Article

Progress in Rubber Plastics and

Recycling Technology
Influence of layering pattern 1–16
ª The Author(s) 2019
of modified kenaf fiber on Article reuse guidelines:
sagepub.com/journals-permissions
DOI: 10.1177/1477760619895010
thermomechanical properties journals.sagepub.com/home/prp

of epoxy composites

AR Mohammed1, MS Nurul Atiqah2,

Deepu A Gopakumar2, MR Fazita2,
Samsul Rizal3, D Hermawan4, Sabu Thomas5
and HPS Abdul Khalil2

Abstract
Natural fiber-reinforced composites gained considerable interest in the scientific community due
to their eco-friendly nature, cost-effective, and excellent mechanical properties. Here, we
reported a chemical modification of kenaf fiber using propionic anhydride to enhance the com-
patibility with the epoxy matrix. The incorporation of the modified woven and nonwoven kenaf
fibers into the epoxy matrix resulted in the improvement of the thermal and mechanical properties
of the composite. The thermal stability of the epoxy composites was enhanced from 403 C to
677 C by incorporating modified woven kenaf fibers into the epoxy matrix. The modified and
unmodified woven kenaf fiber-reinforced epoxy composites had a tensile strength of 64.11 and
58.82 MPa, respectively. The modified woven composites had highest flexural strength, which was
89.4 MPa, whereas, for unmodified composites, it was 86.8 MPa. The modified woven fiber-
reinforced epoxy composites showed the highest value of flexural modulus, which was 6.0 GPa
compared to unmodified woven composites (5.51 GPa). The impact strength of the epoxy com-
posites was enhanced to 9.43 kJ m2 by the incarnation of modified woven kenaf fibers into epoxy

1
Linton University College, Bandar Universiti Teknologi Legenda (BUTL), Mantin, Negeri Sembilan, Malaysia
2
School of Industrial Technology, Universiti Sains Malaysia, Penang, Malaysia
3
Department of Mechanical Engineering, Universitas Syiah Kuala, Banda Aceh, Indonesia
4
Department of Forestry, Kampus IPB Darmaga, Bogor Agricultural University, Bogor, West Java, Indonesia
5
International and Inter University Centre for Nanoscience and Nanotechnology, Mahatma Gandhi University, Kottayam,
Kerala, India

Corresponding authors:
AR Mohammed, Linton University College, Bandar Universiti Teknologi Legenda (BUTL), Mantin 71700, Malaysia.
Email: manhaji2@yahoo.com
HPS Abdul Khalil, School of Industrial Technology, Universiti Sains Malaysia, 11800 Penang, Malaysia.
Email: akhalilhps@gmail.com
2 Progress in Rubber Plastics and Recycling Technology XX(X)

matrix. This study will be an effective platform to design the chemical modification strategy on
natural fibers for enhancing the compatibility toward the hydrophobic polymer matrices.

Keywords
Kenaf fiber, chemical modification, fiber–matrix interface, mechanical properties, epoxy
composites

Received 10 April 2019; accepted 30 September 2019

Introduction
Nowadays, the scientists were focused on the development of high-performance engineering
materials and composites made from natural resources, which are expanding worldwide due to
the sustainability.1,2 Based on the study by Taj et al.,3 natural fibers have been utilized to reinforce
materials for more than 3000 years. For better engineering materials, natural fiber-reinforced
composites have been used as an alternative candidate to replace the manmade fibers due to their
economical, renewable, easy processing, nontoxic, lightweight, low density, and abundant
nature.4–6 Nowadays, the fiber-reinforced composites are originally developed for various sectors,
such as aerospace, medical science, ports, and building construction. Generally, composites are
engineered materials that consist of two different phases and has the characteristics that are not
depicted by any of the constituents alone.7 Usually, the two reinforcing phases are the fibers,
sheets, or particles that are embedded in the matrix phase, such as thermoset or thermoplastic resin.
When the composite is fabricated and designed nicely and correctly, it combines the strength of the
reinforcement with the toughness of the matrix to achieve a combination of desirable properties
with the specialty, which is not available in any single conventional material. There are many
benefits of fiber-reinforced composites over conventional materials that have been reported by
Karnani et al.8 on thermoplastic- and thermoset-based matrices.
Natural resources that have attained commercial success in industries such as kenaf, jute, flax,
hemp and sisal are type of nonwood fibers that very commonly utilized by researchers for rein-
forcement in biocomposites. At the present level of technology, many researchers have done a lot
of research on this reinforcing fiber as they show a comparable strength and they are 10–30%
lighter than glass fibers and would result in eco-friendly biocomposites.9 Quality of fiber-
reinforced composite products is basically depended on the fiber–matrix interactions and its stress
transferability between fiber–matrix. The weak interfaces bonding between natural fibers (hydro-
philic) and polymer matrix (hydrophobic) give a reduction of great properties and performances of
the composites. Many researchers have done several treatments, especially physical and chemical
modification studies on a variety of natural fibers for understanding and enhancing the interfacial
strength between the natural fibers and polymer matrix.10–13 The combination of natural fiber and
matrix with some modification or treatment would increase the compatibility and the interface
adhesion property, giving rise to continuous covalent bonds between the fibers surface and the
macromolecular matrix.14–16
The mechanical properties of the composite also can be increased by designing the woven and
nonwoven natural fiber mat in the composites. Extensive studies have been done on natural fiber-
reinforced composites with modified woven and nonwoven natural fibers17–31 and they showed
that natural fibers with fibers pattern and modification have the significant role as reinforcement in
Mohammed et al. 3

