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Fibre surface modifications through different treatments with the help of design expert software for
natural fibre-based biocomposites
MR Islam, MDH Beg and MF Mina
Journal of Composite Materials published online 18 June 2013
DOI: 10.1177/0021998313491515

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JOURNAL OF
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Original Article M AT E R I A L S
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Fibre surface modifications through Reprints and permissions:
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different treatments with the help DOI: 10.1177/0021998313491515
jcm.sagepub.com
of design expert software for natural
fibre-based biocomposites

MR Islam, MDH Beg and MF Mina

Abstract
Composites of untreated and treated kenaf fibres with recycled polypropylene were fabricated by melt-cast technique
with and without using maleic anhydride-grafted polypropylene. To improve interfacial bonding between kenaf fibres and
recycled polypropylene, surface modifications of fibres were performed through ultrasound, enzyme and alkali pre-
treatments. Klason lignin test, Fourier-transform infrared spectroscopy and scanning electron microscopy were used for
the characterization of fibres. For characterization of composites, the samples were examined by density measurements,
mechanical tests, field-emission scanning electron microscopy, X-ray diffraction study, differential scanning calorimetry
and thermogravimetric analysis. Results revealed that ultrasound was able to remove the highest amount of lignin (32%).
Tensile strength of the composites was increased by 57%, 58% and 40% due to the treatment with alkali, ultrasound and
enzyme, respectively. Optimization of treatment parameters was carried out by means of the design expert software.
The optimum treatment parameters, such as alkali concentration, soaking time in alkali, sonication power, temperature,
enzyme concentration and soaking time in enzyme were found to be 4.6 wt%, 4.95 h, 99.96%, 94.46 C, 1.26 wt% and
3.89 h, respectively, which are reasonably close to the experimental ones. The preferential b-axis orientation in recycled
polypropylene crystal was found to be more apparent due to treated kenaf fibres with maleic anhydride-grafted poly-
propylene than untreated kenaf fibres with maleic anhydride-grafted polypropylene. A correlation among crystallinity,
surface morphology, and tensile and thermal properties of composites with the fibre-matrix interactions has been
established.

Keywords
Kenaf fibre, ultrasound treatment, enzymatic treatment, alkali treatment, response surface method

Introduction from their inherent polar groups, which show low com-
Over the past few decades, there has been a growing patibility with non-polar hydrocarbon when they are
interest in the development of polymeric composites combined with polymer matrices.2 As a result, compos-
from various natural fibres and still new fibres are ites tailored from hydrophilic and hydrophobic mater-
being added to this arena. The traditional synthetic ials do not exhibit desirable properties for many
fibres such as glass, aramid and carbon in composite engineering requirements. Moreover, natural fibres
applications are gradually being replaced by natural can readily absorb moisture from the environment
fibres due to their low cost, low density, high specific and can be readily attacked by fungi or microbes,
property, good mechanical properties, non-abrasive
nature, and eco-friendly and bio-degradability charac- Faculty of Chemical and Natural Resources Engineering, Universiti
teristics.1 These advantages of natural fibres over syn- Malaysia Pahang, Malaysia
thetic fibres make them very attractive reinforcing
Corresponding author:
agents in a wide variety of applications for manufactur- MDH Beg. Faculty of Chemical and Natural Resources Engineering,
ing consumer products. Although natural fibres have Universiti Malaysia Pahang,Gambang-26300, Kuantan, Malaysia.
several advantages, they have a few drawbacks arising Email: dhbeg@yahoo.com

