Composites Science and Technology xxx (2010) xxx–xxx

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Composites Science and Technology

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Effect of chemical treatments on the mechanical and thermal behaviour of okra

(Abelmoschus esculentus) fibres
Igor Maria De Rosa a,1, José M. Kenny b, Mohd. Maniruzzaman c, Md. Moniruzzaman c, Marco Monti b,
Debora Puglia b, Carlo Santulli a, Fabrizio Sarasini a,⇑
a
Sapienza – Università di Roma Department of Chemical Engineering Materials Environment, Via Eudossiana 18 – 00184 Rome, Italy
b
University of Perugia, UdR INSTM, Department of Civil and Environmental Engineering, Strada di Pentima 4, 05100 Terni, Italy
c
Department of Applied Chemistry and Chemical Technology, Islamic University, Kushtia 7003, Bangladesh

a r t i c l e i n f o a b s t r a c t

Article history: The effect of a number of chemical treatments on the mechanical (tensile), thermal (FTIR, TGA) and water
Received 6 September 2010 absorption properties of okra (Abelmoschus esculentus) fibres has been studied. These included: bare
Received in revised form 23 November 2010 scouring of the fibres; bleaching (pure, and followed by acetylation or alkalisation); pure acetylation;
Accepted 25 November 2010
sodium sulphite; sulphuric acid with potassium permanganate. Tensile properties of the fibres were
Available online xxxx
studied using Weibull statistics and correcting the values obtained by the void content measured from
SEM images. A separate set of SEM images allowed also characterising their failure mode. The general
Keywords:
trend of the results shows some decrease in mechanical properties by all treatments, although the effect
A. Polymer-matrix composites (PMCs)
B. Mechanical properties
is partially concealed by the high variation of fibre dimensions and the relative variation of void content.
D. Infrared (IR) spectroscopy Fracture surfaces present an increased level of twisting as an effect of chemical modification resulting in
D. Thermogravimetric analysis (TGA) reduced adhesion force between the fibrils, though seldom in their physical separation. Treatments
Okra fibres involving acetylation result in limited fibre degradation, whilst bleaching, scouring and particularly per-
manganate treatment, though mechanically damaging for the fibres, have lower influence on their ther-
mal behaviour. Water absorption profile is significantly improved by all applied treatments.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction Abelmoschus esculentus). The recent study of their thermal and

In recent years, a number of bast-extracted fibres, alternative to
the most used ones, such as jute, flax, hemp and kenaf, have been
also proposed as a reinforcement for plant fibre composites: these
fibres are mainly from herbaceous plants, and include among oth-
ers ramie [1], nettle [2], vetiver [3], esparto [4], roselle [5], etc. In
general, trying to broaden the number of botanical species from
which fibres are extracted may present interest e.g., for local pro-
ductions or when investigating the possibility of making hybrids
introducing in the laminate different types of plant fibres with dif-
ferent characteristics. One of the principal questions in this respect
is whether the morphological, thermal and especially mechanical
properties of the fibres would enable them to be used as an effec-
tive reinforcement for polymer matrices or rather confine them to
an ‘‘agro-waste’’ disposal use, when introduced in materials.
Okra (Lady’s finger) fibres are extracted from the bark of
okra bahmia, a plant of the Malvaceae family (botanical name
⇑ Corresponding author.
E-mail addresses: fabrizio.sarasini@uniroma1.it, fabrizio.sara@libero.it
(F. Sarasini).
1
Present address: Dept. Materials Science – University of California Los Angeles,
E-V 2122, 410 Westwood Plaza Los Angeles, CA 90095, United States.
mechanical behaviour indicated some potential as reinforcement
in polymer-matrix composites [6]. Also, FTIR investigations con-
firmed their chemical properties not to be dissimilar to those of
other common lignocellulosic fibres e.g., pineapple [7]. To propose
their application in composite materials, the question of chemical
treatment is crucial: a preliminary study, uniquely based on the
introduction of a small quantity of alkali-treated or bleached okra
fibres in a phenolic matrix, did raise some concern on the real pos-
sibilities of chemical treatments to improve the properties of com-
posite laminates [8]. As a consequence, a profound need exists for a
sounder investigation of the physical, mechanical and morpholog-
ical modifications produced by a wide range of chemical treat-
ments on okra fibres.
On plant fibres, a number of surface treatments have been ap-
plied [9]. Some of them, such as alkali-treatment e.g., with sodium
hydroxide (NaOH), bleaching with sodium hypochlorite (NaClO) or
chlorite (NaClO2), are applied on the fibre bundles to try to obtain
the technical fibre, which is the one that afford loading in tension
and twisting, to be possibly used in textile products [10].
This would at the same time expose as much as possible of the
cellulose structure to increase the number of reaction sites [11].
This is achieved by removing as much as possible non-structural
matter i.e., hemicellulose, lignin and pectin [12]. However, alkaline

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doi:10.1016/j.compscitech.2010.11.023

Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
fibres. Compos Sci Technol (2010), doi:10.1016/j.compscitech.2010.11.023
2 I.M. De Rosa et al. / Composites Science and Technology xxx (2010) xxx–xxx
treatment has been recognised capable of regenerating cellulose by
addition of hydroxyl groups, dissolving microscopic pits or cracks
on the fibres e.g., in a study on kenaf fibres [13]. Other treatments,
such as those using silane or maleated agents, provide an effective
surface coating through a chemical link to improve fibres adhesion
to the polymer matrix by reducing the hydrophilic character of cel-
lulose. The two types of treatment can be applied in succession on
the fibres to provide first cellulosic structure exposure and then
surface coating: this was carried out e.g., on pineapple leaf fibres
in [14]. Concentrating on the former type of treatment, aimed at
technical fibre sorting and non-structural matter removal, it ap-
pears that obtaining a substantial improvement of mechanical
properties in the fibres through the chemical treatment of their
surface strongly depends on the concentration of the chemical ap-
plied. As Mishra et al. reported [15], a too high alkali concentration
leads to excess delignification of fibres, which heavily affects their
tensile strength.
As a general consideration, the improvement of fibre compati-
bility with polymer matrices through chemical treatment is ob-
tained usually at the expenses of their tensile properties. This
decrease may be due to substantial delignification and degradation
of cellulose chains during treatment, which has usually a lesser ef-
fect on the extension at break of these fibres [16]. In this respect,
this work is aimed at evaluating the extent of the modification ob-
tained on okra fibre surface by applying some of the usual treat-
ments for plant fibres. All of these are intended for a primary
action on the fibre bundles, capable of isolating the technical fibres
and of removing non-structural matter from them. A subsequent
objective would be evaluating whether the resulting fibres would
retain sufficient strength and stiffness to allow using them as a
reinforcement for polymer matrices.
2. Materials and methods
Okra (Abelmoschus esculentus), whose local name is Dherosh, is a
monocotyledon plant. The plant has been collected in Kushtia Dis-
trict (Bangladesh). After collection, the fresh plant was kept under
water to allow microbial degradation. Within 15–20 days the
stems degraded sufficiently to enable fibre extraction. The fibres
were isolated from the degraded stems by being washed three
times using deionised water. They were then tied with ropes, dried
in open air and kept in moisture-proof container afterwards.
In Table 1 the treatments applied on the fibres are reported, to-
gether with the indication of the relative letter associated to the
series. In particular, in some cases (series AABOF, BOF, SHBOF),
bleaching of raw okra fibre, as retted from the plants, was carried
out as a pre-treatment. This was done by using 10% NaClO2 with
1:80 fibre liquor ratio (volume/volume), pH = 4, at 85–90 °C up to
90 min. The bleached fibre was treated with sodium metabisul-
Table 1
Chemical treatments applied on okra fibres.
Categories Chemical treatment
ROF No treatment applied (raw fibres)
SOF Scouring with a solution of 3.2% sodium carbonate and 6.3% soap
flake
AAROF Acetylation with 10% acetic acid
AABOF Bleaching with 10% sodium chlorite followed by acetylation with
10% acetic acid
BOF Bleaching with 10% sodium chlorite
SAKPOF Treatment with 1% sulphuric acid followed by 0.055% potassium
permanganate
SSROF Treatment with 10% sodium dodecyl sulphate
SHBOF Bleaching with 10% sodium chlorite followed by 1% sodium
hydroxide alkalisation
Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
fibres. Compos Sci Technol (2010), doi:10.1016/j.compscitech.2010.11.023
phate with 1:20 fibre liquor ratio up to 15 min to neutralize active
chlorine.
Raw and bleached okra fibres were cut into 50 cm length and
were soaked in solutions of the relevant analytical grade chemicals
at 30 °C maintaining a liquor ratio of 1:50. The fibres were kept im-
mersed in the solutions for 2 h. They were subsequently washed
several times with fresh water to remove any chemical sticking
to the fibre surface and then washed again with distilled water.
In the case of alkaline treatment, an intermediate neutralization
using a dilute acetic acid solution was also applied between the
two washing phases. A final pH = 7 was maintained. The fibres
were then dried at room temperature for 48 h followed by oven
drying at 100 °C for 6 h.
Untreated and treated okra fibres were examined under an FEI
Quanta FEG 600 Environmental Scanning Electron Microscope
(ESEM) to see the effect of treatments on the modification of their
surface properties both along their length and on their section. To
analyse their cross-section, okra fibres were cut by hand and
mounted into an epoxy-based compound and then polished to
achieve a flat surface. These images were used for measurement
of fibre diameters and internal void content, as specified below.
A separate set of micrographs were taken to investigate the fibre’s
microstructure and morphology using a Hitachi S-2500 scanning
electron microscope (SEM).
Technical fibres were manually separated from the larger bun-
dles: it is noteworthy observing that in reality this does not mean
obtaining ultimate fibres, but the smallest fibres that allow being
loaded in tension with conventional systems. Tensile tests were
carried out according to ASTM D 3379–75 at room temperature
on a Lloyd dynamometer LR 30 K with 20 N as load cell full range.
Fibres were tested in the as-received state at a gauge length of
10 mm in displacement control and at a crosshead speed of
1 mm/min.
The data obtained on the mechanical properties of the fibres can
be represented by a two-parameter Weibull [17] equation, which
expresses the cumulative density function of the strength of the fi-
bres as:
  a 
rf
Fðrf Þ ¼ 1  exp  ð1Þ
ro
where a is the Weibull modulus and r0 is a location parameter. The
same function was applied for the evaluation of cumulative density
function of the elastic modulus, in which rf and ro were replaced by
Ef and Eo.
The stresses on the okra fibres were firstly calculated measuring
the diameter from optical microscopy assuming a circular cross
section of the fibres, but modification of the calculation was done
considering not only the diameter measured using the optical
microscope, but also the effective percentage of voids in the cross
section of the fibres obtained by SEM analysis.
The SEM micrographs were firstly elaborated by a graphic soft-
ware, in order to delete the part of the images not occupied by the
fibre. After this first step, the software Nikon NIS-Elements BR was
employed to calculate the area contained in the outer perimeter of
the fibres, and the area effectively occupied by the fibres. Initially,
just the area enclosed by the outer perimeter (green line in the pic-
ture) was calculated, not considering the presence of voids. After-
wards, the effective area of the fibre was considered and
calculated. This area corresponds to the total area enclosed by
the outer perimeter excluding the voids, the white-edged area in
the picture.
Thermogravimetry (TG) and differential thermogravimetry
(DTG) techniques were used to analyse the thermal stability of okra
fibres. The measurements were performed using a thermobalance
TG/DTA Seiko Exstar 6000 in nitrogen atmosphere (250 ml/ min)
 I.M. De Rosa et al. / Composites Science and Technology xxx (2010) xxx–xxx 3