thermoset and thermoplastic matrix. Alkaline, silane, acetylation, benzoylation, maleated coupling
agents, permanganate, peroxide, isocyanate, and other chemicals (stearic acid, sodium chlorite,
and triazine) have been used to improve adhesion between polymer matrix and the fiber surface by
enhancing the compatibility between the hydrophilic fiber and hydrophobic polymer matrix. These
treatments could also result in the reduction of composite’s water absorbability and improve their
mechanical properties. The extent of fiber–matrix adhesion would depend on the methods and
chemicals used.32 In this context, here, we incorporated both modified and unmodified kenaf fibers
into the epoxy matrix using a woven and nonwoven layering pattern.

Experimental
Materials
The thermoset epoxy resin type D.E.R 331 was procured from Zarm Scientific & Supplies Sdn.
Bhd., Malaysia. Epoxy hardener (A 062) as the curing agent was also supplied by Zarm Scientific
& Supplies Sdn. Bhd. A nonreactive diluent (benzyl alcohol) was supplied by Aldrich Company.
The kenaf bast woven and nonwoven mat used in this research were procured from a local
plantation source, Nibong Tebal Paper Mills (NTPM), Seberang Prai, Penang, Malaysia.

Methods and techniques

Modification of kenaf fiber using propionic anhydride. The kenaf woven and nonwoven mats were dried
in the oven at 105 C for 24 h to remove moisture and then placed in a desiccator. Then, the samples
were extracted in a Soxhlet apparatus with a 4:1:1 (v/v) mixture of toluene, ethanol, and acetone
for 5 h to remove impurities. After this, extracted samples of woven and nonwoven fibers were
dried overnight in an oven at 105 C. The cleaned kenaf fiber was then modified with propionic
anhydride in a reaction flask. The reaction was performed at 100 C for varying time intervals of
30, 60, 90, 120, 180 and 240 min without catalyst. After the appropriate time period, the anhydride
was decanted off and all the fiber mats were cleaned by refluxing in acetone for another 3 h.

Fabrication of composites. Fabrication of composites was done according to Jawaid.33 For the pre-
paration of the epoxy matrix, firstly, the clear epoxy resin and 10% by weight of benzyl alcohol were
mixed using a mechanical stirrer at 1000–1500 rpm. Then, a stoichiometric amount (60 parts curing
agents:100 parts epoxy by weight) of the polyamide was added and mixed evenly by mechanical
stirring process for 15 min with the same speed in a plastic container. The different weight ratio of
woven and nonwoven kenaf mat was kept with the total fiber loading at 40% by weight. For
development of composite, a stainless-steel thickness bar of 5 mm was used. The thickness bar was
coated with a thin layer of silicone oil solution that reacts as a releasing agent. The woven and
nonwoven fiber mats were fabricated in the mixture of epoxy resin via hand lay-up method. After the
fabrication process, the sample was covered with a stainless steel plate and was left to cure at 105 C
for 1 h in the hot press at 200 kg cm2. Once the composite was cured, the composite was transferred
into the oven at 105 C for another 1 h for postcuring to complete the polymerization process.

Characterization of modified kenaf fiber

Fourier-transform infrared spectroscopy. Fourier-transform infrared (FTIR) spectroscopy (Nicolet
Avatar Model 360 Spectrometer, Intertek Plastics Technology Laboratories, Pittsfield, USA) was
used to examine the functional groups present in the fibers. About 1–2 mg of powdered fiber
4 Progress in Rubber Plastics and Recycling Technology XX(X)

samples was mixed with 100 mg of potassium bromide powder. FTIR spectra of each sample were
obtained in the range of 4000–400 cm1.
Contact angle studies. Contact angle was measured with a KSV CAM 101 (KSV Instrument LTD,
Finland) series drop shape analysis contact angle meter. Each modified and unmodified mat of
woven and nonwoven kenaf fibers was pressed at 300 kg cm2 to make sure the surface of the
kenaf mat was flat before the test. Using a syringe, a drop of water was placed on the sample
surface. Then, the contact angle (q) was determined from digital silhouette drop images. The test
was done at ambient temperature and the average value of the contact angle was calculated by the
computer and recorded.

