JOM, Vol. 71, No.

2, 2019
https://doi.org/10.1007/s11837-018-3239-8
Ó 2018 The Minerals, Metals & Materials Society

TECHNICAL ARTICLE

Influence of Graphene Oxide on Mechanical and Hydrophilic

Properties of Epoxy/Banana Fiber Composites

PREETAM S. BHARADIYA,1 MUKESH K. SINGH,2

and SATYENDRA MISHRA1,3

1.—University Institute of Chemical Technology, Kavayitri Bahinabai Chaudhari North Maha-

rashtra University, Jalgaon, Maharashtra 425001, India. 2.—Department of Textile Technology,
Uttar Pradesh Textile Technology Institute, Kanpur, Uttar Pradesh 208001, India. 3.—e-mail:
[email protected]

Epoxy/banana fiber (EBF) composites with fiber length of 5–7 mm and fiber
content of 5.0 wt.% were prepared by hand layup technique. Graphene oxide
(GO) was dispersed at different concentrations (1.0 wt.%, 2.5 wt.%, and
5.0 wt.%) in the EBF matrix using cetyltrimethylammonium bromide (CTAB),
and its effect on the mechanical and hydrophilic properties of the EBF com-
posites was assessed. The highest tensile strength of 11 MPa, flexural
strength of 55 MPa, impact strength of 92 J/m and contact angle of 57° were
recorded for the 5.0 wt.% GO-reinforced EBF composite, compared with
5 MPa, 27 MPa, 38 J/m, and 64° for the EBF composite and 4 MPa, 23 MPa,
31 J/m, and 65° for neat epoxy, respectively. It was observed that GO was
dispersed uniformly in the EBF matrix by the CTAB treatment, improving the
mechanical and hydrophilic properties of the EBF composites.

chemical modification. Natural fiber from banana

INTRODUCTION
plant is a waste material that has found applica-
Graphene oxide (GO) is an exciting material that tions in various products such as prostheses,15
has found applications in various fields such as construction materials,16 food packaging,17 tex-
photocatalysis, gas sensing, drug delivery,1 compos- tiles,18 etc. Also, due to its higher strength, banana
ites,2,3 energy storage,4,5 etc. due to its extraordinary fiber is more suitable for increasing the mechanical
mechanical, thermal, and electrical properties and properties of epoxy resin. However, the presence of
also because the presence of epoxide, carbonyl, and primary cellulose, hemicellulose, and lignin in its
carboxyl groups as defects on the surface enhances structure11 results in poor adhesion with epoxy
its reactivity with other functional materials.1–5 matrix,17 necessitating chemical16 or plasma treat-
Epoxy resin is in demand for use in various ment19 before use in high-performance applications.
applications such as automobile components, aero- To enhance the toughness of epoxy resin, modifica-
space parts, electronic encapsulation, coatings, etc. tion using GO as filler and banana fiber as rein-
because of its high strength and ease of processabil- forcing agent is necessary. Such modification will
ity.6 However, the inherent brittle nature of epoxy enhance the overall mechanical properties of epoxy
resin results in poor toughness, restricting its use in resin to a greater extent due to the good compati-
high-performance applications.2,3 Thus, various mod- bility of hydrophilic groups of banana fiber with
ifications have been applied to improve the tough- oxide groups of GO.19 However, the poor dispersibil-
ness, stiffness, and strength of epoxy resin, including ity of GO is a major drawback, because of agglom-
mixing with natural or synthetic fibers7–9 and addi- eration due to van der Waals forces20 and poor
tion of carbon nanomaterials such as graphene oxide, interaction of hydrophilic groups of banana fiber
graphene, carbon nanotubes,2,10 etc. as filler. with epoxy resin.21
Natural fibers are lower in density, cost-effective, To solve this problem, in the work presented
biodegradable, and recyclable,7,8,11 and can enhance herein, GO was premixed with cetyltrimethylam-
electrical,12 mechanical,12 and water absorption monium bromide (CTAB) and simultaneously dis-
properties13,14 when incorporated in polymers after persed in epoxy/banana fiber (EBF) composites to

838 (Published online November 12, 2018)