in a programmed temperature range from 30 to 600 °C at a heating

rate of 10 °C/min. Sample weights between 5 and 10 mg were
placed in a platinum pan.
Fourier transform infrared spectrometry (FTIR) was carried out
on okra fibres, as well. IR spectra of the fibres were recorded using
a Jasco FT-IR 615 spectrometer in the frequency range 4000–
500 cm1, operating in ATR (attenuated total reflectance) mode.
Water absorption tests of untreated and treated okra fibres
were carried out by taking a small amount (about 1.0 g) of each
set of fibres. Fibre samples were first dried by heating them in an
electric oven at 70 °C for about 2 h, weighed and then soaked in
a bath of distilled water at room temperature. At several times,
the fibre samples were removed from water, dried by a cotton
cloth and weighed again. The percentage of water absorption by fi-
bre was calculated considering the weight of the wetted sample
and the weight of the dried sample.

3. Results

3.1. Mechanical properties

In Table 2 the mechanical properties of the raw and treated fi-

bres are reported: here, the conventional method of diameter mea-
surement for calculation of cross-sectional area was considered.
Excluding some slippage at the beginning of the test, okra fibres
exhibit the single linear elastic deformation until failure with no
plastic deformation, which is typical of vegetable fibres and has
been observed already in [6] on raw okra fibres.
Okra fibres exhibited a variability in tensile strength and Fig. 1. (a) Untreated okra fibre SEM micrograph (b) the same image prepared for
void content measurements.
Young’s modulus, which is also quite common to natural fibres.
Therefore, the values obtained by mechanical characterization
were statistically analysed using a two-parameter Weibull distri-
Table 4
bution, A single set of parameters for each property (i.e. tensile Diameter, void content, tensile strength and modulus with SD values of okra fibers
strength and Young’s modulus), r0–E0 and a, which simulta- obtained from improved method.
neously fit all the data, was obtained. Fig. 3a and b shows the
Diameter Void Tensile strength Young’s
Weibull distributions for tensile strength and Young’s modulus of (lm) content (%) (MPa) modulus (GPa)
okra fibres. This two-parameter Weibull distribution provides a
ROF 77.1 ± 15.9 24.2 ± 6.0 370.7 ± 186.7 16.9 ± 8.1
reasonable approximation of experimental data for mechanical SOF 96.7 ± 28.3 12.4 ± 5.7 293.5 ± 114.7 1.9 ± 0.8
properties. The Weibull modulus and location parameters (which AAROF 107.5 ± 33.7 27.3 ± 5.2 200.6 ± 72.5 6.2 ± 2.2
are characteristic values of the distribution) for each property AABOF 92.5 ± 30.3 34.2 ± 2.9 495.5 ± 122.1 5.3 ± 2.0
BOF 73.4 ± 15.8 19.7 ± 5.8 620.4 ± 128.0 4.1 ± 1.9
SAKPOF 128.30 ± 39.3 17.4 ± 9.1  
Table 2 SSROF 130.40 ± 72.5 17.6 ± 6.3 250.1 ± 55.6 4.2 ± 1.7
Diameter, tensile strength and modulus with SD values of okra fibres obtained from SHBOF 113.8 ± 39.0 15.8 ± 2.8 211.8 ± 49.7 4.3 ± 2.2
conventional method.

Diameter (lm) Tensile strength (MPa) Young’s modulus (GPa)

(tensile strength and Young’s modulus) for the investigated sys-
ROF 88.3 ± 27.3 233.8 ± 126.4 12.8 ± 6.1
tems are reported in Table 3. It should be noted that the acid trea-
SOF 218.9 ± 50.5 52.6 ± 23.0 1.7 ± 0.7
AAROF 188.3 ± 54.2 60.1 ± 28.7 4.5 ± 1.6 ted fibre (SAKPOF) was not tested for mechanical characterization,
AABOF 184.4 ± 40.0 82.4 ± 48.8 3.5 ± 1.3 since the damage of the fibre was so high to prevent the selection
BOF 153.5 ± 41.2 82.6 ± 47.2 3.2 ± 1.5 of the fibre itself for a suitable preparation of the sample (see
SAKPOF 161.5 ± 46.8  
Fig. 1).
SSROF 174.3 ± 39.1 73.7 ± 40.8 3.5 ± 1.4
SHBOF 134.6 ± 47.0 71.6 ± 45.2 3.7 ± 1.9 Standard deviations (SDs) for both strength and modulus are
exceptionally high, even if specimens were carefully selected for

Table 3
Mechanical parameters for okra fibres – Weibull model.

