 and the presence
mould in the glovebox with the aid of the programmable of single band stretching mode of (–NH) peaks appear at
dip coater machine (PTL-MMB01, MTI Corporation, United 3300 cm−1 further prove the presence of secondary amides
States). The speed of the dip coater machine was fixed at (–NHCO–) of PU in the polymeric structure [17]. Further-
200 mm/min for all the samples analyzed. Flow chart of the more, the existences of stretching mode of carbonyl ure-
sensing layer coating process was provided in Appendix B. thane group (–C = O) (∼1709 cm−1 ) and carbamate group
The performance of the FBG sensor was carried out to (C–N and –O–C = O (ester)) (∼1600 cm−1 and
study the sensitivity of the FBG sensor. Figure 1 shows the ∼1220 cm−1 ) confirm a success formation of PU [18].

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FIGURE 3. Proposed schematic of physical crosslink between urethane

linkages.

The functional group of carbonyls (–C = O) for ter- FIGURE 4. TGA analysis for pristine PU and PU-graphene nanocomposite.
tiary amides of monoester polyols PKO-p is observed at
1738 cm−1 is independent of its physical state as it is not TABLE 1. Thermal properties of pristine PU and PU-Graphene
possible to form hydrogen bonding with another tertiary nanocomposite.
amide group [19]. Whereas, with the presence of graphene
flakes, the stretching mode of carbonyl urethane group
(–C = O) and bending mode of –NH (amide) shifted
from ∼1709 cm−1 and 1530 cm−1 to higher wavenumber,
∼1711 cm−1 and 1532 cm−1 , respectively.
After the addition of graphene, the ether (–O–C–O) peak
at ∼1220 cm−1 is shifted to ∼1218 cm−1 . The lower fre-
quencies absorption indicates that the stronger intermolec- stability of PU increased to 217 ◦ C with higher weight loss.
ular interaction (physical crosslink) between hydrogen in A relatively strong intermolecular force in semi-crystallinity
graphene and –O–C = O (ester)) led to shorter bond in PU-graphene nanocomposite requires higher temperature to
–C = O stretching mode vibration. Thus, produce more brit- disruption even above the glass transition temperature. The
tle coating on FBG fiber due to the increase of crystallinity. increase in thermal stability and glass transition tempera-
The proposed mechanism in Figure 3 indicates how inter- ture may also due to the thermally conductive properties
molecular interaction; hydrogen bond is greatly affected by of graphene as its unique two-dimensional structure, further
the presence of graphene flakes. Notably, with the presence offers a lower thermal resistance between the surfaces.
of graphene, the physical crosslink between urethane is iden- Fundamentally, the percolation theory can be applied to
tified to weaken physical-chemical interaction observed in analyses the thermal conductivity in nanocomposites; in
PU as indicated by unaffected single band stretching mode amorphous polymer, phonons (lattice vibrations) are known
of (−NH) at 3300 cm−1 . as the major mode of thermal conduction. The phonon scat-
tering at the filler-matrix and interface can be reduced by the
B. THERMAL ANALYSIS formation of physical/chemical bond between the filler and
Thermal analyses were carried out to determine the thermal matrix, thus enhance the thermal conductivity of nanocom-
stability and phase transition of the materials. The degree of posites [23]. Whereas, the second degradation (Td2 ) stage
crystallinity is found to be increased with the presence of begins at Td2 = 251 ◦ C with Tmax = 432 ◦ C where later
graphene and Tm is insignificantly increased from 102 ◦ C reduced after the addition of graphene. The Td2 degradation is
to 103 ◦ C. Whereas, two glass transition temperature was contributed by the thermal decomposition of soft segments of
identified; Tg PU = 40 ◦ C, 77 ◦ C and Tg PU-graphene 47 ◦ C, PU (ester linkages), which was seldom affected by the chem-
65 ◦ C. The thermal decomposition stage (Td ) of pristine ical composition and the three-dimensional arrangement of
PU and PU-graphene nanocomposite occur at two stages as polyurethane structure [20], [24]. The degradation region
can be seen in Figure 4 and summarized in Table 1. The corresponds to the liberation of free isocyanate at the range
first decomposition (Td1 ) stage of pristine PU was started at of 240-370 ◦ C is not observed probably due to overlapping
120 ◦ C and reached its maximum (Tmax ) at 204 ◦ C due to peak [11], [25]. Although Td1 , and Td2 shifted significantly
degradation of the hard-segmented block co-polymer of the but the residue after 600 ◦ C decomposition is equivalent to
urethane linkages that resulted to the three decomposition both samples [24].
mechanisms for urethane bonds: (i) dissociation to isocyanate
and alcohol, (ii) formation of primary amine, carbon dioxide C. RESISTIVITY AND ELECTRICAL CONDUCTIVITY
and (iii) formation of secondary amine and carbon diox- Electrochemical impedance spectroscopy (EIS) was carried
ide [20]–[22]. With the addition of graphene flakes, thermal out to study the influence of the governing physical and