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resulting in low life cycle and poor interfacial bonding employed at a time on the structural, mechanical and
with polymer matrix. These features call for improving thermal properties of KF-reinforced recycled polypro-
the fibre surface that can be done through various fibre- pylene (RPP) composites are still limited in the litera-
modification processes such as chemical, enzymatic and ture. Thus, the objective of this study is to optimize the
coupling agent treatments. For example, chemical processing conditions of KFs by ultrasound, enzyme
modifications of fibres led to significant reduction of and alkali treatments based on the notion that promis-
moisture absorption reported in previous research.3 ing composites of KFs-based RPP can be developed by
Among various chemical modifications, alkali treat- treated fibres. Utilization of this bio-resource in various
ment has been found to be fruitful for improving inter- applications can be strengthened on the one hand and
action behaviour of fibre and matrix as well as disposable/combustible problems of PP can be over-
mechanical properties of the composites.4–6 Similar to come on the other.
chemical treatment, use of enzymes in processing of nat-
ural fibres has a significant effect on removal of non-
cellulosic compounds.7 The potential beneEts of Experimental
enzyme technology include cost reduction, energy and
water savings, improved product quality and potential
Materials
process integration.8 Another technique useful for Raw KFs (RKFs) were collected from Kampung
modifying fibre surface is the ultrasound treatment, Merchong, Pahang, Malaysia. RPP, commercial name
which involves physical and chemical processes due to PP black copo, consisting of isotactic PP and PP-copo-
ultrasound cavitations’ effect in the liquid medium, lymer, having density 0.91 g/cc and melting point
resulting in a growth and explosive collapse of micro- 163 C, was kindly supplied by Efficient Growth Sdn
scopic bubbles.9 Due to sudden collapse of bubbles, Bhd, Selangor, Malaysia. Maleic anhydride-grafted
localized high temperature, high-pressure shock waves polypropylene (MAPP) (Polybond 3200, density
and severe shear force generated are able to break the 0.91 g/cc and MA level 1.0 wt%) was kindly supplied
chemical bonds. The purpose of these three treatment by MTBE Sdn Bhd, Gebeng, Kuantan, Malaysia.
processes is to compare the removal of lignin (the Laccase enzyme (Novozyme-51003, Denmark),
cementing material that holds and binds the cellulose sodium hydroxide (NaOH) of purity >99% (Merck,
fibres tightly) from the fibre so that a better adhesion or Germany) and acetic acid of purity >98.8% (Sigma
mechanical entanglement among polymer molecules Aldrich, USA) were used in this study.
and fibres can be achieved. On the other hand, use of
coupling agent like maleic anhydride is also notable to
improve the adhesion between natural fibres and poly-
Sample preparation
mer matrices.10 Fibre surface modification. An ultrasonic cleaner, model-
Nowadays, use of recycled materials for composite DAIHAN-DH.D 300H, was used to treat KFs in the
fabrication is attracting the attention of researchers for water medium. Sonication power and treatment tem-
some value-added products. Compared with virgin perature was maintained at 50100% and 6095 C,
polymer, the properties of polymer composites made respectively. For alkali and enzyme treatment, alkali
of recycled materials has been reported to be equally concentration (37 wt%), soaking time in alkali
good or even better.11,12 Thus, our current work is (26 h), enzyme concentration (1.0–2.0 wt%) and soak-
based on recycled polypropylene, which is a recycling ing time in enzyme (26 h) were considered as treat-
material obtained from bumper and battery case of ment variables. The pH of enzyme solution was
vehicles. adjusted to 5.5 as specified for favourable treatment
Selection of processing parameters for fibre treat- condition by adding acetic acid. In each case, 100 g
ments is a major challenge because the optimum treat- fibres were taken for 2 l of solution. After the treat-
ment condition is always expected to find out the best ment, fibres were washed with water until their pH
processing route of a material for minimizing the cost reached 7 to neutralize the acidic or basic character of
of huge time. In this context, response surface method the fibre. They were then air-dried for 24 h and subse-
(RSM) is a statistical technique that uses a sequence of quently oven-dried at 80 C for 24 h.
designed experiments to obtain an optimal response,
making it suitably enabled to reduce the time consump- Optimization through RSM. Performance optimization in
tion of trail experiments.13,14 For this reason, the RSM terms of fibre treatment parameters was carried out by
has been utilized in optimizing treatment parameters to means of a Design Expert Software (DES), Version
complete this study within the shortest possible time. 8.0.6, Stat-Ease Inc, USA. Alkali concentration, soak-
Besides, comparative reports on the effects of ultra- ing time in alkali, sonication power, treatment tempera-
sound-, enzyme- and alkali-treated kenaf fibres (KFs) ture, enzyme concentration and soaking time in enzyme