(r0) Tensile strength (MPa) a (E0) Young’s modulus (GPa) a

ROF 281.6819 1.9088 16.5541 2.0237
SOF 66.3823 1.9967 2.3291 2.0463
AAROF 84.1149 1.8642 4.6764 1.9704
AABOF 101.9054 1.7567 4.3868 2.6709
BOF 100.3415 1.8914 3.921 1.9883
SSROF 95.5389 1.6852 4.085 2.6105
SHBOF 110.6403 1.3094 4.43345 2.0611

Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
fibres. Compos Sci Technol (2010), doi:10.1016/j.compscitech.2010.11.023
4 I.M. De Rosa et al. / Composites Science and Technology xxx (2010) xxx–xxx

ROF SOF

AAROF AABOF

BOF SAKOF

SSBOF SHBOF

Fig. 2. Measurement of fibre diameters from SEM micrographs.

the test and a large number of specimens was used for the test. The
inaccuracy of the diameter determined by the conventional testing
method (optical microscopy observation) is possibly one of the ma-
jor reasons for this large SD in strength and modulus [18]. As the
fibre was carefully selected before test to limit the effects of fibre
non-uniformity and defects on results, the problem should be
mainly due to the poor approach of fibre cross-section determina-
tion. In order to clarify whether the results reflect the real inhomo-
geneous nature of the natural fibres or the limitations of the
conventional SFTT and to obtain more consistent results, SEM
micrographs of the fibres were taken, with the aim of providing a
more accurate cross-sectional area determination. In Table 4 the
evaluation of fibre and voids content in fractured sections are re-
ported and the mechanical properties are recalculated, including
the improved method of SEM calculation of diameters (Fig. 2)
and correction of the area with fibre/voids content. The average
values and the standard deviation of the diameters have all been
corrected by the average void content. It is anticipated that this

Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
fibres. Compos Sci Technol (2010), doi:10.1016/j.compscitech.2010.11.023
 I.M. De Rosa et al. / Composites Science and Technology xxx (2010) xxx–xxx 5

(a) 1

0,8

0,6
F (σ)

ROF
0,4 SOF
AAROF
AABOF
BOF
0,2 SSROF
SHBOF
model

0
0,5 1 1,5 2 2,5 3
log (σ)

(b) 1
ROF
SOF
AAROF
0,8 AABOF
BOF
SSROF
SHBOF
0,6 model
F (E)

0,4

0,2

0
3 3,5 4 4,5 5
log (E)

Fig. 3. Weibull modulus of raw and treated fibres.

method may introduce some error whenever the variation of void

content across the fibres is significant, but on the other side it al-
lowed making sense of some mechanical results. In particular, as
can be observed from Table 6, the variability is very high, leading
for all treatments and also for raw fibres to the possibility that
the lowest values of Young’s modulus are quite close to zero.
The effect on the mechanical properties by some of the treat-
ments as compared with the raw fibre structures is also described
by the SEM micrographs showing fracture surfaces, reported in
Fig. 4a–d. Fracture surfaces present a variable level of twisting as
an effect of chemical modification, which results in a variable
Fig. 4. Fracture surfaces of raw (a), bleached (b), acetic bleached (c), permanganate
adhesion force between the fibrils. In general, treatment tends to treated fibres (d).
expose the lumens, as can be observed by comparing Fig. 4a re-
ferred to the untreated fibres with Fig. 4b–d. Also, along their
length the treated fibres appear to be ‘‘cleaner’’ than the raw ones. tion (acetone) has been observed also on sisal [21]: however, the
Comparing bleached (Fig. 4b) and acetylated and bleached (Fig. 4c) effect on okra in acid solution (sulphuric acid) appears far more
fibres, the surface both along the length and in section appear destructive.
smoother in the latter, which may be ascribed to the regeneration
effect of the fibres due to acetylation, which has been frequently 3.2. FTIR spectra analysis
described on plant fibres [19,20]. Permanganate treated fibres
(Fig. 4d) show the presence of small holes around the mid section FTIR spectra are reported in Fig. 5: in particular raw fibres (ROF)
of the fibrils, which may be ascribed to some degradation of the spectrum is traced for comparison in all of Fig. 5a–c. In addition,
structural part of the fibres owed to the treatment. The increase Fig. 5a includes AAROF and SSROF, Fig. 5b all the treatments
of porosity with a 0.02% permanganate treatment in alkaline solu- involving bleaching (BOF, AABOF, SSBOF) and Fig. 5c scouring

Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
fibres. Compos Sci Technol (2010), doi:10.1016/j.compscitech.2010.11.023
6 I.M. De Rosa et al. / Composites Science and Technology xxx (2010) xxx–xxx

(a) principal components are therefore alkenes, aromatic groups and

ROF various functional groups containing oxygen (ester, ketone and
AAROF alcohol). A broad absorption band in the region 3600–3100 cm1
SSROF corresponds to the characteristic OAH stretching vibration and
hydrogen bond of the hydroxyl groups. The peaks at 2925 and

1358
Absorbance

1238
2854 cm1 are the characteristic band for the CAH stretching
vibration from CH and CH2 in cellulose and hemicellulose compo-

1451
1624
1731
nents, whilst the absorbance at 1743 cm1 belongs to the carbonyl
C@O stretching vibration of linkage of carboxylic acid in lignin or
ester group in hemicellulose and the small peak at 1517 cm1 is
3340

attributed to C@C stretching of aromatic ring of the lignin.