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F. Jasmi et al.: Ionic Conductive PU-Graphene Nanocomposite

TABLE 2. Conductivity of pristine PU and PU-Graphene nanocomposite.

FIGURE 6. Electrical modulus behavior of PU-graphene nanocomposites

at applied frequency between 30 to 100 ◦ C.

dielectric loss with temperature can be attributed to the

increase in charge carrier density at the space charge accu-
mulation region, which causes equivalent capacitance to be
enhanced [29]. The low frequency dispersion region cor-
FIGURE 5. Electrochemical impedance spectrum for pristine PU and
PU-graphene at ambient temperature. responds to the contribution of charge accumulation at the
electrode–electrolyte interface.
At high frequencies, the periodic reversal of the electric
chemical phenomena that may be isolated and distinguished fields occurs so fast that there is no time for ion to build up at
at a given applied frequency. Table 2 shows electrical prop- the interface. Hence, the polarization due to the charge accu-
erties of pristine PU and PU-graphene nanocomposites, mulation decreases, which caused the decrease in the value
whereas Figure 5 indicates the impedance spectra for both of εr [30]. Figure 6 shows electrical modulus behavior of
samples. According to Nyquist plot, the pristine PU sam- PU-graphene nanocomposites at applied frequency between
ple has higher resistance than PU-graphene sample [26], 30 to 100 ◦ C. The complete analysis of electrical properties
which indicates the insulating properties of pristine PU. for pristine PU and PU-graphene nanocomposite is provided
With addition of graphene, the conductivity was increased in supplementary material (Figure S3-S6).
two magnitudes, from 9.43 × 10−11 Scm−1 to 1.39 ×
10−9 Scm−1 at ambient temperature. The conductivity was E. CONDUCTIVITY DEPENDENCE ON TEMPERATURE
clearly affected by the electron transfer provide highly elec- Figure 7 shows the conductivity, σ dependence on temper-
trically conductive, graphene, where it forms a network that ature, T curve for the PU-graphene nanocomposite sample.
led to an increase in the electrical conductivity of compos- According to Figure 7, the conductivity of PU-graphene
ites [27]. This proves that the addition of graphene as a filler increased when the temperature is raised [30]. The relation-
in PU managed to increase the conductivity of composite ship between conductivity and temperature for PU-graphene
coatings on optical FBG-based compared to fiber without nanocomposite was found to be linear with the regression
graphene-coating. line of 0.9916 which obeyed Vogel-Tamman Fulcher (VTF)
equation, which given by the equation (3) below:
D. ELECTRICAL MODULUS 1 −B
σ = AT −( 2 ) exp( k (T −To )) (3)
Dielectric relaxation studies of polymeric materials are
related to the relaxation of dipoles in polymeric host. Dielec- where, A = m1 = pre-exponential factor (σ0 ), B = m2 =
tric constant is a measure of the amount of charge stored. The pseudo activation energy (Ea ), m3 = To (temperature).
observed variation in εr with frequency could be attributed to Vogel-Tamman Fulcher rule is applied as a part of the
the formation of a space charge region at the electrode and analysis on the temperature reliance of the consistency of the
electrolyte interface at the low frequency region. fluid or unwinding time, dispersion coefficient and electri-
This behavior is known as the non-Debye type of behav- cal conductivity in a wide assortment of liquids including
ior, where diffusion of ions occurs in the space charge metallic glass framing materials. Its condition is frequently
regions [28]. The increase in the dielectric constant and used to portray the behavior observed particularly in the