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Islam et al. 3

were taken as different variables merely on the basis of mixing by extrusion into the fibre at a ratio of 1:10 for
characterizing tensile strength (TS) as the response. fabricating untreated- and treated fibre-reinforced com-
When the experimental ranges of values were applied posites. The samples subjected to characterization for
to DES, it predicted TS values for a combination of two comparison of structures and properties were RPP,
variables, with which RKFs were again treated to fab- RPP/raw fibre composites (RKP), MAPP-loaded
ricate a series of new composites. Examples of predicted RKP (RKMP), MAPP-loaded AKF/RPP composites
parameters, such as alkali concentration ¼ 37 wt% (AKMP), MAPP-loaded UKF/RPP composites
and soaking time in alkali ¼ 26 h, are shown in (UKMP) and MAPP-loaded EKF/RPP composites
Table 1. Using experimental and predicted (suggested (EKMP).
by DES) TS values, various graphs were plotted by
means of the software, showing optimal performances
Characterizing techniques
of the composites.
Acid-insoluble lignin measurement. The percentage of acid-
Preparation of composites. The individually treated fibres insoluble lignin content of untreated and treated KF
were separately shredded by a shredder to lengths of fibres was determined using the APPITA P11s-78
25 mm, dried at 80 C in an oven and compounded Klason lignin test method.15
with RPP by means of a twin-screw extruder (Prism
Eurolab 16) followed by injection moulding machine
(NESSEI, model-PNX60) at 190 C. The average diam- Fourier-transform infrared spectroscopy. The functional
eter of raw fibre was 0.05–0.08 mm and calculated aver- groups of untreated and treated fibres were detected
age aspect ratio (length/diameter) found to be 54. Due by a Nicolet 6700 FT-IR spectrometer, Thermo
to treatments, the average diameter was decreased to Scientific, Germany. Fourier-transform infrared
0.04–0.06, 0.04–0.05 and 0.05–0.07 mm and aspect ratio (FTIR) spectroscopy was performed using the standard
became 70, 78 and 58 for the case of ultrasound-, alkali- KBr pellet technique in the wave number range of
and enzyme-treated fibre, respectively. Fibre contents 500–4000 cm1.
in composites were considered as 10, 20, 30, 40 and
50 wt%. The optimized KF fibres obtained from ultra- Density. The density of KF, RPP, MAPP and compos-
sound, enzyme and alkali treatments corresponding to ites was measured by a pycnometer (micromeritics,
the maximum tensile value of the composites are here- AccuPyc II 1340 gas pycnometer) using helium gas.
in-after referred to as UKFs, EKFs and AKFs, respect- Approximately 2–3 g of each material was measured
ively. Coupling agent MAPP was incorporated during using a digital balance machine up to four decimals.

Table 1. Proposed parameters obtained by using DES for alkali treatment and experimentally observed TS values.

Response 1 Response 1
Factor 1 Factor 2 (theoretical) (experimental)

NaOH concentration
Standard Run Block (%) Time (h) TS (MPa) TS (MPa)

4 1 Block 1 7.00 6.00 – 27.43

9 2 Block 1 5.00 4.00 – 27.88
8 3 Block 1 5.00 6.00 – 26.98
11 4 Block 1 5.00 4.00 – 27.88
6 5 Block 1 7.00 4.00 – 27.11
13 6 Block 1 5.00 4.00 – 28.77
1 7 Block 1 3.00 2.00 – 26.79
7 8 Block 1 5.00 1.17 – 25.23
5 9 Block 1 2.17 4.00 – 26.32
3 10 Block 1 3.00 6.00 – 28.51
12 11 Block 1 5.00 4.00 – 28.53
2 12 Block 1 7.00 2.00 – 25.43
10 13 Block 1 5.00 4.00 – 27.98
TS: tensile strength; DES: Design Expert Software.