3606
3713

The absorbance at 1430 cm1 is associated to the CH2 symmetric

bending present in cellulose, while the absorbance peaks at
1384 cm1 and 1243 cm1 correspond to the CAO stretching vibra-
tion of the acetyl group in lignin and hemicellulose component,
respectively. The two peaks observed at 1370 cm1 and 1320 cm1
4000 3600 3200 2800 2400 2000 1600 1200 800 indicate the bending vibration of CAH and CAO groups of the aro-
-1 matic ring in polysaccharides. The absorbance peak at 1160 cm1
wavenumber (cm )
is due to the anti-symmetrical deformation of the CAOAC band.
The strong absorption peak at 1035 cm1 is ascribed to the CAO
(b) and OAH stretching vibration which belongs to polysaccharide in
ROF
cellulose. The peak observed at 894 cm1 is attributed to the pres-
BOF
AABOF ence of b-glycosidic linkages between the monosaccharides. Fur-
1241

SHBOF thermore the absorbance at 598 cm1 corresponds to the CAOH

1357
1451

bending.
Absorbance

Acetylated fibres (AAROF) (Fig. 5a) exhibited the absorption

peaks in the regions 1730–1745 and 1235–1240 cm1. The peaks
located at 1730–1745 cm1 are attributed to the C@O stretching
of carbonyl in the ester. The vibration peaks, between 1235 and
1240 cm1, are attributed to CAO stretching of acetyl groups. As
seen from the FTIR results, the low intensity of absorbance peaks
in the analysed regions indicates that the fibres have a low degree
of acetylation. In addition, esterification of fibres lowered the peak
area at 3330–3350 cm1 attributed to stretching vibrations of OH,
indicating a partial acetylation. The number of OH groups was de-
creased due to the substitution of the acetyl groups during the
4000 3600 3200 2800 2400 2000 1600 1200 800 acetylation in the fibre walls. Acetylation improves water repel-
-1 lence in wood as a result of decreased OH groups. Another peak
wavenumber (cm )
at wave number 1358 cm1, which has been assigned to CAH
deformation in cellulose and hemicelluloses, was found to increase
(c) 1050 due to acetylation [22,23]. The peaks at 3606 cm1 and 3713 cm1
ROF are due to adsorbed water.
SOF
1235

In the case of sodium dodecyl sulphate treated fibres (SSROF)

SAKPOF
1360

(Fig. 5a), the reaction with the aromatic rings of the lignin forms
1731
1625

water-soluble lignosulfonates which are then easily removed from

Absorbance

the fibre core. Hydroxyl absorption peaks appear strongly at 3650–

3729

3200 cm1, which indicates that considerable amounts of hydrox-

3607

2920
2850

yls appear when treated It is seen that SS treated okra fibre has a
weak absorption peak of carbonyl group at 1733 cm1 in the spec-
trum. The absorbance peaks at 1384 cm1 and 1243 cm1 corre-
spond to the CAO stretching vibration of the acetyl group in
lignin and hemicellulose component, respectively. A decrease in
the splitting of the band in the range of stretching vibrations of
CH bonds of methyl and methylene groups (2850–2920 cm1) also
suggests removal of lignin-like structures.
Bleached (BOF) fibres (Fig. 5b) show limited differences with
4000 3600 3200 2800 2400 2000 1600 1200 800
the raw fibres. The main spectral changes revealed were an in-
-1
wavenumber (cm ) crease of the 898 cm1 band, attributed to the symmetric in-phase
ring-stretching mode, and a decrease in the 1430 cm1 band attrib-
Fig. 5. FTIR spectra of raw and differently treated okra fibres.
uted to CH2 bending. It appears that with the bleaching treatment,
a substantial portion of uric acid, which is a constituent of
(SOF) and potassium permanganate treatment (SAKPOF). All peaks hemicellulose xylene, wax, impurities are removed, resulting in
are summarised in Table 5. the disappearance of the carbonyl peak [24,25]. The bands around
As reported already in [6], FTIR spectrum of the okra shows 1423 and 1325 cm1 are assigned to CH2 scissoring and OH bend-
absorption bands of chemical groups characteristic of lignocellu- ing vibration, respectively. Again, the peaks at 3604 cm1 and
losic fibre compounds: cellulose, hemicellulose and lignin. The 3716 cm1 are due to adsorbed water.

Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
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 I.M. De Rosa et al. / Composites Science and Technology xxx (2010) xxx–xxx 7

Table 5
Summary of peaks in FTIR spectra observed for each treatment.