Characterization of kenaf fiber-reinforced epoxy composites

Water absorption test. The composite samples were immersed in distilled water at room tem-
perature. Five samples were repeated using a dimension of 20  20  5 mm3 according to ASTM
D570 standard. The water absorption was determined by equation (1) for various periods of time.
Samples were weighed before and after removing from water at various time intervals:
W1  W0
Water absorption ð %Þ ¼  100 ð1Þ
W0
where W1 is the weight of composite samples after immersion and W0 is the weight of composite
samples before immersion.
Thickness swelling test. Samples were prepared according to the ASTM D570 standard. Before the
samples were immersed in distilled water at room temperature, the thickness of every sample was
measured and labeled. After 24 h, the samples were taken out and dried before measuring the
thickness value. The thickness swelling test was continued for several days until the constant
weight of the samples was obtained. The methods of determining the percentage of thickness
swelling were evaluated by equation (2):
T1  T0
Thickness swelling ð %Þ ¼  100 ð2Þ
T0
where T1 is the thickness of the samples after immersion (mm) and T0 is the thickness of the
samples before immersion (mm).
Scanning electron microscope. Morphology of the modified and unmodified fibers was investi-
gated using a scanning electron microscope (SEM) (Leo Supra, 50 VP, Carl Ziess, SMT, Germany)
with an acceleration voltage of 5 kV. The samples were coated with gold prior to their morpho-
logical observation.
Thermogravimetric analysis. A piece of kenaf fiber composite (about 4–5 mg) was used for the
analysis. The fiber samples were characterized for their thermal stability using a PerkinElmer
thermal gravimetric analyzer (TGA-6). All three samples were heated from 30 C to 800 C under
nitrogen environment with a heating rate of 20 C min1.
Tensile test. A tensile test was performed according to ASTM D3039 standard using the Instron
model 5582 (MECOMB, Malaysia) universal testing machine. Rectangular strips of dimension 120
 15  5 mm3 were prepared using a circular saw. The gauge length was set at 60 mm with a testing
speed of 5 mm min1. The tensile strength, tensile modulus, and elongation at break were recorded.
Mohammed et al. 5

Figure 1. FTIR spectra of unmodified and modified kenaf fiber.

FTIR: Fourier transform infrared.

Flexural test. Flexural analysis was carried out at room temperature through three-point bend
testing, as specified in ASTM D790 standard by using Instron universal testing machine model
5582. The rectangular samples of dimension 160  20  5 mm3 were cut using a circular saw. The
speed of the crosshead was 5 mm min1. Five composite specimens were tested for each sample
and the average value was tabulated.
Impact test. Impact test was done according to ASTM D256 standard. Izod notched impact tests
were performed using the Gotech testing machine model GT-7045 MD (Gotech Sdn. Bhd., Selan-
gor, Malaysia). The impact test was carried out on samples with a dimension of 70  15  5 mm3.
The samples were rigidly mounted in a vertical position and were struck using a pendulum with 10
J force at the center of the samples. The number of fracture values was repeated five times and their
average load at first deformation was noted and tabulated as impact strength.

Results and discussion

Characterization of the kenaf fibers
FTIR analysis of modified kenaf fibers. Figure 1 displays the FTIR spectra of both modified and
unmodified kenaf fibers. As shown in Figure 1, the FTIR spectra of modified and unmodified
kenaf fibers showed broad and strong absorption band at 3200–3600 cm1 region corresponds to
hydroxyl (–OH) group stretching of hydrogen bond in the cellulose, hemicellulose, and lignin of
kenaf fibers. The unmodified fibers assigned a broad peak of the –OH vibration at 3422 cm1, and
after chemical modification, the spectra observed less intensity of –OH stretching for modified
fibers might be due to breaking of intermolecular hydrogen bonding between the –OH groups of
cellulose and hemicellulose molecules of the fibers resulting in the hydroxyl groups reduction.
Besides that, the peaks occurred at 2600–3090 cm1 region were due to the C–H of methylene
groups stretching vibrations, which indicated the presence of alkyl chains and ester groups formed
6 Progress in Rubber Plastics and Recycling Technology XX(X)

Figure 2. Contact angle of modified and unmodified fiber-reinforced epoxy composites.

during anhydride modification in the cellulose and hemicelluloses.34 For unmodified kenaf fibers,
the peak located at 1737 cm1 was assigned to the C¼O stretching of the acetyl group in the
“xylan” component of hemicellulose or the ester linkage of carboxylic group in the ferulic and
p-coumaric acids of lignin and hemicellulose.35,36
The increase of peak in the region of 1700–1750 cm1 after modification with propionic
anhydride indicated increment of carbonyl (C¼O) group stretching. The region between
1400 cm1 and 1300 cm1 showed an increase of the carbon–hydrogen (C–H) bond that associated
with the C–H in the plane deformation of CH2 and CH3 bending in the fibers. Furthermore, the
band in the region at 1240–1040 cm1 exhibited the carbon–oxygen (C–O) stretching vibration in
the acetyl group, thereby supporting the bond formation between hydroxyl groups of fiber and C–O
groups of anhydrides. The C–O bands also corresponded to aliphatic primary and secondary
alcohols in cellulose, hemicelluloses, lignin, and extractive components in the fibers.37