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One sample from each category was taken for this Results and discussion
study.
Analysis of lignin
Mechanical test. Tensile tests were carried out according The highest amount of lignin content in RKFs is mea-
to ASTM D638-Type I using a SHIMADZU (MODEL sured to be 14.2%. From this total content, the range
AG-1) universal testing machine with a load cell of percentage of lignin removal by alkali treatment is
5 kN at a cross-head speed of 10 mm/min and with a found to be 3.5–26.1% under the following treatment
gauge length of 65 mm. Flexural tests were conducted parameters: alkali concentration, 3–7 wt% and soaking
only for the strongest composites according to ASTM time in alkali, 2–4 h. This means that about 75% of the
D790-97 standard with a static load of 1 kN, using the original lignin content cannot be removed. Similarly,
same apparatus as that used for tensile test. The sup- the range of lignin removal (from total lignin con-
port spans were set at 50 mm and the cross-head speed tent ¼ 14.2%) obtained by ultrasound treatment is
was maintained at 10 mm/min. The measurements were 4.9–31.9% under the following treatment parameters:
made at a temperature of 24  2 C and relative humid- sonication power, 50–100% and treatment tempera-
ity of 50  5%. Five replicates were considered for each ture, 60–95 C. The range of lignin removal is 0.7–
category of sample and the average value was taken for 23.2% by enzyme treatment with the following treat-
data analysis. ment parameters: enzyme concentration, 1–2 wt% and
soaking time in enzyme, 2–6 h. Thus, a significant
amount of lignin (32%) is eliminated by ultrasound,
X-ray diffraction measurements. X-ray diffraction (XRD)
when sonication power is 100% and treatment tem-
measurements were conducted to observe the crystal-
perature is 95 C. Thus, ultrasound treatment appears
line structure of the RPP and the composites. A Rigaku
as an effective method to remove the lignin content
Mini Flex II, Japan, was used for XRD analysis. The
from KFs.
operating voltage and the tube current of the X-ray
generator were 30 kV and 15 mA, respectively. The spe-
cimens were step-wise scanned over the scattering angle FTIR analysis
(2y) from 5 to 40 , with a step of 0.02 , using Cu Ka
The FTIR spectra for RKF, AKF, UKF and EKF are
radiation of wavelength  ¼ 1.541Å.
shown in Figure 1. The important variations found in
the range 800–1800 cm1 are highlighted with arrows
Thermal test. A TA instrument, Q-1000, was used to and enclosures. The peak at 1739 cm1, in the dotted
perform differential scanning calorimetry (DSC) of enclosure, is due to C ¼ O stretching vibrations of the
the samples in an aluminium pan with a heating rate carboxyl and ester groups in hemicellulose of RKFs. A
of 20 C/min. A heat/cool/heat method was applied in a considerable decrease in intensity of C ¼ O stretching
temperature range of 25250 C. The percentage of
DSC crystallinity (dsc) was obtained using the
method described elsewhere.16 Thermogravimetric
measurements were carried out using a thermogravi-
metric analyser (TGA; TA instrument, TGA Q500).
Each sample was weighed and heated in the tempera-
ture range of 25–600 C at a heating rate of 20 C/min.
TGA analyses were conducted in a platinum crucible
under nitrogen atmosphere at a flow rate of 40 ml/min
to avoid unwanted oxidation. Kinetic parameters for
the thermal degradation were determined from the
TGA graphs using the Broido’s method.17

Scanning electron microscopy. The surface morphologies

of RKF and treated KFs (UKF, AKF and EKF)
were monitored by a scanning electron microscope
(SEM) (model-ZEISS, EVO 50) and that of composites
were examined by field emission scanning electron
microscopy (FE-SEM) (model-JEOL, JSM-7800F). Figure 1. FTIR spectra of RKF, AKF, UKF and EKF.
Prior to observations, samples were coated with gold KF: kenaf fibres; FTIR: Fourier-transform infrared spectroscopy;
for fibres and platinum for composites by means of a AKF: alkali-treated KFs; RKF, raw KFs; UKF: ultrasound-treated
vacuum sputter-coater for ease of conduction. KFs; EKF: enzyme-treated KFs.