Influence of Graphene Oxide on Mechanical and Hydrophilic Properties of Epoxy/Banana 839
Fiber Composites

evaluate the influence of GO (1.0 wt.%, 2.5 wt.%, coupled with a microscope in reflectance mode with
and 5.0 wt.%) on the mechanical and hydrophilic excitation by a laser source at 633 nm and spectral
properties of EBF composites. resolution of 0.3 cm 1.
The functional groups were confirmed by Fourier-
EXPERIMENTAL PROCEDURES transform infrared spectrophotometer (FTIR, model
8400; Shimadzu, Japan) with resolution of 4 cm 1,
Materials
over the wavenumber range from 400 cm 1 to
Graphite powder, methanol, and hydrogen perox- 4000 cm 1 using KBr.
ide (30%) were purchased from S. D. Fine Chemi- The crystallinity and structural properties of the
cals, Mumbai, India. Hydrochloric acid, sulfuric GO were determined by x-ray diffractometer (XRD,
acid, orthophosphoric acid, CTAB, ethanol, potas- D8 Advance; Bruker Limited, Germany) using
sium permanganate (99.9%), polyvinyl alcohol monochromatic Cu Ka1 radiation (k = 1.5406 Å) at
(PVA), and petroleum ether were purchased from 40 kV and 40 mA. The diffraction patterns were
Merck Chemicals, Mumbai, India. Epoxy resin optimized with step size of 0.020° over the 2h
LY556 and hardener HY951 were purchased from angular range of 5°–80° at scan speed of 1°/s.
Variety Plywood, Mumbai, India. All chemicals The mechanical properties of the GO/EBF com-
were used without further purification. All experi- posites were evaluated using a universal testing
ments were carried out using double-distilled water. machine (model UT2302, HI-TECH Instrument and
Services, Mumbai) at cross-head speed of 50 mm/
Extraction of Banana Fiber min. Tensile and three-point flexural tests were
carried out according to ASTM D 3039 and ASTM
Banana fiber was obtained using a retting process
D790, respectively. Mean values from five samples
as described elsewhere.12–14
are reported.
The impact strength of the GO/EBF composites
Synthesis of GO and Preparation of
was tested on an Izod impact tester 293 (Interna-
GO-Reinforced Epoxy/Banana Fiber (GO/EBF)
tional Equipments, Mumbai) by clamping a speci-
Composites
men vertically as a cantilever beam. The test was
GO was synthesized using an improved Hum- conducted according to ASTM D 256. The tests were
mers’ method as mentioned elsewhere.22 GO/EBF repeated five times, and average values are
composites were prepared using a hand layup reported.
technique. In the first step, GO was dispersed in Surface hardness tests of the GO/EBF composites
methanol using CTAB by bath sonication for 3 h were carried out using a Shore D durometer accord-
then simultaneously mixed with epoxy resin. The ing to ASTM D2240. The tests were repeated five
methanol present in the GO–epoxy mixture was times, and mean values are reported.
removed by heating in an oven at temperature of Contact angle measurements were carried out on
50°C for 24 h. Later, this mixture was stirred to the GO/EBF composites by sessile drop method
become homogeneous. PVA was applied on the mold using double-distilled water as probe liquid on a
as a mold-release agent. Banana fibers (size 5 mm contact angle goniometer (model-200 P/N 200-FU,
to 7 mm, 5.0 wt.% of epoxy resin) were mixed with ramé hart, USA). All samples were analyzed at
resin by glass rod for 1 h, then hardener was added room temperature in solid form.
to the mixture at ratio of 1:10 (wt.:wt.) followed by
pouring the mixture into the mold (270 mm 9 50 RESULTS AND DISCUSSION
mm 9 5 mm). The mold was covered with its core,
Morphological, Structural, and Functional
and kept for a week for postcuring at normal
Properties of GO and GO/EBF Composites
temperature (approx. 31°C) and one atmospheric
pressure. The cured composite was removed and cut Figure 1a and b shows FE-SEM and TEM images
according to the desired specimen size and shape. of the GO, revealing a wrinkled, sheet-like mor-
phology with thickness of 50 nm and micrometer
lateral size,4,22 confirming formation of GO sheet by
Characterization of GO and GO/EBF
oxidation of graphite.
Composites
The XRD peak observed at 7.14° (002) (Fig. 1c)
The morphology of the GO was investigated by confirms exfoliation of GO due to attachment of
transmission electron microscopy (TEM, Philips oxygenated functional groups.4,22,23
CM-200, Eindhoven, The Netherlands) with fila- The Raman spectrum of GO (Fig. 1d) showed the
ment current of 75 lA and accelerating voltage of G band of sp2-hybridized carbon and D band of
200 kV and by field-emission scanning electron defects at 1600 cm 1 and 1356 cm 1, respectively.
microscopy (FE-SEM, model S-4800 type II; Hitachi The higher intensity of the D band as compared
High Technology Corporation Limited, Japan) at with the G band confirms the oxidation of
15.0 keV. graphite.4,23
Raman spectra of the GO were recorded on a The functional groups and curing degree were
Raman spectrometer (Horiba JY LabRAM HR 800) analyzed using FTIR spectroscopy (Fig. 2a). The
840 Bharadiya, Singh, and Mishra

Fig. 1. (a) FE-SEM, (b) TEM, (c) XRD, and (d) Raman spectra of GO.