Contact angle studies. The contact angles of nonwoven and woven kenaf fibers before and after
modification are shown in Figure 2. Both modified woven and nonwoven kenaf fibers showed an
enhancement in contact angle compared to unmodified ones. Propionylated nonwoven kenaf fiber
showed a contact angle of 98.79 , whereas propionylated woven kenaf fiber showed 99.26 . From
Figure 2, it was evident that the chemically modified fibers become hydrophobic after chemical
modification. This was due to the introduction of carboxyl and dispersive aliphatic chain (–CH2–
CH3) groups on the surface of both woven and nonwoven kenaf fibers during propionylation.
Similar work was reported by Khalil and Suraya,28 where they studied the contact angle of kenaf
bast fiber and they also reported for propionylated (60.77 ) and succinylated (43.8 ) modified
fiber. It can be concluded that the enhancement in contact angle of the fiber could enhance the
compatibility with the hydrophobic polymer matrix like epoxy.

Morphology of the woven and nonwoven modified kenaf fibers. Figure 3(a) and (b) shows the SEM
image of woven and nonwoven kenaf fiber. The structure of nonwoven fibers showed a linear and
random structure of fibers while woven fibers showed a weave and very compact structure. Woven
fibers gave more advantages, including dimensional stability, higher impact resistance, and
Mohammed et al. 7

Figure 3. SEM image of (a) nonwoven kenaf fibers, (b) woven kenaf fibers, (c) unmodified kenaf fibers, and (d)
modified kenaf fibers.
SEM: scanning electron microscope.

particularly, for parts with complex shape and design compared to unidirectional single randomly
structure of nonwoven fibers.
The scanning electron micrograph of both unmodified and modified kenaf fibers surfaces is
shown in Figure 3(c) and (d). The unmodified kenaf fibers (Figure 3(c)) show rough surface due to
the presence of lignin, pectin, and waxy substance in the fibers. These cementing materials act as a
protective layer to the fiber surface. In case of modified kenaf fibers, it displayed a smooth surface
due to the removal of the cementing materials like lignin, pectin, and so on, from the surface of
fiber during chemical modification using propionic anhydride.28 Hence, propionic anhydride
modification resulted in the significant changes in morphology of fiber surfaces and enhanced the
fiber/matrix adhesion. Similar study was done by Sreekala et al. on oil palm fibers, and they found
that the fiber surface could be smoother with lesser impurities after surface modification.38

Characterization of kenaf fiber-reinforced epoxy composites

Water absorption and thickness swelling of composites. It is crucial to study the water absorption of
the fiber-reinforced polymer composites, as the mechanical properties of the composite could
deteriorate as a result of moisture absorption. Figure 4(a) shows the water absorption behavior
of epoxy and its modified and unmodified woven and nonwoven composites. From Figure 4(a),
unmodified woven fiber-reinforced epoxy composite showed the highest water absorption (7.48%)
8 Progress in Rubber Plastics and Recycling Technology XX(X)

Figure 4. (a) Water adsorption of epoxy, modified and unmodified fiber-reinforced epoxy composites and
(b) thickness swelling of epoxy, modified and unmodified fiber-reinforced epoxy composites.

compared to others. This higher water absorption was due to the high porous and hydrophilic
nature of the unmodified woven fiber-reinforced epoxy composite. When compared with the
unmodified one, the modified composite exhibited excellent water resistance due to the hydro-
phobic nature of the fiber after modification with propionic anhydride. Propionic anhydride could
reduce the hydroxyl (–OH) group in the fiber structure and hence lower the water absorption and
attributes to better fiber–matrix interface bonding. Epoxy composite showed a lower value of water
absorption of 0.58% due to its hydrophobic nature.
The modified and unmodified composites showed moderate water absorption in between 4.56%
and 7.22%. This proved that the chemical modification and woven nature of the kenaf fibers
reduced the water adsorption of the composites.33 Natural fiber-based composites have poor water
resistance due to the presence of polar groups, which attract water molecules through hydrogen
bonding and caused moisture built up in cell wall (fiber swelling) and in the fiber/matrix inter-
face.33,39 The result of thickness swelling test of the unmodified and modified composites after
several days being immersed in water until constant weight is shown in Figure 4(b). Surface
chemical modification of kenaf fiber-reinforced epoxy composites resulted in the lower value of
thickness swelling while the highest thickness swelling was observed in unmodified composites.
As shown in Figure 4(b), thickness swelling values increase proportionally with soaking time until
a certain period and long-term soaking time resulted in swelling of the fibers. Moreover, the
dimension was increased by the hydrophilic nature of lignocellulosic materials and the capillary
action that will cause the water intake when the samples were soaked into water. Hence, it will
cause fiber swelling and thus increase the dimensional stability.40,41

Thermogravimetric analysis. Thermogravimetric analysis (TGA) curve of modified (M) and

unmodified (UM) woven and nonwoven kenaf fiber-reinforced epoxy composites is shown in
Figure 5. According to Vanaja and Rao, thermal stability of a composite is governed by the matrix
as well as the individual reinforcement constituents of the composites. 42 From the TGA
Mohammed et al. 9