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 F. Jasmi et al.: Ionic Conductive PU-Graphene Nanocomposite

FIGURE 7. Conductivity, σ dependence on temperature, T plots for the

PU-graphene nanocomposite.

fragile system. Pseudo-activation energy (Ea ) is found at

Ea = 42.2 eV, which regarded as the minimum amount of
energy needed before the electron can move from one posi-
tion to another. Whereas, the pre-exponential factor (σ0 ) =
1.2 × 10−3 Scm−1 is related to the number of charges at
the maximum point. The electrical conductivity symbolizes
electron mobility of the overall polymer where it might be
controlled by the free volume which leads to an expansion
in electron mobility and segmental that help to transport FIGURE 8. SEM images of FBG coated with (a) pristine PU and
particles or electrons. (b) PU-graphene nanocomposite.

F. MORPHOLOGICAL STUDY
PU-graphene was integrated with optical fiber-based Grat-
ing and the scanning electron microscopy (SEM) was car-
ried out to study the surface morphology of the samples.
Figure 8 shows the SEM micrograph of FBG coated with
(a) pristine PU and (b) PU-graphene nanocomposite.
A smooth surface was observed for FBG coated with PU
without graphene as can be seen in Figure 8(a). However,
an inhomogeneous, rough and uneven texture was observed
on the surface of FBG coated with PU-graphene nanocom-
posite in Figure 8(b), which clearly shows visible flakes of
graphene on FBG surface coating. The dispersion of graphene
flakes can be improved by using ultrasonic dispenser, sputter
coating, etching or immersion technique to obtain more even
texture on the surface of the FBG. Figure 9 shows the SEM
micrograph for FBG coated with PU-graphene nanocompos- FIGURE 9. Surface morphology of FBG coated with PU-graphene.

ite at 5000X magnification. It shows that graphene flakes are

completely coated by polyurethane polymer, thus improves
the thermal conduction of the FBG. The bright and dark The grating period and index of refraction of the optical
tones on the surface topography represent the crystalline and fiber is highly dependent on the temperature variation, hence
amorphous phase structures respectively. produce different value of Bragg wavelength [1] due to the
thermal expansion of the fiber and strain induced by thermal
G. FIBRE BRAGG GRATING FOR TEMPERATURE SENSOR expansion of the pristine PU and PU-graphene nanocompos-
In this work, various range of temperatures were carried out ite coatings [7].
to observe the effect towards FBG wavelength using FBG Figure 10(a) and (b) shows the Bragg grating power
coated with pristine PU and PU-graphene nanocomposite. based optical fiber using pristine PU and PU-graphene

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F. Jasmi et al.: Ionic Conductive PU-Graphene Nanocomposite

FIGURE 11. Calibration plot for bare FBG, FBG coated with pristine PU
and FBG coated with PU-graphene nanocomposite.