Fig. 2. (a) FTIR spectra of (i) GO, (ii) banana fiber, (iii) uncured epoxy, (iv) EBF, and (v) 5.0 wt.% GO/EBF composite; (b) tensile strength,
percentage elongation at break, and Young’s modulus of GO-reinforced EBF composites.

FTIR spectrum of GO showed peaks at 3369– stretching, respectively, confirming the oxidized
3220 cm 1, 1720 cm 1, 1624 cm 1, and 1043 cm 1, form of graphite.4,22 The peaks observed at
corresponding to hydroxyl stretching, C-O stretch- 2922 cm 1, 1643 cm 1, 1330 cm 1, 1244 cm 1, and
ing, unoxidized sp2 C-C bond, and skeletal C-O 1035 cm 1 correspond to OH stretching vibration,
Influence of Graphene Oxide on Mechanical and Hydrophilic Properties of Epoxy/Banana 841
Fiber Composites

cellulose group C=O stretching, lignin groups, and the EBF composites (Fig. 2b). Neat epoxy showed
ether linkage groups of banana fiber.11 The spec- Young’s modulus of 443 MPa, as compared with
trum for uncured epoxy resin (Fig. 2a) showed 502 MPa for the EBF composite, 717 MPa for the
absorption peaks at 3055 cm 1,1184 cm 1, 1.0 wt.% GO/EBF composite, and 901 MPa for the
1132 cm , 914 cm , and 829 cm 1 corresponding
1 1
2.5 wt.% GO/EBF composite. The highest Young’s
to symmetric stretching of oxirane groups, C-O modulus of 1076 MPa was recorded for the 5.0 wt.%
aromatic ring stretching, C-O-C stretching of ether GO/EBF composite. Thus, GO also improved the
groups, C-O oxirane group, and aromatic absor- Young’s modulus of the EBF composites in a similar
bance, respectively.24 The oxirane peak at way to the tensile strength due to good dispersion of
3055 cm 1 was absent while new peaks were GO in the epoxy matrix and improved compatibility
observed at 3040 cm 1, 1244 cm 1, and 1031 cm 1 with the banana fiber.
for the EBF composite and 5.0 wt.% GO/EBF com-
posites, corresponding to hydroxyl group,25 lignin Flexural Strength and Flexural Modulus
groups, and ether linkage groups of banana fiber,11
The flexural strength and flexural modulus of all
respectively. These results confirm that the C=O
the GO/EBF composites increased with increase in
bond of cellulose (of banana fiber) interacted well
the GO content (Fig. 3a). Neat epoxy showed flex-
with epoxy and GO functional groups, while a
ural strength of 23 MPa and flexural modulus of
certain amount of unreacted lignin groups remained
720 MPa, while flexural strength of 27 MPa,
present in the EBF matrix. The C-O oxirane peak at
33 MPa, and 39 MPa and flexural modulus of
914 cm 1 was absent for all nanocomposites cured
974 MPa, 1105 MPa, and 1418 MPa were obtained
at room temperature for 1 week, confirming that all
for the EBF, 1.0 wt.% GO/EBF, and 2.5 wt.% GO/
epoxy groups were utilized for curing. Also, the shift
EBF composite, respectively; the maximum flexural
of the C-O skeletal peak of GO from 1043 cm 1
strength of 55 MPa and flexural modulus of
towards the ether linkage peak at 1031 cm 1 in the
1729 MPa were recorded for the composite rein-
5.0 wt.% GO/EBF composite confirms uniform dis-
forced with 5.0 wt.% GO. These results prove that
persion of GO with banana fiber and epoxy matrix
the synergistic effect of GO resulted in an increase
when using CTAB, resulting in the improved
in flexural strength and flexural modulus of the
mechanical properties described below.
EBF composites in a similar way to that observed
for the tensile strength.
Mechanical Properties of GO/EBF Composites
Tensile Strength, Elongation at Break, and Young’s Impact Strength and Shore D Hardness
Modulus The impact strength of the GO/EBF composites
It is observed from Fig. 2b that the tensile was found to increase with increasing GO content,
strength increased with increase in the GO concen- like the tensile and flexural properties (Fig. 3b).
tration from 1.0 wt.% to 5.0 wt.% in the GO/EBF Neat epoxy showed impact strength of 31 J/m, as
composites. Neat epoxy showed tensile strength of compared with 38 J/m, 46 J/m, and 63 J/m for the
4 MPa, whereas the maximum tensile strength of EBF, 1.0 wt.% GO/EBF, and 2.5 wt.% GO/EBF
11 MPa was recorded for the 5.0 wt.% GO/EBF composite, respectively. The highest impact
composite, as compared with 5 MPa for the EBF strength of 92 J/m was recorded for the composite
composite, 6 MPa for the 1.0 wt.% GO/EBF com- reinforced with 5.0 wt.% GO. These results prove
posite, and 8 MPa for the 2.5 wt.% GO/EBF com- that the increase in the GO content was responsible
posite. These results prove that the tensile strength for the increment in the impact strength of the EBF
of the EBF composites was enhanced with increas- composites.
ing GO concentration due to proper interlocking of Unlike the increase in the impact strength, the
GO with banana fiber and epoxy resin. opposite behavior was observed for the Shore D
Figure 2b also shows the percentage elongation at hardness of the GO/EBF composites (Fig. 3b). Neat
break of the GO/EBF composites. Unlike the tensile epoxy showed Shore D hardness of 75, as compared
strength, the opposite behavior was observed for the with the values of 67, 61, and 54 for the EBF,
percentage elongation at break. Neat epoxy showed 1.0 wt.% GO/EBF, and 2.5 wt.% GO/EBF composite,
5.75% elongation at break, as compared with 5.01%, respectively. The lowest Shore D hardness value of
4.73%, and 3.04% for the EBF composite and 48 was recorded for the 5.0 wt.% GO/EBF compos-
1.0 wt.% and 2.5 wt.% GO/EBF composite, respec- ite. These results prove that GO decreased the
tively. The lowest elongation at break of 1.84% was brittleness of the EBF composite, which is respon-
recorded for the 5.0 wt.% GO/EBF composite. These sible for the decrease in the Shore D hardness of the
results confirm that GO decreased the percentage GO/EBF composites.
elongation at break of the EBF composites, in the
opposite sense to the tensile strength, due to the
Hydrophilic Properties of GO/EBF Composites
synergistic effect of GO on the EBF composites.
Like the tensile strength, the Young’s modulus A material exhibits hydrophilicity due to the
was found to increase with increasing GO content in presence of groups with affinity for water.
842 Bharadiya, Singh, and Mishra