Figure 5. TGA curves of epoxy, modified and unmodified fiber-reinforced epoxy composites.
TGA: thermogravimetric analysis.

thermogram, it was observed that epoxy, unmodified and modified composites showed two steps
of degradation. The initial weight loss was found to be between 90 C and 100 C, and the results
were same for all the samples. This was probably due to dehydration of the samples, degradation of
hemicellulose, and evaporation of excess benzyl alcohol in epoxy mixture. The lignocellulosic
materials could decompose between 150 C and 500 C. The first decomposition happens at 150 C
which is hemicellulose followed by cellulose at 275-350 C and the last stage is lignin between
250 C to 500 C.43 The temperature at which specific weight losses occurred is summarized in
Table 1 and it shows to be higher for modified composites compared to unmodified composites and
epoxy.
The initial degradation temperature (TIDT) for unmodified woven fiber-reinforced epoxy compo-
site was 223 C, whereas the modified woven fiber-reinforced epoxy composite was 231 C. Simi-
larly, the initial degradation temperature (TIDT) for unmodified nonwoven fiber-reinforced epoxy
composite was 161 C, whereas the modified nonwoven fiber-reinforced epoxy composite was
179 C. From these results, it can be concluded that the modified fibers showed better thermal
stability than unmodified fibers. This is due to the fact that the modified fiber-reinforced epoxy
composites could be able to form a good bonding between the fiber and matrix. Furthermore, it can
be seen that the thermal stability of the epoxy composite has enhanced from 403 C to 677 C by
incorporating modified woven kenaf fibers into the epoxy matrix. The unmodified composites had
low char residue, which was 6.74%, as compared with propionylated composite char residue, which
was 14.97%, indicating the enhancement of thermal stability of the epoxy composites by incorpor-
ating modified kenaf fibers into the epoxy matrix. The observed char formation may be attributed to
the substantial chemical bonding after modification of propionic anhydride to the composites.33

Morphology of the kenaf fiber-reinforced epoxy composites. SEM images after flexural test of modified
and unmodified kenaf fiber-reinforced epoxy composites are shown in Figure 6(a) to (d). From the
images, the unmodified composite exhibited coarse structure compared to modified woven com-
posite. At higher magnification, Figure 6(b) showed the presence of silica and waxy substances
10 Progress in Rubber Plastics and Recycling Technology XX(X)

Table 1. Thermal properties of epoxy, unmodified and modified composites.

Degradation temperature ( C)

Composites TIDT TFDT Char residue (%)

Epoxy 119 403 2.68

Unmodified
Woven 223 582 6.74
Nonwoven 161 512 0.16
Modified
Woven 231 677 14.97
Nonwoven 179 560 8.15

IDT: initial decomposition temperature; FDT: final decomposition temperature.

Figure 6. SEM image of (a) unmodified kenaf composites (150), (b) unmodified kenaf composites (400),
(c) modified kenaf composites (150), and (d) modified kenaf composites (400).
SEM: scanning electron microscope.
Mohammed et al. 11

Figure 7. The (a) tensile strength, (b) tensile modulus, and (c) elongation at break of epoxy, unmodified and
modified composites.

that probably covered the unmodified fibers.35 Furthermore, fiber–matrix debonding, matrix crack,
and fiber pullout were more evident in unmodified composites, as shown in Figure 6(a) and (b)
compared with modified composites (Figure 6(c) and (d)). Meanwhile, from Figure 6(c) and (d),
after chemical modification of propionic anhydride, the surface illustrates much smoother surface
and good fiber–matrix bonding than unmodified composites. For unmodified samples, poor fiber–
matrix bonding and more waxy particles were observed in the composites, resulting in an inferior
stress transfer between phases.

Mechanical properties. Figure 7 shows the tensile strength, tensile modulus, and elongation at break
of epoxy, unmodified woven and nonwoven kenaf fiber-reinforced epoxy composites and modified
woven and nonwoven kenaf fiber-reinforced epoxy composites. As expected, chemical modifica-
tion by propionic anhydride of kenaf mat fibers resulted in a significant increase in tensile strength
and tensile modulus of the composite. From Figure 7(a), the modified and unmodified woven kenaf
fiber-reinforced epoxy composites had a tensile strength of 64.11 and 58.82 MPa, respectively,
12 Progress in Rubber Plastics and Recycling Technology XX(X)