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Islam et al.
vibrations occurs in the spectra of treated fibres. The
b-glucosidic linkage between sugar units of hemicellu-
loses in RKF appears at a wave number 896 cm1.18
The CO stretching vibrations at 1249 cm1 is a char-
acteristic band of the acetyl groups of lignin in RKF.
The peaks at 1449, 1440 and 1035 cm1 in the RKF
spectrum are due to CH3 asymmetric stretching, CH2
deformation and CH in-plane deformation in lignin,
respectively.19 All these absorbance bands are found
to be weakened in case of treated fibres, indicating par-
tial removal of hemicellulose and lignin. From the
intensity decreases in the 1449 cm1 peak, the estimated
removal (%) of lignin content from treated fibres lie in
the range of 2040%, whereas the optimum removal
(%) from three different treatments obtained by the
lignin test is 14–32%, showing a close agreement
between the two observations. Furthermore, the inten-
sity of the broad absorbance peak in the range 3200–
3600 cm1, in the dashed enclosure, which represents
O–H stretching of hydrogen bond, decreases after
fibre treatments. This decrease in intensity indicates a
reduction in hydrogen bonding (intermolecular or
intramolecular) between the hydroxyl groups of cellu-
lose and hemicelluloses.20 This intensity decrease is also
attributed to hemicelluloses removal, and as result, the
OH groups of the cellulose are exposed. This exposition
of OH groups is reported elsewhere.21
Density
The densities of KFs, RPP and MAPP were found to be
1.50, 0.91 and 0.91 g/cm3, respectively. The observed
densities of the composites increased after fibre loading
and further increased due to treated fibre, indicating
better adhesion in between fibre and matrix. To calcu-
late interfacial adhesion, the volume factions of voids
(V) in the composites have been calculated by the fol-
lowing equation
Vv ¼
where dtc and dec is the theoretical and experimental
density of the composites, respectively. The dtc of the
composites can be measured according to the method
established by Agarwal and Broutman22
dtc ¼ wf
df
where wf, wp and wmapp are the weight fractions of fibre,
matrix and coupling agent, whereas, df, dp and dmapp are
the densities, respectively. The dec of RKP, RKMP,
AKMP, UKMP and EKMP were found to be 1.03,
1.08, 1.09, 1.122 and 1.082 g/cm3 and their dtc are
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1.08, 1.10, 1.10, 1.130 and 1.10, respectively. Thus
their respective calculated V are 4.629, 1.818, 0.909,
0.707 and 1.636%, indicating the degree of adhesion
having order of UKMP > AKMP > EKMP >
RKMP > RKP.
Mechanical properties
Tensile properties, such as TS and tensile modulus
(TM) of the composites without and with MAPP as a
function of RKFs content, are presented in Figure 2.
The observed TS value for RPP is 15.46 MPa and that
for composites after RKFs inclusion is found to change
considerably. The maximum TS and TM values are
obtained at 40 wt% RKF content for the samples pre-
pared both with and without MAPP. The mechanical
properties decrease when RKF content is >40 wt%.
This decrease was explained on the basis of poor dis-
persion and agglomeration of the fibres at higher
loading.23
On the other hand, among the various set of pro-
posed parameters, the maximum experimental TS and
TM values were exhibited under the following condi-
tions: alkali concentration, 5 wt% and soaking time in
alkali, 4 h; sonication power, 100% and treatment tem-
perature, 95 C; and enzyme concentration, 1.5 wt%
and soaking time in enzyme, 4 h With these, the stron-
gest composites yielded under alkali, ultrasound and
enzyme treatments are denoted to AKMP, UKMP
and EKMP, respectively. A comparison of TS, TM,
flexural strength (FS) and flexural modulus (FM) for
RKP, RKMP, AKMP, UKMP and EKMP are pre-
sented in Figures 3 and 4. The values of the mechanical
properties are also listed in Table 2. The calculated TS
increments in RKMP, AKMP, UKMP and EKMP
from RKP are approximately 37%, 57%, 58% and
40% along with TM increments of approximately
6%, 27%, 26% and 31%, respectively. Similarly, they
show respective FS-increments of 98%, 138%, 148%
dtc  dec and 142% along with the significant FM-increments
dtc of 207%, 584%, 721% and 507%. This significant
improvement in mechanical performances is most
likely due to the robust TS values of individual KF as
well as the effects of treatments and coupling agents. In
addition, the aspect ratio of differently treated fibre is
found to be different and there is a minimum aspect
ratio, called critical aspect ratio, at which the maximum
1 allowable fibre stress can be achieved at a given load.24
wp
wmapp
þ þ dmapp
dp
The ultrasound treatment most probably renders crit-
ical aspect ratio for better mechanical properties of the
composites. Moreover, the use of coupling agent facili-
tates this improvement further because of increasing
fibres surface roughness and the hydrogen bond forma-
tion between MA and OH group of fibres.25 Therefore,
the enhancement of mechanical properties can be
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Figure 2. TS and TM of the composites without and with MAPP as a function of KFs content.

Figure 3. Comparisons of TS and TM of different samples. Figure 4. Comparisons of FS and FM of various samples.
TS: tensile strength; TM: tensile modulus. FS: flexural strength; FM: flexural modulus.

claimed for the removal of lignin and other undesirable treatments, resulting in the decrease of diameters of
components from fibres, together with the addition of treated fibres. Moreover, AKF, UKF and EKF show
coupling agent. rough surface with exposition of fibrils, indicating
removal of debris and non-cellulosic components
from fibres. Surface morphologies of treated KFs
SEM studies of fibres and their composites were reportedly attributed to the removal of lignin,
Surface morphologies of RKF, AKF, UKF and EKF pectin and hemicelluloses.23
are presented in Figure 5, where RKF shows a com- FE-SEM micrographs of the fractured surfaces for
paratively smoother surface with fibre thickness larger various samples prepared by tensile tests are presented
than others. These findings suggest that cellulose in in Figure 6. The micrographs of RKP show more
RKF is held together by means of binding components uneven surface structures than those of composites
like lignin and pectin, which are removed after with MAPP and treated fibres. For instance, while

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Islam et al. 7

Figure 5. SEM micrographs of (a) RKF, (b) AKF, (c) UKF and (d) EKF.
SEM: scanning electron microscope; KF: kenaf fibres; AKF: alkali-treated KFs; RKF, raw KFs; UKF: ultrasound-treated KFs; EKF:
enzyme-treated KFs.