Peak Untreated AAROF SSROF BOF AABOF SHBOF SOF SAKPOF

1 1 1 1
3600–3100 cm OAH stretching 3606 cm , 3650–3200 cm 3604, 3716 cm 3607, 3729 cm1
3713 cm1, adsorbed water adsorbed water
adsorbed water
(low intensity)
2925 and CAH stretching CH CH (methyl and CH (methyl and
2854 cm1 and CH2 (cellulose methylene methylene
and groups) (2850– groups) (2850–
hemicellulose) 2920 cm1) - 2920 cm1) -
decrease decrease (removal
lignin-like
structures)
1743 cm1 carbonyl C@O 1730–1745 cm1 1733 cm1 weak not present in 1731 cm1 peak
stretching the alkali reduction
treated (removal of
samples hemicellulose)
1430 cm1 CH2 symmetric decrease
bending 1430 cm1 band
CH2 bending
1384 cm1, CAO stretching 1235 and 1235 and
1243 cm1 vibration of the 1240 cm1 (low 1240 cm1,
acetyl group in intensity) higher
lignin and intensity
hemicellulose
1370 cm1 and bending vibration 1325 cm1 AOH 1360 cm1, Decrease skeleton
1320 cm1 of CAH and CAO bending vibration 1625 cm1 vibrations
groups of the (removal of lignin) aromatic ring
aromatic ring in
polysaccharides
1358 cm1, CAH
deformation in
cellulose and
hemicelluloses
1239 cm1 1238 cm1 peak
(CAO stretch reduction
of the acetyl (removal of
group of hemicellulose)
lignin)
disappeared
894 cm1 b-glycosidic 898 cm1 in-phase
linkages ring-stretching
mode - increase
598 cm1 CAOH bending

Bleached and acetylated (AABOF) fibres (Fig. 5b) appear sub-
stantially similar to the barely bleached fibres (BOF). However,
the vibration peak, between 1235 and 1240 cm1, attributed to
C–O stretching of acetyl groups, confirmed the acetylation of the
bleached fibre with higher intensity in comparison with the barely
acetylated ones (AAROF).
In bleached and alkalised fibres (SHBOF) (Fig. 5b), the peak at
1730 cm1, attributed to the C@O stretching of the acetyl groups
of hemicellulose, is not present in the alkali treated samples. The
removal of hemicellulose from the fibre surfaces causes this peak
to disappear. It is well-known that the alkaline deacetylation of
hemicelluloses decreases the peak intensity caused by the alkalin-
ity of sodium hydroxide. The peak at 1239 cm1 (CAO stretch of
the acetyl group of lignin) disappeared, because lignin is partially
removed from the fibre surface [26].
Scouring (SOF) (Fig. 5c) with a solution of 3.2% sodium carbon-
ate and 6.3% soap flake (sodium linear alkyl benzene sulfonate, or
LAS) resulted in the reduction of the absorption peak at 1731 cm1
and the reduction in the peak intensity found at 1238 cm1, which
indicated the hemicellulose could be partially removed by scouring
treatment. In addition, the reduction in the peak intensity found at
1625 cm1 and around 1360 cm1 indicated the partial removal of
lignin.
The treatment with sulphuric acid and potassium permanga-
nate (SAKPOF) (Fig. 5c) led to extensive delignification. As a result,
the intensity of the bands at 1050 (bending vibrations of OH groups
of cellulose) increases, whereas the intensity of absorption in the
range of 1450–1600 cm1, which is related to skeleton vibrations
of the aromatic ring, decreases [27]. A decrease in the splitting of
the band in the range of stretching vibrations of CH bonds of
methyl and methylene groups (2850–2920 cm1) also suggests re-
moval of lignin-like structures. The peaks at 3607 cm1 and
3729 cm1 are due to adsorbed water.
3.3. Differential thermogravimetry (DTG)
Analysis of the DTG curves (Fig. 6 a–c) has shown that the first
stage of decomposition is associated to the thermal depolymerisa-
tion of hemicellulose, pectin and the cleavage of glycosidic linkages
of cellulose whilst, the second one corresponds to the degradation
of a-cellulose present in the fibre. In Table 6, the peak tempera-
tures (maximum degradation rate and T corresponding at the
50% weight loss) are reported. From Fig. 6 we can notice that, while
the treatments (acetylation and sodium sulphate treatment) of raw
fibre decreased the thermal stability of the fibre, in the case of
bleached fibres there is no so much difference in the thermal

Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
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8 I.M. De Rosa et al. / Composites Science and Technology xxx (2010) xxx–xxx

Table 6 0,2
T50% (temperature of 50% weight loss) and temperature
of maximum degradation rate. ROF
SSROF
T(50%) (°C) Tmax (°C) AAROF
ROF 349.9 358.6 0,15

DTG (µg/µgi min)

SOF 347.6 353.3
AAROF 343.4 350.5
AABOF 336.1 339.8
BOF 332.7 342.2
SAKPOF 348.9 353.8 0,1
SSROF 329.8 335.7
SHBOF 339.4 341.1

0,05

behaviour of the treated fibres (both for acetylation and sodium

hydroxide treatment).
0
3.4. Water absorption 200 250 300 350 400 450 500
Temperature (°C)
Water absorption tests (Table 7) showed significant differences
between raw and treated fibres. Three measurements are shown 0,2
for every type of fibre, raw or treated. In particular, raw fibres BOF
(ROF) appear to dissolve more in a long water immersion, whilst AABOF
SHBOF
scoured fibres (SOF) are in a sense protected from dissolution, so
they are able to maintain the greatest majority of water, which 0,15
DTG (µg/µgi min)

they absorbed after 12 days. Other treatments have in general an

intermediate effect over water absorption. Comparison of RWL
(relative weight loss, defined as (WoWf)/Wo in which Wo is the
weight of the sample at time 0 and Wf is the weight at the end 0,1
of the test after drying at 70 °C for 2) confirms that all treatments
reduce the hydrophilic character of the fibres, thus suggesting that
a better adhesion with hydrophobic polymer resins could be
achieved. 0,05