whereas the modified and unmodified nonwoven kenaf fiber-reinforced epoxy composites had a
tensile strength of 54.28 and 52.13 MPa, respectively. The reason for the enhancement in the
tensile strength of modified fiber-reinforced composites was due to the better interfacial bonding
and compatibility between fiber and matrix. The mechanical behavior and durability of composite
materials depend on the properties of matrix and fiber and also interfacial properties of fibers.
Besides the increase in the interface adhesion between fiber and matrix, it also depends on the
removal of foreign particles by chemical modification of propionic anhydride. It can also be
attributed to the gain of mechanical interlocking between fiber and matrix and dipolar interactions
between anhydride groups and cellulosic hydroxyl (–OH) group. The results proved that woven
mat fiber gave higher strength as the tensile stress was absorbed and distributed evenly in the
composites. Similar studies were reported by Thiruchitrambalam et al. and Jawaid, they found that
woven banana/kenaf and jute/Empty Fruit Bunch (EFB) hybrid composites showed better prop-
erties than their nonwoven composites.23,33
Figure 7(b) shows the tensile modulus of epoxy, unmodified woven and nonwoven kenaf fiber-
reinforced epoxy composites and modified woven and nonwoven kenaf fiber-reinforced epoxy
composites. As shown in Figure 7(b), tensile modulus results display a similar trend like tensile
strength. The propionylated composites showed higher tensile modulus than unmodified compo-
sites and this proves that chemical modification had gained the ability of composite to resist the
deformation and breaking under tensile stress. Figure 7(c) shows the elongation at break of epoxy,
unmodified woven and nonwoven kenaf fiber-reinforced epoxy composites and modified woven,
and nonwoven kenaf fiber-reinforced epoxy composites. From Figure 7(c), the elongation at break
for epoxy (16.33%) was much higher than modified and unmodified composites. The results of
modified and unmodified composites were in the range of 3.13–4.87%. However, the unmodified
composites have higher elongation at break compared to modified composites. The reason for the
decrease in elongation at break for modified composite was due to the improvement of fiber–
matrix bonding. Propionylated fiber gives more stiffness to the composites compared with unmo-
dified composites. Based on the study by Abdul Khalil et al.,16 the enhancement of fiber and matrix
bonding would improve the stiffness, strength, and interfacial adhesion of the composites. Figure 8
shows the flexural strength and flexural modulus of epoxy, unmodified woven and nonwoven
kenaf fiber-reinforced epoxy composites and modified woven and nonwoven kenaf
fiber-reinforced epoxy composites. Modified woven composites had highest flexural strength,
which was 89.4 MPa, whereas, for unmodified composites the flexural strength was 86.8 MPa
[Figure 8(a)]. Also, the epoxy composites without reinforcement of kenaf fibers show the lowest
flexural strength of 36.2 MPa.
As reported by Abdul Khalil et al.,16 a weak fiber and matrix interfacial bonding could be
resulted in low flexural properties. Figure 8(b) shows the flexural modulus of epoxy, unmodified
woven and nonwoven kenaf fiber-reinforced epoxy composites and modified woven and nonwo-
ven kenaf fiber-reinforced epoxy composites. As shown in Figure 8(b), modified woven fiber-
reinforced epoxy composites showed the highest value of flexural modulus, which was 6.0 GPa,
compared to unmodified woven composites (5.51 GPa). This was due to better interaction between
modified kenaf fibers and epoxy matrix, which would enhance the flexural modulus.
Impact strength of a composite is defined as a measure of the ability of the material to resist
fracture failure when they are subjected to an impact load at high speed. The overall toughness of a
composite material is directly related to impact properties, which is highly influenced by the nature
of the constituent materials (matrix and fiber properties), the interfacial bond strength, test
Mohammed et al. 13

Figure 8. (a) Flexural strength and (b) flexural modulus of epoxy, unmodified and modified composites.

Figure 9. Impact strength of epoxy, unmodified and modified composites.

condition, construction, and geometry of the composites.34,35 Figure 9 shows the impact strength of
epoxy, unmodified woven and nonwoven kenaf fiber-reinforced epoxy composites and modified
woven and nonwoven kenaf fiber-reinforced epoxy composites. As shown in Figure 9, the mod-
ified woven composites had the high impact strength value of 9.43 kJ m2, whereas the unmodified
nonwoven composites showed an impact strength of 5.96 kJ m2 only. The results apparently
depicted that the chemical modification of kenaf fiber-reinforced epoxy composites leaded to high
impact strength compared to unmodified composites. The chemical modification of the fiber
facilitates more compatible interface with the epoxy matrix and thereby more force could be
required to break the composite. This resulted in the enhancement of the impact strength.
14 Progress in Rubber Plastics and Recycling Technology XX(X)