huge fibres are pulled out from RKP after stretching, a originated from the amorphous parts such as hemicel-
few fibres come out from RKMP, and only exception is lulose, lignin, pectin, and so forth, of KF (Figure 7(a)),
found in the cases of AKMP, UKMP and EKMP, while the two peaks at 2y ¼ 22.5 and 2y ¼ 22.5 corres-
which show relatively very few fibres being pulled out. pond to (002)KF and (110)KF planes of the crystalline
The fibre pull out corresponds to poor compatibility cellulose material of RKF.26 On the other hand, the
and weak adhesion between fibre and matrix. The most prominent peaks of RPP are analyzed to show
SEM examinations clearly reveal poor interfacial adhe- the monoclinic a-phase, as indexed by (110), (040),
sion between KFs and RPP in RKP. In contrast, less (130), (041) and (060) planes (Figure 7(b)).27 Apart
fibre pull out in case of MAPP-loaded composites clar- from these indexed peaks, other sharp peaks in the pro-
ify a good adhesion between fibre and polymer. Thus, file of RPP probably arise from other unknown com-
FE-SEM micrographs show improved interfacial adhe- pounds included for their recycling and are of no
sion in treated fibre-reinforced composites with MAPP. interest here. Evidently, the a-form of RPP changes
Therefore, it is evident that the adhesion between fibre neither by reinforcement nor by treatments of KFs.
and matrix is improved by fibre treatments and is sub- However, a careful observation shows that the (040)
stantially strengthened by the addition of MAPP. peak position for AKMP, UKMP and EKMP is the
same as that for RPP but is shifted slightly to a lower
angle for RKP and RKMP. Therefore, the lattice spa-
Structural analyses cing along the b-axis of the RPP crystal in untreated
XRD patterns of (a) RKF, (b) RPP, (c) RKP, (d) KF-reinforced RPP composites is enlarged, suggesting
RKMP, (e) AKMP, (f) UKMP and (g) EKMP are dis- a distorted or loose packing of the PP molecules.
played in Figure 7. The diffraction profile of RKF Moreover, the estimated intensity increase in (040)
shows two peaks on a diffused halo, which has plane of AKMP, UKMP, EKMP and RKMP from

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Figure 6. Fractured surface micrographs of various samples observed by FE-SEM: (a) RPP, (b) RKP, (c) RKMP, (d) AKMP, (e) UKMP
and (f) EKMP.
FE-SEM; field emission scanning electron microscopy; RPP: recycled polypropylene; RKP: RPP/raw fibre composites; MAPP: maleic
anhydride-grafted polypropylene; RKMP: MAPP-loaded RKP; KF: kenaf fibres; AKF: alkali-treated KFs; AKMP: MAPP-loaded AKF/RPP
composites; UKMP: MAPP-loaded UKF/RPP composites; EKMP: MAPP-loaded EKF/RPP composites.

the same plane of RPP is 31%, 27.5%, 27.8% and planes with respect to (110) planes indicates that b-axis
24.8%, respectively. These results suggest an enhance- oriented crystal in RPP is developed more in treated
ment of crystallinity due to treated fibres, wherein KF-based composites than in untreated ones.28 Other
ultrasound shows better result. The intensity ratios of remarkable changes found in the diffractograms are
(040) and (110) planes of RPP, RKMP, AKMP, enclosed by two vertical lines. Clearly, both the
UKMP and EKMP are 1.38, 1.56, 1.56, 1.63 and (041)RPP and (002)KF in the profiles of AKMP,
1.47, respectively. The pure RPP exhibits both a- and UKMP and EKMP distinctly appear, whereas they
b-axes oriented a-crystal. Increase in intensity of (040) are smeared in the profiles of RKP and RKMP.

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Islam et al. 9

All these results strongly demonstrate that treatments observed at approximately 125 C and 164 C, corres-
increase in the crystallinity in cellulose fibres, and the ponding to the melting temperatures (Tm1 and Tm2) of
treated KFs increase in the crystallization, crystallinity PP copolymer and isotactic PP, respectively. An add-
and b-axis oriented crystal in RPP. itional peak appears at around 80 C (indicated by
arrows) due to the release of water molecules from
KFs. After incorporation of treated KFs in RPP, the
Thermal analysis peak position of Tm1 does not change at all but that of
The DSC thermograms of different samples are pre- Tm2 is slightly shifted to a higher temperature. The Tm2
sented in Figure 8. Two endothermic peaks are increase may be attributed to the increase in lamellar
structure and crystallinity of isotactic PP, as influenced
by the surface-modified KF fibres. The values of melt-
ing enthalpy (
Hm) for isotactic RPP are shown in
Table 2. Considering
Hm ¼ 209 J/g for the 100%