temperature range of 25 ◦ C to 60 ◦ C, hence shows better

sensitivity and good stability for this material compared to
non-coated FBG (R2 = 0.9094) and FBG coated with pristine
PU (R2 = 0.8797).
The surface of the FBG is made of silica, which has low
thermal expansion coefficient and leads to low sensitivity to
temperature [5]. By coating the bare FBG with PU material
which has higher thermal expansion coefficient than silica
improves the sensor sensitivity. Furthermore, by the addition
of the graphene flakes into pristine PU, the stability of this
material increases due to the strong intermolecular force in
FIGURE 10. The wavelength shift of FBG coated with (a) pristine PU and
semi-crystallinity PU-graphene nanocomposite as confirmed
(b) PU-graphene nanocomposite at various temperature by the TGA analysis in Figure 4.
The stability of the material affects the sensitivity of the
temperature sensor. Hence, the sensitivity of the material
nanocomposite with the power value of −50 dB and −45 dB increases at higher temperature in comparison to the pris-
respectively. The power value was increased from −50 dB to tine PU. Consequently, the FBG coated with PU-graphene
−45 dB when pristine PU was substituted with PU-graphene nanocomposite has a good potential for the temperature sen-
nanocomposite as the coating material. The graph trend of sor application with the sensitivity of 6 pm/◦ C.
the wavelength changes for FBG coated with pristine PU as
seen in Figure 10(a) is not uniform in contrast to the wave- VII. CONCLUSION
length change in FBG coated with PU-graphene nanocom- The material characterization results confirm that the
posite. The gradual raised in temperature causes the constant polyurethane-graphene was successfully synthesized. The
change in wavelength for the FBG coated with PU-graphene addition of graphene in PU greatly improves the properties of
nanocomposite. Furthermore, the adjacent wavelength peaks PU-graphene nanocomposite. A better thermal stability was
were more prominent as the graphene were introduced in observed for PU-graphene with 217 ◦ C. The electron con-
the later FBG coated optical fiber as seen in Figure 10(b). ductivity of the coating material increases from 9.43 × 10−11
Interestingly, these adjacent peaks can be used as alternative Scm−1 to 1.39 × 10−9 Scm−1 . The increase power of 5 dB
for calculating the wavelength shift of the peak for FBG was observed when PU-graphene nanocomposite was used
coated with PU-graphene, which is not observed in the FBG as the coating material in FBG sensor. A good linearity was
coated with pristine PU graph. obtained for FBG coated with PU-graphene nanocomposite
with the sensitivity of 6 pm/◦ C, hence suitable to be applied
H. SENSOR SENSITIVITY as a temperature sensor for various applications.
Figure 11 shows the difference in wavelength dependence
on temperature for non-coated FBG, FBG coated with pris- ACKNOWLEDGMENT
tine PU and FBG coated with PU-graphene nanocompos- The authors would like to extend their gratitude towards
ite. The FBG sensitivity was calculated to be 6 pm/◦ C for UKM for allowing this research to be carried out and all
FBG coated with PU-graphene nanocomposite. According supports that have been given throughout the process of this
to Figure 11, a good linearity was depicted for FBG coated work. They would like to extend our appreciation towards
with PU-graphene nanocomposite (R2 = 0.9832) within the KGC Sdn. Bhd. for sponsoring graphene flakes, Photonics

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 F. Jasmi et al.: Ionic Conductive PU-Graphene Nanocomposite

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Storage Materials Research Group of Solar Energy Research and Their Properties. London, U.K.: InTech, 2012, ch. 2, pp. 17–36.
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polyurethane–imide copolymers with multiple hard segments,’’ J. Appl.
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Optik, vol. 127, no. 22, pp. 10740–10745, 2016. FAREEZA JASMI received the B.Sc. degree
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and the temperature sensing character after metallization,’’ Opt. Fibre from Universiti Kebangsaan Malaysia, Bangi,
Technol., vol. 15, no. 4, pp. 391–397, 2009. Selangor, Malaysia, in 2017. She is currently
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Energy, vol. 39, no. 6, pp. 3005–3017, 2014. Malaysia Sarawak in 2009, and the Master of
[12] L. Liu, X. Wu, and T. Li, ‘‘Novel polymer electrolytes based on cationic Environment and Ph.D. degrees in smart sens-
polyurethane with different alkyl chain length,’’ J. Power Sources, vol. 249,
ing materials from Universiti Putra Malaysia
pp. 397–404, Mar. 2014.
in 2012 and 2017, respectively. She is currently
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a Post-Doctoral Researcher with the Centre of
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Sep. 2013. monitoring. Her current research interests include optical materials, and
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[16] P. Pokharel et al., ‘‘Effects of functional groups on the graphene sheet for received the bachelor’s degree in electrical and
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ites,’’ Compos. B, Eng., vol. 78, pp. 192–201, Sep. 2015. Nasional in 2002, the M.Sc. degree in commu-
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Universiti Putra Malaysia in 2004, and the Ph.D.
[18] K. B. H. Badri, W. C. Sien, M. S. B. R. Shahrom, L. C. Hao, degree in electrical engineering from The Uni-
N. Y. Baderuliksan, and N. R. A. Norzali, ‘‘FTIR spectroscopy analysis
versity of Queensland, Australia, in 2010. He is
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currently an Associate Professor with the Cen-
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tre of Advanced Electronic and Communication
[19] P. S. Kalsi, Spectroscopy of Organic Compounds. New Delhi, India:
New Age Int. Pub, 2007. Engineering, Faculty of Engineering and Built Environment, Universiti
[20] M. A. Corcuera et al., ‘‘Effect of diisocyanate structure on the properties
Kebangsaan Malaysia. He is actively involved in the Optical Society of
and microstructure of polyurethanes based on polyols derived from renew- America and Fiber Optic Association Inc., USA. He is devoting his research
able resources,’’ J. Appl. Polym. Sci., vol. 122, no. 6, pp. 3677–3685, 2011. work on optical sensors in environmental and biomedical application, spe-
[21] S. Chuayjuljit, T. Sangpakdee, and O. Saravari, ‘‘Processing and properties cialized in plasmonic waveguide sensor, polymeric electro-optic modulator
of palm oil-based rigid polyurethane foam,’’ J. Met., Mater. Minerals, waveguide, interferometer, evanescent field sensors, and devices based on
vol. 17, no. 1, pp. 17–23, 2007. nanoparticles and nanostructures. He has been a member of OSA since 2014.