Conclusion
The kenaf fiber was successfully modified using propionic anhydride to improve the compatibility
with the hydrophobic matrix like epoxy. The chemical modification using propionic anhydride was
confirmed via FTIR and contact angle studies. FTIR results revealed the enhancement in peak
intensity in the region of 1700–1750 cm1 after modification with propionic anhydride due to the
introduction of carbonyl (C¼O) group stretching after chemical modification. The contact angle
studies showed that the kenaf fibers become hydrophobic in nature after the modification with
propionic anhydride. Unmodified woven fiber-reinforced epoxy composite showed the highest
water absorption (7.48%) compared to others. The unmodified woven fiber-reinforced epoxy
composites showed the highest thickness swelling with a value of 6.61% among the composites.
TGA analysis revealed that the thermal stability of the epoxy composites was enhanced from
403 C to 677 C by incorporating modified woven kenaf fibers into the epoxy matrix. The modified
and unmodified woven kenaf fiber-reinforced epoxy composites had a tensile strength of 64.11 and
58.82 MPa, respectively, whereas the modified and unmodified nonwoven kenaf fiber-reinforced
epoxy composites had a tensile strength of 54.28 and 52.13 MPa, respectively. The modified
woven composites had highest flexural strength, which was 89.4 MPa, whereas, for unmodified
composites, it was 86.8 MPa. The modified woven fiber-reinforced epoxy composites showed the
highest value of flexural modulus, which was 6.0 GPa compared to unmodified woven composites
(5.51 GPa). The impact strength of the epoxy composites was enhanced to 9.43 kJ m2 by the
incarnation of modified woven kenaf fibers into the epoxy matrix.

Acknowledgment
The authors wish to appreciate the collaborative efforts between Linton University College, Department of
Chemical Engineering, Universitas Syiah Kuala, Banda Aceh Indonesia, and School of Industrial Technol-
ogy, Universiti Sains Malaysia for the successful completion of this research work.

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publi-
cation of this article: The authors gratefully acknowledged the financial support from Universiti Sains
Malaysia, Penang, Malaysia, for providing Research University Grant (RUI-1001/PTEKIND/8014119).

ORCID iD
HPS Abdul Khalil https://orcid.org/0000-0003-2403-809X

References
1. Suki FM, Ismail H and Hamid ZA. Preparation and properties of polyvinyl alcohol/banana frond flour
biodegradable film. Prog Rubber Plast Re 2014; 30: 103–114.
2. Ismail H, Ishak S and Hamid ZAA. Comparison effect of mica and talc as filler in EPDM composites on
curing, tensile and thermal properties. Prog Rubber Plast Re 2013; 29: 109–122.
Mohammed et al. 15

3. Taj S, Munawar MA and Khan S. Natural fiber-reinforced polymer composites. Proc Pakistan Acad Sci
2007; 44: 129.
4. Gaceva BG, Avella M, Malinconico M, et al. Natural fiber eco-composites. Polym Composite 2007; 28:
98–107.
5. Graupner N, Herrmann AS and Müssig J. Natural and man-made cellulose fibre-reinforced poly(lactic
acid) (PLA) composites: an overview about mechanical characteristics and application areas. Compos A
Appl S 2009; 40: 810–821.
6. Xue Y, Du Y, Elder S, et al. Temperature and loading rate effects on tensile properties of kenaf bast fiber
bundles and composites. Compos B Eng 2009; 40: 189–196.
7. Ahmad S and Jamal Y. Machining of polymer composites. New York: Springer, 2009.
8. Karnani R, Krishnan M and Narayan R. Biofiber-reinforced polypropylene composites. Polym Eng Sci
1997; 37: 476–483.
9. Abilash N and Sivapragash M. Environmental benefits of eco-friendly natural fiber reinforced polymeric
composite materials. Int J Appl Innov Eng Manage 2013; 2(1): 53–59.
10. Van De Weyenberg I, Ivens J, De Coster A, et al. Influence of processing and chemical treatment of flax
fibres on their composites. Compos Sci Technol 2003; 63: 1241–1246.
11. Herrera-Franco PJ and Valadez-González A. A study of the mechanical properties of short natural-fiber
reinforced composites. Compos B 2005; 36: 597–608.
12. Aji I, Sapuan S, Zainudin E, et al. Kenaf fibres as reinforcement for polymeric composites: a review. Int J
Mech Mater Eng 2009; 4: 239–248.
13. Utsel and Simon. Surface modification of cellulose-based materials for tailoring of interfacial interac-
tions, Stockholm: KTH Royal Institute of Technology, 2012.
14. Belgacem MN and Gandini A. The surface modification of cellulose fibres for use as reinforcing
elements in composite materials. Compos Interface 2005; 12: 41–75.
15. Alvarez VA and Vazquez A. Influence of fiber chemical modification procedure on the mechanical
properties and water absorption of MaterBi-Y/sisal fiber composites. Compos A Appl S 2006; 37:
1672–1680.
16. Abdul Khalil H, Issam A, Ahmad Shakri M, et al. Conventional agro-composites from chemically
modified fibres. Ind Crop Prod 2007; 26: 315–323.
17. Ray D and Sarkar B. Characterization of alkali-treated jute fibers for physical and mechanical properties.
J Appl Polym Sci 2001; 80: 1013–1020.
18. Ahmed KS and Vijayarangan S. Tensile, flexural and interlaminar shear properties of woven jute and
jute-glass fabric reinforced polyester composites. J Mater Process Tech 2008; 207: 330–335.
19. Jawaid M and Khalil HA. Effect of layering pattern on the dynamic mechanical properties and thermal
degradation of oil palm-jute fibers reinforced epoxy hybrid composite. Bioresources 2011; 6: 2309–2322.
20. Joseph S, Sreekala M, Oommen Z, et al. A comparison of the mechanical properties of phenol formal-
dehyde composites reinforced with banana fibres and glass fibres. Compos Sci Technol 2002; 62:
1857–1868.
21. Idicula M, Malhotra SK, Joseph K, et al. Effect of layering pattern on dynamic mechanical properties of
randomly oriented short banana/sisal hybrid fiber–reinforced polyester composites. J Appl Polym Sci
2005; 97: 2168–2174.
22. Jannah M, Mariatti M, Bakar AA, et al. Effect of chemical surface modifications on the properties of
woven banana-reinforced unsaturated polyester composites. J Reinf Plast Comp 2009; 28: 1519–1532.
23. Thiruchitrambalam M, Alavudeen A, Athijayamani A, et al. Improving mechanical properties of banana/
kenaf polyester hybrid composites using sodium laulryl sulfate treatment. Mater Phys Mech 2009; 8:
165–173.
16 Progress in Rubber Plastics and Recycling Technology XX(X)