Figure 7. XRD profiles of (a) RKF, (b) RPP, (c) RKP, (d) RKMP,
(e) AKMP, (f) UKMP and (g) EKMP.
XRD: X-ray diffraction; RPP: recycled polypropylene; KF: kenaf
fibres; RKF, raw KFs; RKP: RPP/raw fibre composites; MAPP:
maleic anhydride-grafted polypropylene; RKMP: MAPP-loaded
RKP; AKMP: MAPP-loaded AKF/RPP composites; UKMP:
MAPP-loaded UKF/RPP composites; EKMP: MAPP-loaded EKF/ Figure 8. DSC thermograms of composites.
RPP composites. DSC: differential scanning calorimetry.

Table 2. Mechanical properties as well as enthalpy, crystallinity and activation energy values for various samples.

Mechanical properties DSC TGA

Samples TS (MPa) TM (MPa) FS (MPa) FM (MPa)
H (J/g) dsc (%) Stage Tmax (oC) Ea (kJ/mol)

RKP 18.29 796 27.72 409 30.1 24.0 1st 365 44.37
2nd 473 67.44
RKMP 25.17 846 32.09 759 39.2 31.3 1st 351 50.90
2nd 477 78.84
AKMP 28.77 1045 33.9 911 46.3 36.9 1st 353 49.53
2nd 477 96.04
UKMP 28.84 1035 34.69 1092 48.23 38.5 1st 366 49.36
2nd 488 91.05
EKMP 25.77 1078 33.31 806 45.8 36.3 1st 343 46.28
2nd 470 87.71
TS: tensile strength; TM: tensile modulus; FS: flexural strength; FM: flexural modulus; TGA: thermogravimetric analyzer; DSC: differential scanning
calorimetry; RKP: RPP/raw fibre composites; MAPP: maleic anhydride-grafted polypropylene; RKMP: MAPP-loaded RKP; AKMP: MAPP-loaded AKF/
RPP composites; UKMP: MAPP-loaded UKF/RPP composites; EKMP: MAPP-loaded EKF/RPP composites.

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10 Journal of Composite Materials 0(0)

crystalline polypropylene,29 analysis shows that the dsc The TGA thermograms of various samples are
value increases up to 60% due to fibre treatment and shown Figure 9(a), indicating a two-stage transition
coupling agent and this increase is pertinent to the find- with a similar trend, where the amount of weight
ings of XRD. Hence, the incorporated KFs apparently loss at a particular temperature is different, depending
act as nucleating agents, which ultimately increase the on the samples. This difference in thermal degradation
crystallinity (Table 2) of composites. On the other of the samples is due to the presence of fibres, the
hand, crystallinity increases by treated fibres in the surface treatments of fibres and the presence of
presence of coupling agent, because a strong interaction MAPP. The temperature of maximum degradation
between fibre and matrix provides a transcrystallinity (Tmax) for all samples is tabulated (Table 2).
effect, which was found by Marcovich and Villar30 in Obviously, the weight loss commences at approxi-
linear low-density polyethylene composite with wood mately 280 C, known as the onset temperature of
flour. Moreover, the observed increase in Tm of com- thermal degradation. The onset temperatures for
posites with treated fibres and MAPP from that of RKP, RKMP, AKMP, UKMP and EKMP are ana-
RKPC strongly demonstrates that coupling agent lyzed to be 282, 283, 304, 309 and 295 C, respectively.
retards crystal melting of RPP owing to the hydrogen These findings clarify that the maximum thermal deg-
bonding between MA and fibres. radation in treated fibre-loaded composites occurs
relatively at a higher temperature, where UKMP exhi-
bits the highest value. To understand the thermal deg-
radation mechanism, Broido’s plots for some samples
are shown in Figure 9(b) and the values of activation
energy (Ea) estimated for all samples are shown in
Table 2. The Ea represents the energy barrier prevent-
ing polymer molecules from moving from one location
to the other. The higher value of Ea shows more ther-
mal stability of a sample. The observed results thus
strongly demonstrate that UKMP is thermally more
stable than other composites.