47362 VOLUME 6, 2018

F. Jasmi et al.: Ionic Conductive PU-Graphene Nanocomposite

MOHD SAIFUL DZULKEFLY ZAN (M’15) MOHD SUKOR SU’AIT received the B.Sc.,
received the bachelor’s degree in electronics, infor- M.Sc., and Ph.D. degrees in chemistry from Uni-
mation, and communication engineering from versiti Kebangsaan Malaysia (UKM), Malaysia,
Waseda University, Japan, in 2006, and the in 2007, 2010, and 2014, respectively. He is cur-
master’s and Ph.D. degrees from the Shibaura rently a Research Fellow with the Solar Energy
Institute of Technology, Japan, in 2011 and 2014, Research Institute and an Associate Researcher
respectively. During his Ph.D. study, he proposed with the Polymer Research Center, UKM. He had
the optical pulse coding technique to improve the published about 15 papers in international refereed
sensing performance of Brillouin optical time- journal with an h-index, 5. His research interest in
domain analysis (BOTDA) fiber-optic sensor. He electrochemistry covers the synthesis and charac-
is currently a Senior Lecturer with Universiti Kebangsaan Malaysia. His terization of electrochemical materials for energy storage and conversion
research interests include Brillouin scattering-based fiber-optic sensors, such devices (lithium batteries and solar cell). In 2009, he has been selected as
as BOTDA, BOTDR, optical pulse coding technique for fiber sensors, and a Young Scientist to represent The Association of Southeast Asian Nations
Brillouin scattering-based fiber laser. He is also conducting research on fiber (ASEAN), in the 59th Nobel Laureates Meeting, dedicated to chemistry at
Bragg grating sensor. Lindau, Germany, and honored as an ASEAN Scientist for Tomorrow by
ASEAN at Jakarta, Indonesia, in 2009. He was a recipient of the Erasmus
Mundus Mobility Program, University of Trento, Italy, in 2011, the Attach-
ment Program at the Georgia Institute of Technology, USA, in 2012, and
Cadi Ayyad University, Morocco, in 2014.
KHAIRIAH HAJI BADRI received the bache-
lor’s degree in chemistry and the B.E. degree in
chemical and petroleum refining engineering from
the Colorado School of Mines, USA, in 1993,
and the Ph.D. degree in material sciences with a
specialization in polymer synthesis and technol-
ogy. She is currently a Professor with the Fac-
ulty of Science and Technology, School of Chem-
ical Sciences and Food Technology, Universiti
Kebangsaan Malaysia. She is also the Head of the
Polymer Research Center, pioneering in thermosetting polymers from natural
resources, such as palm oil, coconut oil, soybean oil, and agricultural biomass
and converts them to polyurethanes. She is also intensively running a pre-
commercialization project on the utilization of palm kernel oil and converted
to polyol.

VOLUME 6, 2018 47363

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