4. Discussion
0
A broad programme of chemical treatments have been applied 200 250 300 350 400 450 500
on okra fibres: this was especially intended to clarify whether Temperature (°C)
these fibres can withstand a more or less aggressive action of
non-structural matter removal, in order to reduce their natural 0,2
variability in terms of fibre diameters, void content and irregular SOF
geometry. In general, the decrease in mechanical properties, SAKPOF
although partially concealed by the large standard deviation both
of tensile strength and Young’s modulus, can be considered as a 0,15
negative indication: however, this is only partially significant in
DTG (µg/µgi min)

terms of prediction of scarce performance, when inserting the fi-

bres as a reinforcement for polymer matrix. Even on hard fibres,
such as hemp, treatment, together with extensive fibrillation and 0,1
removal of non-cellulosic components, can result in reduced
mechanical properties [28]. The principal question, however, is
whether treatment can effectively act to decrease inherent vari-
ability of geometrical characteristics of okra fibres. 0,05
In this respect, treatments do appear to compress the values, as
regards Young’s modulus, on the lower end of the scale, whilst in
some cases, taking into account also the effect of the void content,
average fibre strength is even improved by treatment, as it hap- 0
pens with bleached fibres, and bleached and acetylated ones. It is 200 250 300 350 400 450 500
noteworthy that internal void content is considerably increased Temperature (°C)
by acetylation, by effect of matter removal on the fibre surface, fol-
Fig. 6. DTG thermograms of raw and treated fibres.
lowed by fibre homogenisation due to its partial esterification. In
contrast, bleaching acts more into depth, so that it results more
in a decrease of fibre section with limited effect on internal void aging. In contrast, scouring, in spite of its negative effect on
content, suggesting that in this case matter is removed in a non- mechanical properties, appears substantially reducing porosity
selective way, and this effect is even worsened mechanically by and is effective in keeping absorbed water inside the fibre struc-
possible alkalisation after bleaching. About the other treatments, ture, which is promising in view of a use of okra fibres in polymer
permanganate treatment was discussed above as being quite dam- resins.

Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
fibres. Compos Sci Technol (2010), doi:10.1016/j.compscitech.2010.11.023
 I.M. De Rosa et al. / Composites Science and Technology xxx (2010) xxx–xxx 9

Table 7 Congresso Iberoamericano de Investigação em Celulose e Papel (CIADICYP)