Optimization of treatment parameters by RSM

Using the suggestive parameters by DES, the compos-
ites prepared show the experimental TS values and
with these TS values, further parameters sought by
DES provide a set of plots for actual versus predicted
TS value and three-dimensional (3D) plots containing
optimal performances. The variations in predicted
versus actual TS drawn for (a) alkali, (b) enzyme
and (c) alkali treatments are illustrated in Figure 10.
The values lie very close to the best-fitting straight line
for the case of ultrasound-treated samples but are
slightly dispersed for alkaline- and enzyme-treated
samples, suggesting that the model is more significant
for ultrasound treatment than the other two treat-
ments. Besides, 3D plots show the variation in
response with respect to two different parameters
(Figure 10 (e)–(g)). The best set of treatment condi-
tions, as suggested by the software, are alkali concen-
tration, 4.6 wt%, soaking time in alkali, 4.95 h;
Figure 9. (a) TGA thermograms of various composites and (b)
sonication power, 99.96%, treatment temperature,
Broido’s plots for RKP, RKMP and AKMP to calculate activation
energy. 94.46 C; enzyme concentration, 1.26 wt%, soaking
TGA: thermogravimetric analyzer; RPP: recycled polypropylene; time in enzyme, 3.89 h, which give rise to the highest
RKP: RPP/raw fibre composites; MAPP: maleic anhydride-grafted TS values of 28.3, 28.86 and 25.59 MPa. These results
polypropylene; RKMP: MAPP-loaded RKP; AKMP: MAPP-loaded are reasonably close to our experimentally observed
AKF/RPP composites. values.

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Islam et al. 11

Figure 10. Plots of predicted versus actual TS value for (a) alkali, (b) ultrasound and (c) enzyme treatments and 3-D plots of the
response as a function of (d) sonication power and temperature, (e) NaOH concentration and time and (f) enzyme concentration and
time.
TS: tensile strength.

Conclusions studied. FTIR analyses reveal information of the

Different types of treatment techniques such as enzyme, removal of lignin and hemicelluloses from KF by ultra-
ultrasound and alkali have been performed for the sur- sound, enzyme and alkali treatments. A strong adhe-
face-modification of KF. Process optimizations sion between KFs and RPP matrix in the composites
through the DES as well as a comparative analysis of has been achieved by treated fibres with coupling agent,
the properties of fibre and composites have also been as demonstrated by FE-SEM. The experimentally

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12 Journal of Composite Materials 0(0)

observed optimum treatment parameters, such as alkali 11. Adhikary Kamal B and Pang Shusheng and Staiger MP.
concentration, 5 wt%, soaking time in alkali, 4 h, son- Long-term moisture absorption and thickness swelling
ication power, 100%, treatment temperature, 95 C, behaviour of recycled thermoplastics reinforced with
enzyme concentration, 1.5 wt% and soaking time in Pinus radiate sawdust. Chem Eng J 2008; 142(2, 15):
190–198.
enzyme, 4 h evaluated by RSM, respectively, results in
12. Alireza A and Nourbakhsh A. Characteristics of wood–
4.6%, 4.95 h, 99.96%, 94.66 C, 1.26 wt% and 3.89 h, fiber plastic composites made of recycled materials.
rendering the maximum mechanical properties of the Waste Manag 2009; 29(4): 1291–1295.
resulting composites with close agreement. The treat- 13. Karunanithy C and Muthukumarappan K. Optimization
ment parameters suggested by RSM reduce the time of switch grass and extruder parameters for enzymatic
consumption significantly in the quest of optimal per- hydrolysis using response surface methodology. Ind
formances of the composites. Treated fibres in the pres- Crops Prod 2011; 33(1): 188–199.
ence of coupling agent improve the crystalline packing, 14. Islam MR, Beg MDH, Gupta A, et al. Optimal perform-
crystallinity and b-axis orientation in RPP crystals, as ances of ultrasound treated kenaf fibre reinforced
revealed by XRD and DSC. recycled polypropylene composites as demonstrated by
response surface method. J Appl Polym Sci 2013;
128(5): 2847–2856.
Funding 15. APPITA P11s-78. Klason lignin in wood and pulp.
The authors acknowledge the Universiti Malaysia Pahang, Australia: APPITA Testing Committee, 1998.
Malaysia, for funding this research work (RDU100339). 16. Inagaki T, Siesler HW, Mitsui K, et al. Difference of the
crystal structure of cellulose in wood after hydrothermal
and aging degradation: a NIR spectroscopy and XRD
Conflict of interest study. Biomacromolecules 2010; 11: 2300–2305.
None declared. 17. Broido A. A simple, sensitive graphical method of treat-
ing thermogravimetric analysis data. J Polym Sci Part A:
Polym Phys 1969; 7(10): 1761–1773.
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