Fig. 3. (a) Flexural strength and flexural modulus; (b) impact strength and Shore D hardness; (c–g) contact angle measurements of GO-
reinforced EBF composites.

Figure 3c, d, e, f, and g shows the contact angle for the 5.0 wt.% GO/EBF composite as compared
results for the GO/EBF composites, revealing a with neat epoxy. GO also enhanced the hydrophilic
decreasing trend from 65° to 64°, 62°, 59°, and 57° property of the EBF composites due to an increase
for neat epoxy, and the EBF, 1.0 wt.% GO/EBF, in the hydrophilic groups with increase in the GO
2.5 wt.% GO/EBF, and 5 wt.% GO/EBF composite, concentration. Thus, the 5.0 wt.% GO/EBF compos-
respectively. This decrease in contact angle is ite showed enhanced mechanical as well as hydro-
observed due to an increase in hydrophilic groups philic properties compared with neat epoxy and
with increasing GO concentration in the EBF EBF composite due to the proper interlocking and
composites. synergistic effect of GO with banana fiber and epoxy
resin, obtained due to the good dispersion of GO in
CONCLUSION the epoxy matrix when using CTAB.
GO was synthesized by an improved Hummers’
method and used as a reinforcing agent in epoxy/ ACKNOWLEDGEMENTS
banana fiber composites. Addition of GO enhanced P.S.B. is grateful to TEQIP-III MHRD, New Delhi
the overall mechanical properties of the EBF com- for providing financial assistance to carry out this
posites due to its higher surface area and good research work. S.M. is grateful to UGC New Delhi
compatibility with banana fibers and epoxy resin for awarding a BSR Faculty Fellowship.
with CTAB treatment. For the 5.0 wt.% GO/EBF
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