Water absorption of raw and treated okra fibres. Conference Proceedings. Guadalajara, Jalisco, Mexico; October 2008.
[5] Junkasem J, Menges J, Supahol P. Mechanical properties of injection-molded
(%) 24 h 12 days 24 days Wo – dry Wf – dry %, RWL isotactic polypropylene/roselle fibre composites. J Appl Polym Sci 2006;
weight (g) weight (g) (relative 101(5):3291–300.
(at time 0) (after 2 h at weight [6] De Rosa IM, Kenny JM, Puglia D, Santulli C, Sarasini F. Morphological and
70 °C) loss) thermal characterisation of okra (Abelmoschus Esculentus) fibres as potential
reinforcement in polymer composites. Compos Sci Technol 2010;70(1):
ROF 57.9 60.5 52.8 0.456 0.329 27.9 116–22.
SOF 60.3 60.7 60.6 0.276 0.257 6.9 [7] Saikia D, Bora MN. Study of hygroscopic properties of some plant fibres under
AAROF 56.3 57.8 56.7 0.322 0.290 9.9 thermal condition. Indian J Pure Appl Phys 2003;41(6):484–7.
AABOF 55.4 60.5 58.6 0.364 0.326 10.4 [8] Moniruzzaman Md, Maniruzzaman Mohd, Gafur Ma, Santulli C. Lady’s finger
BOF 56.7 60.2 58.4 0.462 0.427 7.6 fibres for possible use as a reinforcement in composite materials. J Biobased
SAKPOF 56.7 58.7 57.5 0.455 0.375 17.6 Mater Bioenergy 2009;3(3):286–90.
SSROF 58.4 62.3 58.8 0.332 0.290 12.7 [9] Li X, Tabil HG, Panigrahi S. Chemical treatments of natural fibre for use in
SHBOF 57.4 59.6 58.4 0.403 0.389 3.5 natural fibre-reinforced composites: a review. J Polym Environ 2007;15(1):
25–33.
[10] Msahli S, Sakli F, Drean J-Y. Study of textile potential of fibres extracted from
Tunisian Agave Americana L. AUTEX Res J 2006;6(1):9–13.
5. Conclusions [11] Valadez-Gonzalez A, Cervantes-Uc JM, Olayo R, Herrera-Franco PJ. Effect of
fibre surface treatment on the fibre–matrix bond strength of natural fibre
reinforced composites. Composites Part B 2005;36(8):597–608.
The application of different chemical treatments on okra fibres [12] John MJ, Anandjiwala RD. Recent developments in chemical modification and
appears to have a contradictory effect on their mechanical and characterization of natural fiber-reinforced composites. Polym Compos
thermal properties. The expected reduction in geometrical and 2008;29(2):187–207.
[13] Keshk S, Suwinarti W, Sameshima K. Physicochemical characterization of
mechanical variability of these fibres was obtained in a very lim- different treatment sequences on kenaf bast fibre. Carbohydr Polym 2006;
ited way and only relatively to some treatments, such as acetyla- 65(2):202–6.
tion. The general trend of the results suggest some decrease in [14] Threepopnatkul P, Kaerkitcha N, Athipongarporn N. Effect of surface treatment
on performance of pineapple leaf fibre- polycarbonate composites.
mechanical properties, particularly of Young’s modulus, by all Composites: Part B 2009;40(7):628–32.
treatments. However, this effect is partially concealed by the high [15] Mishra S, Mohanty AK, Drzal LT, Misra M, Parija S, Nayak SK, et al. Studies on
variation of fibre dimensions and the relative variation of void con- mechanical performance of biofibre/glass reinforced polyester hybrid
composites. Compos Sci Technol 2003;63(10):1377–85.
tent, especially as regards mechanical strength. As a general point, [16] Kalia S, Kaith BS, Kaur I. Pretreatments of natural fibres and their application as
the treatment may make the fibre more permeable to resin when reinforcing material in polymer composites—a review. Polym Eng Sci
used as composite reinforcement, as suggested by lower weight 2009;49(7):1253–72.
[17] Weibull WA. A statistical distribution function of wide applicability. J Appl
reduction observed after drying following water absorption tests,
Mech 1951;18:293–7.
and possibly less prone to moisture-triggered degradation. Looking [18] Hu W, Ton-That M-T, Perrin-Sarazin F, Denault J. An improved method for
into more depth, some differences among the treatments can be single fiber tensile test of natural fibers. Polym Eng Sci 2010;50(4):819–25.
[19] Khalil HPSA, Ismail H, Rozman HD Ahmad MN. The effect of acetylation on
indicated: in particular, those involving acetylation result in a low-
interfacial shear strength between plant fibres and various matrices. Eur
er level of fibre degradation, whilst bleaching, scouring and partic- Polym J 2001;37(5):1037–45.
ularly permanganate treatment appear all at some extent (and in [20] Tserki V, Zafeiropoulos NE, Simon F, Panayiotou C. A study of the effect of
growing order) damaging for the fibres. Fracture surfaces present acetylation and propionylation surface treatments on natural fibres.
Composites Part A 2005;36(8):1110–8.
an increased level of twisting as an effect of chemical modification [21] Sreekumar PA, Thomas SP, Saiter JM, Joseph K, Unnikrishnan G, Thomas S.
and of reduced adhesion force between the fibrils. This seldom pro- Effect of fiber surface modification on the mechanical and water absorption
duces their physical separation, but results in an unpredictable le- characteristics of sisal/polyester composites fabricated by resin transfer
molding. Composites Part A 2009;40(11):1777–84.
vel of fibrillation during loading. [22] Jonoobi M, Harun J, Mathew AP, Hussein MZB, Oksman K. Preparation of
cellulose nanofibers with hydrophobic surface characteristics. Cellulose
References 2010;17(2):299–307.
[23] Mohebby B, Hadjihassani R. Moisture repellent effect of acetylation on polar
fibers. J Agric Sci Technol 2008;10(2):157–63.
[1] Lodha P, Netravali AN. Characterization of stearic acid modified soy protein
[24] Keshk S. Homogenous reactions of cellulose from different natural sources.
isolate resin and ramie fibre reinforced ‘green’ composites. Compos Sci Technol
Carbohydr Polym 2008;74(4):942–5.
2005;65(7–8):1211–25.
[25] Arifuzzaman Khan GM, Shaheruzzaman Md, Rahman MH, Abdur Razzaque SM,
[2] Vogl CR, Hartl A. Production and processing of organically grown fibre nettle
Sakinul Islam Md, Shamsul Alam MD. Surface modification of okra bast fiber
(Urtica dioica L) and its potential use in the natural textile industry: a review.
and its physico-chemical characteristics. Fibers Polym 2009;10(1):65–70.
Am J Altern Agric 2003;18(3):119–28.
[26] Griccia N, Hawley MC, Misra M. Characterization of natural fiber surfaces and
[3] Ruksakulpiwat Y, Suppakarn N, Sutapun W, Thomthong W. Vetiver–
natural fiber composites. Compos. Part A, Appl Sci Manuf 2008;39(10):1632–7.
polypropylene composites: physical and mechanical properties. Composites
[27] Petrova SN, Volkova IY, Zakharov AG. Oxidative delignification of flax fiber.
Part A 2007;38(2):590–601.
Fibre Chem 2004;36(6):393–5.
[4] López JP, Vilaseca F, Méndez JA, Franco E, Boufi S, Belhassen R, Mutjé P,
[28] Korte S, Staiger MP. Effect of processing route on the composition and
Carvalho AJF, Curvelo AAS. Preparation of fully biodegradable composites
properties of hemp fibre. Fibres Polym 2008;9(5):593–603.
based on thermoplastic starch reinforced with tunisian esparto grass fibres,

Please cite this article in press as: De Rosa IM et al. Effect of chemical treatments on the mechanical and thermal behaviour of okra (Abelmoschus esculentus)
fibres. Compos Sci Technol (2010), doi:10.1016/j.compscitech.2010.11.023