24. Ramaswamy GN, Sellers T, Tao W, et al. Kenaf nonwovens as substrates for laminations. Ind Crop Prod
2003; 17: 1–8.
25. Aziz SH and Ansell MP. The effect of alkalization and fibre alignment on the mechanical and thermal
properties of kenaf and hemp bast fibre composites: part 1 – polyester resin matrix. Compos Sci Technol
2004; 64: 1219–1230.
26. Shibata S, Cao Y and Fukumoto I. Lightweight laminate composites made from kenaf and polypropylene
fibres. Polym Test 2006; 25: 142–148.
27. Lai W, Mariatti M and Jani SM. The properties of woven kenaf and betel palm (areca catechu) reinforced
unsaturated polyester composites. Polym-Plast Technol 2008; 47: 1193–1199.
28. Khalil HA and Suraya NL. Anhydride modification of cultivated kenaf bast fibers: morphological,
spectroscopic and thermal studies. Bioresources 2011; 6: 1121–1135.
29. Khalil HA, Hanida S, Kang C, et al. Agro-hybrid composite: the effects on mechanical and physical
properties of oil palm fiber (EFB)/glass hybrid reinforced polyester composites. J Reinf Plast Comp 2007;
26: 203–218.
30. Khalil HA, Fazita MN, Jawaid M, et al. Empty fruit bunches as a reinforcement in laminated bio-
composites. J Compos Mater 2011; 45: 219–236.
31. Jacob M, Thomas S and Varughese KT. Mechanical properties of sisal/oil palm hybrid fiber reinforced
natural rubber composites. Compos Sci Technol 2004; 64: 955–965.
32. Li X, Tabil LG and Panigrahi S. Chemical treatments of natural fiber for use in natural fiber-reinforced
composites: a review. J Polym Environ 2007; 15: 25–33.
33. Jawaid M. Development and characterization of oil palm empty fruit bunch/jute fibres reinforced epoxy
hybrid composites. PhD, Universiti Sains Malaysia, Malaysia, 2011.
34. Tronc E, Hernández-Escobar CA, Ibarra-Gomez R, et al. Blue agave fiber esterification for the reinforce-
ment of thermoplastic composites. Carbohyd Polym 2007; 67: 245–255.
35. Tserki V, Zafeiropoulos NE, Simon F, et al. A study of the effect of acetylation and propionylation
surface treatments on natural fibres. Compos A Appl S 2005; 36: 1110–1118.
36. Sgriccia N, Hawley MC and Misra M. Characterization of natural fiber surfaces and natural fiber
composites. Compos A Appl S 2008; 39: 1632–1637.
37. El-Meligy MG, El-Zawawy WK and Ibrahim MM. Lignocellulosic composite. Polym Advan Technol
2004; 15: 738–745.
38. Sreekala MS, Kumaran MG and Thomas S.Oil palm fibers: morphology, chemical composition, surface
modification, and mechanical properties. J Appl Polym Sci 1997; 66: 821–835.
39. Ashori A and Sheshmani S. Hybrid composites made from recycled materials: moisture absorption and
thickness swelling behavior. Bioresource Technol 2010; 101: 4717–4720.
40. Yang HS, Kim HJ, Park HJ, et al. Water absorption behavior and mechanical properties of lignocellulosic
filler–polyolefin bio-composites. Compos Struct 2006; 72: 429–437.
41. Abdul Khalil H, Hanida S, Kang C, et al. Agro-hybrid composite: the effects on mechanical and physical
properties of oil palm fiber (EFB)/glass hybrid reinforced polyester composites. J Reinf Plast Comp 2007;
26: 203–218.
42. Vanaja A and Rao R.Fibre fraction effects on thermal degradation behaviour of GFRP, CFRP and hybrid
composites. J Reinf Plast Comp 2002; 21: 1389–1398.
43. Kim HS, Yang HS, Kim HJ, et al. Thermogravimetric analysis of rice husk flour filled thermoplastic
polymer composites. J Therm Anal Calorim 2004; 76: 395–404.